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CROSS-REFERENCE TO RELATED APPLICATION
This regular utility patent application is derived from Provisional Patent Application Ser. No. 60/102,897 filed on Oct. 2, 1998.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of the invention is the art of walk-through ladders, inclusive of fixed ladders, which are permanently attached to a structure such as a building.
2. Description of the Related Art
A so called "through" ladder requires a climber getting off at the top to step through the ladder in order to reach a landing. "Walk-through" fixed ladders are also well known; they typically include a flared section at the top through which the climber walks. See the prior art device in FIGS. 8 and 9 which will be more fully described below.
Fall protection is mandatory through OSHA regulations on fixed ladders over 20 feet tall in general industry and 24 feet tall in construction. The addition of a post or a rail in the center or at the side of the ladder creates an impediment to circumvent so an outside fitting is safer. Ladders could be upgraded by having climbing safety devices installed as extra protection. About half of the ladders in use are less than 20 feet high so such improvements would serve the purpose well if no fall protection exists for these ladders.
One problem with the flared walk-through ladder is that the climber routinely holds a side rail while descending until the moment the flared section is reduced to 16 inches in width. Unless users observe the need to place the hands closer to the body in order to grasp the side rails or rungs on the main body of the ladder, a person will grasp at thin air and will be subject to a fall at that moment if he has transitioned his feet and assumed the location of the handhold by getting ready to release the other hand.
Moreover, when 21/2-3-inch width angle iron is used as the side rail, only a push-pull pinch grip can be made on the side rails and any fall at the walk-through portion of the ladder is likely to be catastrophic in its outcome. In fact, the ability to hold any vertical shape of the side rails sufficiently to regain balance is not possible. The problems with side rail holdings are several.
First, the hand slides down due to the weight of the body. Second, the force of arresting a free fall up to three feet, i.e. the length of the arm, is dynamic. From rope tests, it is known that the maximum force of a moving rope which can be held is 50 pounds and the least is approximately 10 pounds, both far below a person's body weight. These references are found in the ISFP Newsletter of October, 1996.
Third, a swing fall into the side of the ladder produces an impact of the body with the ladder since the body's center of gravity has to move eight inches from center to side because a ladder rung is 16 inches long. If a person is standing far over to the side, then a movement of 16 inches will occur with an even higher swing fall collision which further tends to destabilize the hand grip.
Fourth, some ladder side rails are impossible to encircle with the hand, e.g., three-inch angle irons or two-inch flange I-beams. Because these shapes cannot be encircled with the hand for a good grip, only a pinch grip can be used and no fall arrest is remotely possible. With two-inch or 21/2-inch widths, grips are possible but, due to the factors described above, the grip cannot become an effective grasp under foreseeable methods of climbing on these ladders and a catastrophe must necessarily follow, if the climber falls.
Fifth, the ground or surface below a fixed ladder is almost always unyielding, thus providing the maximum possible deceleration upon impact and therefore the greatest injury to a falling worker.
Sixth, ladders constitute the primary cause of injurious occupational falls based on current OSHA statistics. Since these statistics include portable ladders as well as fixed ladders, it is evident that a climber, who loses his balance on a ladder, needs all the help possible to maintain a grasp that can be reasonably effective if a foot were to slip at the most vulnerable transition points on the ladder.
All climbers eventually misstep no matter how well they are trained. Usually, the climber is preoccupied about achieving the purpose for which the ladder is climbed, not the actual climbing of the ladder. Therefore, exposure to fall hazards cannot be expected to be controlled effectively solely by training workers to climb ladders with the utmost attention to human factors and back-up safety features.
Typical of walk-through ladders in the prior art is the fixed ladder illustrated in FIGS. 8 and 9. A lower section of a walk-through ladder L is shown below a surface A which schematically represents a level to which a climber C is ascending from a lower surface G. The ladder L includes side rails 1 with a plurality of round foot rungs 2. By way of example, each rung 2 can be 16 inches long at a minimum and 3/4 to one inch in diameter. Each side rail 1 can be 21/2 inches wide by 33/8 inch to one-half inch in thickness or any size or shape which provides a power grip with materials, such as carbon steel or aluminum, being selected appropriately for the ladder length, usage and environment.
As best shown in FIG. 8, the ladder L at its top above the surface A flares outwardly to form a walk-through section W. The architecture of the walk-through section W may vary depending upon requirements. However, the walk-through section W has parallel vertical side rails 21 and 22 forming an opening O generally, in order to meet code requirements, spaced apart at a distance one from the other about 24 to 30 inches.
As it is also seen in FIG. 9, the walk-through opening O is minimally 31/2 feet in height. In this case, if the climber C is about 5'8" tall, the opening O may be about four feet high.
In FIG. 9, the climber C ascends the ladder L normally. As the climber C negotiates his way into and through the opening O, as indicated by arrows R, onto the surface A, the climber's feet may slip. The vertical side rails 21 and 22 of FIG. 8, regardless of shape or configuration, cannot be grasped without great risk of the climber's grip sliding and/or opening up, depending upon the nature of the slip. Furthermore, a free fall can develop from zero to twice the climber's arm length, resulting in an impact on any grip that the climber C may have. In addition, a swing to one side of the ladder L may result in an impact against the side rails 1 of the ladder L. Consequently, the climber's grip cannot be maintained and a hard fall to the surface C below usually occurs, resulting in serious injury or death.
SUMMARY OF THE INVENTION
This invention relates to a modification of walk-through ladders, namely, providing a second plurality of horizontal grasping rungs associated with the walk-through section which ordinarily does not have any such rungs. These extra rungs are provided for the climber to maintain a continuum of hand grips on the ladder. Such additional rungs are situated above the highest ladder rung. These higher horizontal grasping rungs are easier for the climber to grab and hold than the vertical side rails during passage up into and down from the walk-through section of the ladder, if a foot of the climber slips during such mounting and dismounting of the ladder.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a front elevational view of a first embodiment of the invention.
FIG. 2 is a front elevational view of a second embodiment.
FIG. 3 is a front elevational view of a third embodiment.
FIG. 4 is a front elevational view of a fourth embodiment.
FIG. 5 is a front elevational view of a fifth embodiment.
FIG. 6 is a schematic perspective view of a sixth embodiment.
FIG. 7 is a front elevational view of a seventh embodiment.
FIG. 8 is a front elevational view of a prior art ladder.
FIG. 9 is a side elevational view of the prior art ladder.
FIG. 10 is an alternative embodiment wherein a non-flared walk through section receives elongated sleeves at an upper end thereof so that rungs of the sleeves extend outwardly.
FIG. 11 is an alternative embodiment wherein side rails of a flared walk through section receive elongated sleeves such that the rungs of the sleeves are situated within a flared opening.
FIG. 12 is an alternative embodiment wherein horizontal grasping rungs replace traditional rungs.
FIG. 13 shows the horizontal grasping rung of FIG. 12.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
As shown in FIG. 1, a second plurality of parallel, horizontal grasping rungs 15 are provided in association with the opening O in the walk-through section W of the fixed ladder L, thus allowing a climber C to grab one of the rungs 15 in the same fashion as the grasp enabled by the first plurality of rungs 2 in the lower climbing section of the ladder L.
As seen in the simplest embodiment illustrated in FIG. 7, the horizontal grasping rungs 15 extend freely at one end into the plane formed by the side rails 21 and 22 defining the opening O in the walk-through section W of the ladder above the surface A.
Any secure fixation or placement of the horizontal grasping rungs 15, whether by affixing them to the side rails 21 and 22 directly or otherwise by placing them securely at the required sites, is satisfactory. Moreover, although not necessarily in every structure providing the same level of protection, where the size of the opening O permits, the horizontal grasping rungs 15 may be placed proximate the opening O.
As seen in the third embodiment in FIG. 3, the rungs 15 may be placed outside of the side rails 21 and 22 of the walk through section W. Thus, the horizontal grasping rungs 15 may be in the same plane as the opening O but affixed to the side rails 21 and 22 and extending outwardly therefrom rather than into the opening O of the walk-through section W.
This walk-through ladder improvement of the present invention is applicable to other fixed ladders used in industry and construction. For example, as seen in FIG. 1, it is applicable to a job-made ladder L by bolting the rungs 15 at one end to vertically oriented uprights 23 and 24 which extend above the surface A and are aligned parallel to the side rails 21 and 22.
Furthermore, the rungs 15 can be either built into new ladders at the time of fabrication or retrofitted to existing ladders.
The purpose of the improvement of the present invention is to provide rung-like grab-bars with spacing similar to the ladder rungs 2 which are further down in the lower section of the ladder L. Thus, the climber C who has the task of climbing up or down the ladder L can do so with greater security by holding onto the horizontal grasping rungs 15 rather than onto the vertical uprights 23 and 24 or the side rails 21 and 22 which cannot be grasped effectively for even short time periods if the climber's feet slip during mounting or dismounting from the walk-through section W. Dismounting is typically to a landing onto a roof, mezzanine, platform, parapet or other surface A that may be flat or sloped.
The results of a lost grip on the side rails 21 and 22 at the top of the ladder L can be catastrophic with long falls to the ground G or to a lower platform, thus resulting in serious injury or death in many cases each year. This kind of accident can occur even if there is a protective ladder cage (not shown) or if the climber's protection cable (not shown) has been disconnected.
It is preferable that the horizontal grasping rungs 15 associated with the walk-through section W be long enough for the climber's hand, either bare or gloved, to hold preferably 4 to 5 inches and up to 6 inches of the rung 15. Also, a diameter of about 1.5 inches is preferred for the rungs 15. Alternatively, rungs 15 of 0.75 inch diameter or other sizes may be welded or bolted for uniformity with the other rungs 2 to meet codes that require this uniformity over ergonomics.
Ordinarily after a slip, the hand of the climber C cannot hold the vertical side rail 21 or 22 long enough to regain his balance. Thus, a power grip is now required in the 1992 ANSI A14.3 Code Section. Such a power grip cannot be achieved with the prior art ladder which use side rail 2 of flat material with dimensions of either 3/8"×2" or 3/8"×21/2".
The preferred material may be galvanized steel, stainless steel, aluminum, fiberglass or any other sturdy substance capable of holding the human body when the material is bolted on the ladder L. Improved fastening devices can be used to permit a mechanical attachment without the need to drill holes through the ladder L to attach metal bolts thereto. Instead, a single coupling 25, shown schematically in the first embodiment in FIG. 1, could be used for easy fitting of the rungs 15 on each side of the opening O to the side rails 21 and 22 of the walk-through section W.
The assembly including the walk-through section W with the horizontal grasping rungs 15 can be bolted together or welded with seamless joints in such a way that the welds will not break under a normal load or through corrosion or by any other reasonably destructive means.
The embodiment illustrated in FIG. 2 recognizes that the codes generally call for the flared walk-through section W at the top of the fixed ladder L to broaden outwardly from the rungs 2, which have a 16-inch minimum clear width, to the opening O, which has a clear width of 24 to 30 inches. The additional rungs 15 for climbing protection on the ladder L are accommodated in the opening O which is essentially a higher clear space up to 36 inches in width. However, as one skilled in the ladder art will readily appreciate, the opening O may be decreased in width for safety if it is so desired.
Because of the capability of the climber C to span 36 inches which is the maximum allowed by the 1992 A14.3 Code Section without loss of gripping power, the present invention is valuable for increasing safety. If an authority determines that the flaring of the walk through section W is unnecessary for safety and permits the present invention to be placed inside the flared walk-through section W, thereby narrowing the opening O and decreasing the fall space in the opening O, the improvement can be of great help to the climber C without sacrificing his ability to dismount properly, even if necessary to do edgewise, because of the increased hand grasping power allowed by the invention. Thus, the climber C can remount the ladder L for descent more easily and safely since the spacing and location of the rungs 2 and 15 are uniform for the entire length of the ladder L and the walk-through section W in FIG. 2.
The width of a climber's hips ranges from 11.1 to 16.4 inches across the front and a climber's buttocks range from 7.6 to 14.0 inches from front to back according to U.S. Army Mil-Std. 1472C (1980). Tools on the climber's body can add to these dimensions, so fitting in sideways helps minimize the climber's contact with the vertical uprights 23 and 24 in FIG. 1.
If there are railings 26 as seen in FIG. 4, along the side rails 21 and 22, a fitting 27 may be added to allow the plurality of rungs 15 to be mounted to the side rails 21 and 22 inside the walk-through section W. This fourth embodiment helps the climber C to pull himself manually onto the surface A. Conversely for descent, the closer accessibility of the grasping rungs 15 will be helpful for maintaining confidence of gripping power as the climber C turns around to face the ladder L for descent.
As shown in FIGS. 5 and 12, a job-made ladder L can be very dangerous because the side rails 21 and 22 are typically lumber which is virtually impossible for the normal climber C to grasp in order to regain his balance when a slip or a fall occurs. The variation of the present invention illustrated in FIG. 5 shows how the improvement can work with 2×6-inch or 4×4-inch side rails 21 and 22 to increase safety through better handholds.
Specifically, the fittings 27 may not be merely attached to one side of the rails 21 and 22, as seen in FIG. 4. Rather, as shown in the fifth embodiment of FIG. 5, fasteners 28 may pass through the side rails 21 and 22 to help secure the fittings 27 thereto.
Where no railings 26 are available as seen in the sixth embodiment of FIG. 6, attachments 29 provide railings back from an edge E of the surface A to which the ladder L is fixed. These attachments 29 extend back preferably six feet or more and provide protection on most commercial roof surfaces A. For a parapet ladder L, the horizontal grasping rungs 15 may be secured on both side rails 21 and 22 to the attachment 29 by double couplings 31 and 32. Such double couplings 31 and 32 may be bolt and nut connections. They are illustrated but were not previously discussed in the embodiments shown in FIGS. 2 through 5.
Other uses for the horizontal grasping rungs 15 as grab bars are also contemplated for any location where a comfortable handhold is needed to support balance, e.g., on machinery, cranes, platforms, and the like. Such arrangements are within the scope of the present invention.
An embodiment of the present invention, where either a flared or non-flared fixed ladder (ladder not shown) is modified by placing elongated sleeves 121 and 122 over side rails 21 and 22, respectively, is shown schematically in FIG. 10. The sleeves are adapted to interfit over and be secured to the side rails. In FIG. 10, rung 15 placement on the sleeves is such that, after the sleeves are secured to the side rails, the rungs extend outwardly from the non-flared walk through area. In FIG. 11, an alternative sleeve configuration is shown schematically where the sleeves 121 and 122 are interfitted over flared side rails 21 and 22, respectively, with rungs 15 situated within the flared opening O.
In yet another embodiment of the present invention, schematically illustrated in FIG. 12, the walk through section of a job made ladder is shown, wherein the side rails 21 and 22 (typically constructed using 1×1 inch or 4×6 inch wooden side rails) are modified by securely affixing horizontal grasping rungs 15 at locations and intervals in accordance with the present invention. Rungs 15 may be affixed to the side rails using rung-forming device 115 schematically shown in FIG. 13. The rung-forming device is comprised of a screw section 117, stop 118 and rung section 116. When device 115 is screwed into the side rail by driving in screw section 117, stop 118 contacts the side rail, when rung section 116 is properly positioned.
It should be apparent to persons of ordinary skill in the ladder art that numerous variations of the preferred embodiments described hereinbefore may be utilized and that, while this invention has been described fully and completely with special emphasis upon preferred embodiments, it should be understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. In particular, the architecture of the walk-through section of the present invention can be used advantageously with numerous types of ladders, as will be appreciated by person's of ordinary skill in the ladder art and is not limited to fixed and/or flared walk-through ladders. | A fixed ladder has a first plurality of parallel rungs arranged along a lower section thereof and also has a walk-through section with vertical side rails arranged at the top thereof. A second plurality of parallel rungs is arranged along the walk-through section. This second plurality of rungs is attached at one end to the vertical side rails of the walk-through section and is easier to hold then the vertical side rails if a foot or a climber slips near the top of the ladder while mounting or dismounting at the walk-through section. | 4 |
BACKGROUND OF TECHNOLOGY
In the fast developing field of biology and medical technology, it is an obstacle to the advancement that people cannot precisely measure the variation of biological phenomenon in real time to realize the function of the variation. Since 1990, a biosensor system has been defined as an apparatus which utilizes immobilized biomolecules in combination with a transducer to detect in vivo or in vitro chemicals or produce a response after a specific interaction with the chemicals. The biomolecules comprise molecule identifying elements for the tissue of an organism or an individual cell. Such elements are used for receiving or generating biosensor signals. The transducer is a hardware instrument element that mainly functions as a physical signal converting element. Consequently, a biosensor system can be constituted by combining specific biologically active materials, which can be obtained by isolating, purifying or inventively synthesizing the materials via biochemical methods, with a precise and fast responding physical transducer.
An earlier biosensor, which was constituted by an enzyme electrode such as the enzyme electrode for use in the blood-sugar test (Clark et al., 1962), was developed and marketed by the YSI Company. Since 1988, pen-shaped and card-shaped enzyme electrodes utilizing a mediator to speed up the time of response, enhance the sensitivity, and reduce the interference caused by other biological materials, have also been developed (Demielson et al., 1988). However, the sensitivity of such first generation biosensors is limited by the weak conjugation between the biomolecule-enzyme and the test target. Even though the enzyme possesses the ability to amplify the signal, there still exists a defect in which a test target of low concentration cannot be detected in a short period of time.
The second generation biosensor, which is an affinity biosensor, is designed to overcome the above-described obstacles. It adopts an anti-body or receptor protein as a molecule identifier. Generally, its conjugation constant between biomolecules and target molecules is above 10 7 M −1 , and its detectable limit value is much more precise and smaller than that of the first generation biosensor.
The transducer of the second generation biosensor can be made of a field effect transistor (FET), a fiber optic sensor (FOS), a piezoelectric crystal (PZ), a surface acoustic wave (SAW) device, etc. The second generation biosensor was developed by a Swedish company, Pharmacia Biosensor AB, in the year 1991 by employing the technologies of micromachining and genetic engineering to develop the affinity biosensors, BIACORE and BIA lite. These products utilize the technologies of surface plasmon resonance (SPR) and micromachining to conduct a real time detection of biomolecules, in general, under the concentration from 10 −3 g/ml to 10 −9 g/ml to achieve an acceptable resolution. Although these products may achieve high resolution, they are not economical and practical because of their difficult technologies and their high price, for example, US $300,000 dollars. In addition, the price of their consumable detection chips, which cost $200 US dollars for each chip, is also very expensive. As a result, it is quite difficult to popularize these products.
Among the second generation biosensors, an alternative one adopts a quartz crystal microbalance (QCM) system using piezoelectric technology as the transducer. Such an apparatus, which costs about $30,000 US dollars and each consumable chip of which costs about $30 US dollars, is much cheaper than that of the aforesaid one, which utilizes the technology of SPR. However, its resolution and sensitivity can merely reach 10 −3 g/ml to 10 −6 g/ml.
SUMMARY OF THE INVENTION
An object of the present invention is to overcome the defect of QCM, and promote the sensitivity and resolution of the QCM biosensor system, in order to make it more economical and practicable. Furthermore, if the present invention is utilized in combination with a transducer of high precision, the detection resolution can be significantly raised.
In accordance with the present invention, a high resolution biosensor system measures the effects of gas or liquid characteristics, such as density, viscosity and temperature of the gas or liquid present at the surface of a piezoelectric quartz crystal, as well as the differential pressure between the two sides of the crystal, on the oscillation frequency of the crystal. The relation among these factors can be illustrated by the following equation:
Δ F=CF 2 ΔM/A+CF ⅔ (Δη L Δρ L ) ½
wherein
C: a constant, −2.3×10 −6 cm 2 /Hz-g
ΔF: the frequency variation caused by mass load
F: oscillation frequency of quartz crystal
ΔM: the variation of mass load carried by the electrode
A: area of electrode
Δη L : variation of solution viscosity
ρ L : variation of solution density
As the density and viscosity of the solution remain constant, the frequency variation (ΔF) is directly proportional to the variation of the mass load (ΔM). However, the precision of the frequency counter used in traditional biosensor systems can only reach 1 Hz. If the base clock is 10 MHz, the ultimately detectable limit can only be 0.43×10 −9 g (approximately corresponding to 4.3×10 −6 g/ml). The present invention utilizes a phase-lock loop (PLL) circuit to generate a counting signal that has the same phase as the base clock, but the frequency thereof is n times higher than that of the base clock, such that the resolution can be raised n times. For instance, if n=100, the frequency for the resolution can reach 0.01 Hz and the ultimately detectable limit can be up to 4.3×10 −12 g (approximately corresponding to 4.3×10 −9 g/ml). This invention may vastly enhance the precision of measurement and improve the identification sensitivity of biological target by up to 100 times, and thus reach the virus level of identification. Furthermore, the PLL circuit comprises a filter for tracing phase error, and utilizes a closed loop servo control to maintain the phase relation. Therefore, the frequency jittering problem customarily caused by noises in input signals can be overcome, because the output signal of PLL does not disappear with the instantaneous variation, such that the S/N ratio can be raised and a stable output frequency can be achieved.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is schematic diagram of a conventional piezoelectric microbalance biosensor;
FIG. 2 is schematic diagram of the high resolution biosensing system according to the present invention;
FIG. 3 shows an embodiment for practicing the concept illustrated in FIG. 2;
FIG. 4 is a block diagram showing the PLL circuit of the present invention;
FIG. 5 is a waveform diagram for signals at each node of FIG. 4;
FIG. 6 illustrates the relationship between the input and the output of the PLL circuit according to the present invention.
FIG. 7 illustrates the timing chart of an embodiment of the PLL circuit according to the present invention.
DESCRIPTION OF THE INVENTION
One of the embodiments of the present invention is a modification of a piezoelectric biosensor ( 100 ) of the type illustrated in FIG. 1, which induces an oscillating electric field along a direction perpendicular to the surface of the chip to make the crystal lattice ( 102 ) inside the chip produce mechanical oscillations similar to a standing wave. This type of mechanical oscillation can be indicated by a specific frequency. A resonant frequency can be measured by applying an appropriate oscillation circuit ( 104 ) and frequency counter ( 106 ), the resulting frequency being made available to a computer (P.C.) through an interface ( 108 ) for analysis.
The following equation shows the relationship between the frequency of the piezoelectric quartz crystal and the solution of the detected organism:
Δ F=CF 2 ΔM/A+CF ⅔ (Δη L Δρ L ) ½
wherein
C: a constant, −2.3×10 −6 cm 2 /Hz-g
ΔF: the frequency variation caused by mass load
F: oscillation frequency of quartz crystal
ΔM: the variation of mass load carried by the electrode
A: area of electrode
Δη L : variation of solution viscosity
Δρ L : variation of solution density
As the density and viscosity of the solution remain constant, the frequency variation is directly proportional to the mass load, and will be detected by the QCM biological detection crystal. Then, the QCM crystal outputs a signal accordingly.
In the prior art shown in FIG. 1, the known biosensor ( 100 ) transmits the signal to oscillation circuit ( 104 ) to produce an oscillation signal, and the oscillation signal of the oscillator is transmitted to frequency counter ( 106 ) to obtain a frequency value. The principle of the counter is to sum up the counts of the input pulses every second to figure out the frequency value (the sum of pulses per second). For example, if the pulses are summed up one time per second, the minimum unit (resolution) is 1 Hz. If they are summed at ten second intervals, the minimum unit is 0.1 Hz (namely, 0.1 pulse per second). As a result, for the purpose of promoting resolution, the sampling rate must be compromised. If the sampling rate remains at one time per second, when a resolution higher than 1Hz is desired, the pulse would need to be divided into more units for counting.
The present invention provides a solution to overcome the above problem by providing a modified biosensor ( 101 ) that utilizes a phase lock loop (PLL) circuit ( 110 ) and ultra-high frequency counter ( 112 ) in place of the frequency counter ( 106 ) of the conventional biosensor ( 100 ). The PLL circuit ( 110 ) generates a signal that has the same phase as the original one but has a counting frequency which is n times the original frequency.
The relation between the new counting signal and the original one is illustrated in FIG 6 , while FIG. 4 shows details of the phase lock loop circuit ( 110 ). The output signal (f) of the oscillation circuit of the modified biosensor ( 101 ) is transmitted, to a phase comparator ( 402 ) having an a second input the frequency multiplied output of voltage controlled amplifier 408 for comparing the phase of signals. If the phase of the input signal (f) leads the signal at node (b), the signal at node (c) is a positive wave. The more the signal (f) leads the signal at node (b), the broader the pulse width of the signal at node (c) becomes. On the other hand, if the input signal (f) phase lags behind the signal at node (b), the signal at node (c) is a negative wave, and the less the signal (f) lags the signal at node (b), the narrower the pulse width of the signal at node (c). When the phase difference between the signal (f) and the signal at node (b) is quite small, the signal at node (c) is a very narrow impulse.
The phase comparator output signal at node (c) is preferably filtered through a low pass filter ( 404 ) and amplified by an amplifier ( 406 ) to generate a DC voltage signal to control the frequency of the output signal (nF) from voltage controlled oscillator (VCO) ( 408 ). The higher the DC voltage input into the VCO ( 408 ), the higher the frequency of the output signal of the VCD (nf) becomes, and, after feedback, the frequency at node (b) will be raised. On the other hand, if the DC voltage is negative, the frequency at node (b) will descend. Eventually, the phase of the signal (nf) will be stabilized to be similar to the signal at node (b). Furthermore, the frequency of the output signal (nf) which is n times the frequency f of the signal f (namely, nf) is then transmitted to ultra-high frequency counter ( 112 ) so that a high precision of the variation detected by the biosensor can be achieved. The operation principle of the combination of the phase lock loop (PLL) circuit with quartz crystal microbalance is further described below.
Essentially, the piezoelectric quartz crystal sensor ( 102 ) utilizes oscillation to detect and identify the mass variation of target materials, so it intrinsically is an oscillator. The oscillation is converted into pulses by oscillator circuit ( 102 ) and phase lock loop ( 110 ). The number of the pulses are counted by a counter ( 112 ). In the example 1 described below, an oscillation with frequency (f) of 10 MHz is adopted for the purpose of illustration. About 10,000,000 pulses are counted in one second. However, the last pulse, in fact, is not a complete pulse. Therefore, the actual count should be about 9,999,999 and {fraction ( 2 / 3 )} pulses. And yet, the highest resolution is 1 Hz, because such a decimal fraction cannot be directly detected by directly inputting the oscillation with frequency (f) into the counter.
The following examples are presented for illustration purposes and not to limit the scope of the invention.
EXAMPLE 1
As illustrated in FIG. 7, if we incorporate and calculate the time of the last one pulse, φ, then we can raise the resolution of the bio-sensor. This invention employs the PLL circuit to achieve said purpose. The PLL circuit ( 110 ) is used to produce a signal with the same phase as the original signal, but the frequency thereof has been raised n times in a cycle. As shown in FIG. 7, if the original frequency f equals “a+φ”, and “a” is an integer, since φ<1, the detectable frequency f is “a”. Now we raise the frequency by n times, nf, nf=na+b+φ′, wherein b=φ−φ′and is an integer. So, if “na+b” can be detected but φ′, which is less than 1, cannot be detected, (nf) will be “na+b”. If nF is divided by n, then we can get the original frequency f, (na +b)/ n=a+(b/n). Therefore, we get the frequency count number of “a+(b/n)”. In other words, the resolution has been raised n times.
On the other hand, since the PLL circuit ( 110 ) comprises a filter ( 404 ) to trace the phase error and employs a closed loop control to retain the phase, even if the input signal is affected by noise that results in frequency jittering, the PLL circuit will not produce any instantaneous change, and a stable result can therefore be achieved. Such a result is an extraordinary and unexpected advantage of using a PLL circuit.
FIG. 3 shows details of an implementation of the circuit of FIG. 2 in which the signal sensing circuit includes a central processing unit ( 318 ), data recorder ( 320 ), corresponding level and tn-state converters ( 324 , 326 , 328 , and 330 ), latches ( 322 , 334 ), clock ( 336 ), and an RS232 interface ( 338 ). The signal frequency (f) of the oscillator ( 304 ) connected to chip ( 302 ) is input through a signal receiver ( 314 ) to PLL circuit ( 310 ), which generates an output with an n times frequency (nf). The signal nf is sent to an ultra-high frequency counter ( 312 ) before being level converted by converter ( 324 ) and applied to counter ( 306 ). The ultra-high frequency counter ( 312 ) counts the number of pulses produced in every second, and thus a resolution of 1/n can be achieved . For instance, if n=100, the resolution will be 0.01. Since the present invention employs hardware to implement the high speed sampling, the variation sensed by of biosensor can be rapidly and precisely measured. Because the division of frequency (nf) by n results in the frequency of the signal at node (b), which is then used in phase comparison, an output frequency (nf) which is n times the input frequency (f) can finally be obtained, and the phase difference between (f) and (nf) is a fixed value, Z, as shown in FIG. 6 .
Furthermore, as illustrated in FIG 4 , the low pass filter ( 404 ) may not only make the pulse width at node (c) correspond to the DC voltage at node (d), but also eliminate the noise. Therefore, the output of PLL possesses a merit of quite small jittering. Such a merit may overcome the problem of getting a worse S/N ratio after raising the resolution. This is an extraordinary advantage.
The above description fully discloses the invention including preferred embodiments thereof. Modifications and improvements of the embodiments specifically disclosed herein are within the scope of the following claims. Without further elaboration, it is believed that one skilled in the area can, using the preceding description, utilize the present invention to its fullest extent. Therefore, the examples herein are to be construed as merely illustrative and not a limitation of the scope of the present invention in any way. The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows. | A high resolution biosensing system for detecting and identifying a biochemical material to be tested by using proportional relationship between frequency variation of oscillation and mass of the biochemical material to be tested comprises a biosensor; an oscillatorfor generating oscillation based on the sensed result; a phase-lock loop circuit receiving the oscillation of the oscillator and generating pulse signals;an ultra-high frequency counter for counting the pulse signals; and a microprocessor for storing and displaying output from the ultra-high frequency counter and for controlling the oscillator. The phase-lock loop circuit generates the pulse signals of a frequency, which is n times the frequency of the oscillator and with a constant phase difference therebetween to trigger the ultra-high frequency counter. Accordingly, the resolution can be raised up to n times. | 6 |
BACKGROUND OF THE INVENTION
The present invention relates to an apparatus and a method for detecting the washings weight of a washing machine, more particularly, to an apparatus and a method which detects the washings weight before the supplying of water and detects the washings weight again after the water is supplied up to level 2 which is lower level where the washings weight is not more than level 3 which is low level, or detects the washings weight again after water is supplied up to level 3 where the washings weight is not less than level 4 which is medium low level so as to prevent the washings weight detection error and a water level determination error.
As shown in FIG. 1, the conventional washing machine comprises a motor 1 for generating a power according to a control of a microcomputer, a clutch 5 for receiving the power through pulley 2, v-belt 3 and clutch pulley 4 and a wing 7 for rotating by the power and swirling water in a water receiving tub 6. Reference numeral 8 denotes clothing.
As shown in FIG. 2, a washings weight detecting circuit of conventional washing machine comprises the microcomputer 9 controlling the total operation, motor driving means 10 including array resistors R3-R6,R9-R10, TRIACs TA1,TA2, capacitors C1-C4, resistors R7,R8, to control the driving of the motor 1, and a washings weight detecting means 11, which comprises diodes D1,D2, photo-coupler PC, transistors Q1,Q2 and resistors R16-R19 which transmit the data to the micro computer after detecting the washings weight with a residual voltage generated by a force of inertia of the motor 1 when the electric power for said motor 1 cuts off.
FIG. 3 is a water level display diagram of the washing machine. The water level is divided into 5 levels or 7 levels.
Hereinafter, the operation of the conventional washing machine are described in detail with reference to FIGS. 1 to 6.
First, if a user selects a key so as to wash the clothing after detecting the washings weight, the microcomputer 9 performs an initial operation. That is, the microcomputer 9 makes the water supply to a water receiving tub 6 by opening the cold and hot water valves (not shown) through the motor driving means 10 to the predetermined water level.
When the water supply operation is completed, the microcomputer 9 outputs high signal through ports P54,P55 alternatively during certain period of time so as to detect the washings weight in the said tub 6. Namely, the high signal which the port P54 outputs is applied to a gate of TRIAC (bidirectional triode-thyristor) TA1 through the array resistors R4,R6,R10 and a switching element Q4 as a trigger signal and makes the TRIAC TA1 turned on, and the outputted high signal from the port P55 is applied to a gate of TRIAC TA2 through array resistors R3,R5,R9 and the switching element Q3 as a trigger signal and makes TRIAC TA2 turned on. Therefore, the inputted alternating currents are applied to the motor 1 through turned on TRIACs TA1,TA2 and the motor 1 starts to operate to make the wing 7 rotate in clockwise or anticlockwise direction.
When the motor 1 is started to operate, the voltage is generated in the motor during certain period of time and is applied to the washing weight detecting means 11 and then the washings weight detecting means 11 makes the voltage generated from said motor 1 into a waveform and input said shaped waveform into the microcomputer 9.
And the microcomputer 9 also outputs the signals through the ports P55,P54 during a certain period of time and then TRIACs TA1,TA2 become turned off, thereby the alternating currents which are applied to the motor are cut off.
However, although the alternating currents are being cut off, the motor 1 is not stopped. It takes time to a complete stop due to the force of inertia.
That is, if the volume of clothing is large, because the friction between the wing 7 and clothing are increased, the motor 1 is stopped within short period of time. On the other hand, if an volume of clothing is small, because the friction between the wing 7 and clothing are decreased, the motor 1 is stopped slowly. Therefore, the residual voltage is generated in the motor 1 during the certain period of time (T2 period) as shown in FIG. 6(A).
And the washings weight detecting means 11 is detecting the residual voltage of the motor 1 generated by inertia force and is transforming the residual voltage into waveform and inputs said shaped waveform to the microcomputer 9. Namely, said generated residual voltage is rectified in half-wave type through resistors R1,R2 and diode D1 and then the rectangulated waveform of FIG. 6(B) is outputted by a light emitting element and a light receiving element. The outputted waveform is transformed transistor Q1 and then is inverted by the transistor Q2, thereby the waveform of FIG. 6(C) is inputted to the microcomputer 9.
The microcomputer 9 counts the number of the inputted waveform from washings weight detecting means 11, determines the water level after recognizing the number of inputted waveforms. For example, the number of the waveforms (T2 period) is in the minimum range, the water level is determined to be level 7 and the washing time is set up longer. On the other hand, the number of the waveforms (T2 period) is in the maximum range, the water level is determined to be level 1 and the washing time is set up short.
FIG. 4 shows a flow chart of the water level determining process according to the key selection by a user. As mentioned above, the determination of a water level and the washing time is done, the next process is performed. At this time, the microcomputer 9 controls the rotation of the wing 7 according to the determined water level, as shown in FIGS. 5(A)-(G). For example, if the water level is high, a real operating rate (operating rate of wing ON position) is large, and if the water level is low, the real operating rate is small.
The real operating rate in case of 7 level ##EQU1## Where, t Al =driving pulse time period in anticlockwise direction,
t AR =driving pulse time period in clockwise direction,
t AP =OFF pulse time period.
As shown in FIG. 5, the real driving rate (A-G) is proportioned to the water level.
After the above-mentioned process is finished, the following process is performed. If the washing process is only one time, DRAINAGE, Intermittent SPIN-DRY, SPIN DRYING, PAUSE, WATER SUPPLY, WASH is performed in such an order. If the washing process is more than two times, the said step is repeated.
Then, the dehydrating process is performed, that is DRAINAGE, Intermittent SPIN-DRY, SPIN-DRYING, PAUSE is performed in order, thereby all the washing operation is completed.
However, there are problems in this type of conventional washing machine that the washing efficiency is deteriorated just following the selected water level. For example, if the water level is higher compared to the amount of clothing, the washing process is performed successfully but the entanglement rate of the clothing is high, but if the water level is low by compared to the amount of clothing, the entanglement of the clothing is low but the washing process is not performed well and the damage rate of the clothing is increased.
Also, because the washings weight detection process is performed only one time in order to determine the water level, the total washing efficiency is deteriorated when the washing weight is detected erroneously.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an new and improved washings weight detection apparatus and a method, thereof which detects the washings weight before the supplying of water and again detects the washings weight after the water has been supplied to lower level where the washings weight is lower than low level, or detects the washings weight again after water is supplied until low level in case that the washings weight is higher than medium low level so as to prevent the washings weight detection error and a water level determination error.
In order to achieve the above-mentioned object, the present invention comprises the washings weight detecting means which converts a change of magnetic pole of a magnet formed in turned off motor shaft into a electric signal and detects the washings weight both in wet washings situation and in dry washings situation and the microcomputer which determines the water level according to the detected washings weight.
A method for detecting the washings weight according to the present invention comprises the steps of (A) first water level determining process including detecting the washings weight before the supplying of water and determining a first water level, (B) second water level determining process including detecting washings weight again after supplying the water to low level when said first water level is higher than medium low level and determining the second water level, (C) first actual water level determining process including (i) comparing the first water level with the second water level (ii) determining the actual water level according to the difference of said two level (iii) supplying the water (iv) proceed the washing operation, (D) third water level determining process including supplying the water to lower level when said first water level is not level is not higher than low level, detecting the washings weight and determining the third water level, (E) 2nd actual water level determining process including comparing the first water level with the third water level and determining the first water level as the actual water level when the first water level is higher than the third water level or the water level difference between the two levels is not larger than one level supplying the water and proceed the operation, and (F) returning to the step (B) when the water level difference between said first level and said third water level is not smaller than two level after canceling the determination of third water level.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a general structure of a washing machine;
FIG. 2 is the washings weight detecting circuit diagram of conventional washing machine;
FIG. 3(A) is a water level display diagram of 7 levels,
FIG. 3(B) is a water level display diagram of 5 levels;
FIG. 4 shows a flow chart of the water level determining process according to the conventional washing machine;
FIGS. 5(A)-5(G) are a waveform diagram of the driving of the wing according to the conventional washing machine;
FIG. 6(A) is a waveform diagram of the residual voltage of the motor of FIG. 2;
FIG. 6(B) is a waveform diagram of output of photo-coupler in the washing weight detecting means of FIG. 2;
FIG. 6(C) is a waveform diagram the input of the microcomputer of FIG. 2;
FIG. 7 is a block diagram of the washings weight detecting means of the washing machine according to the present invention;
FIG. 8 is a partially sectional view of the washings weight detecting means according to the present invention;
FIG. 9 is a detailed circuit diagram of a waveform shaping circuit;
FIG. 10 is a circuit diagram of the constant-voltage switching circuit;
FIG. 11 is a detailed structure of the magnet of FIG. 7;
FIG. 12 is a waveform diagram of the driving of the motor of FIG. 7;
FIG. 13 is a water level display and a detergent display diagram of the washing machine according to the present invention; and
FIG. 14 shows a flow chart of the washing weight detecting process of the washing machine according to the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Preferred embodiments of the present invention are described in detail hereinafter.
FIG. 7 is a block diagram of the washings weight detecting means of the washing machine according to the present invention. The washings weight detecting means 30 comprises a magnet 31 connected to a shaft 21 of the motor 20, a constant-voltage switching circuit 32 detecting the change of magnetic pole of said magnet 31, a waveform transforming circuit 34 which is connected to said constant-voltage switching circuit 32 through connecting portion 33 and transforms a output signal of said constant-voltage switching circuit and inputs said transformed signal to the microcomputer (not shown).
FIG. 8 is a partially sectional view of the washings weight detecting means according to the present invention. The magnet 31 is connected to the shaft 21 of the motor 31, the constant-voltage switching circuit 32 is installed in the opposite side of said magnet 31 at certain distance, and a casing 35 surrounding the constant-voltage switching circuit 32 is installed.
FIG. 9 is a detailed circuit diagram of waveform transforming circuit. The waveform transforming circuit 34, which comprises capacitors C1,C2, resistors R10-R13, a diode D1, and a switching element Q6, transforms the outputted signal of the constant-voltage switching circuit 32 into rectangulated waveform and is connected to the microcomputer 40 which counts the output pulse of the washings weight detecting means, detects the volume of the clothing of clothes and controls the total operation of the washing machine using said volume data.
FIG. 10 is a circuit diagram of the constant-voltage switching circuit. The constant-voltage switching circuit comprises a hall sensor 32a for of which output voltage is converted according to the change of magnetic pole of magnet 31, a comparator 32b for comparing a reference voltage Vref with the output voltage of said hall sensor 32a and outputting the signal of compared value, a constant-voltage element 32c for converting the drive voltage Vcc into the constant voltage and outputting said constant-voltage, a switching element 32d outputting the voltage for switching ON or OFF the constant-voltage according to the output of the constant-voltage element 32c and outputting the result. Reference numeral 32a denotes a current source.
Hereinafter, the operation and efficiency of the present invention is described in detail with reference to FIGS. 7 to 14.
First, if a user selects start key when the clothing are put in washing machine, the microcomputer 40 detects the washings weight of washings in dry state. That is, the microcomputer 40 makes the motor 20 and makes the wing rotate in clockwise or anticlockwise direction by predetermined number as shown in FIG. 12. After the microcomputer makes the wing rotate in clockwise direction by predetermined number, and cuts off the power supply to detect the washings weight, and, after the microcomputer makes the wing rotate in anticlockwise direction by predetermined number and cuts off the power supply for the motor 20.
If the microcomputer cuts off the power supply, the motor 20 is not stopped immediately and continues to rotate for certain period of time due to the force of the inertia. At this time, if the volume of the washings is large, the rotation of wing is influenced by the high friction force between the clothing the wing. If the volume of the washings is small, then the rotation of the becomes easy.
As above mentioned, when the motor 20 is turned off, the washings weight detecting means 30 detects the residual rotation of the wing, and further detects the washings weight.
When the microcomputer cuts off the power supply after the wing rotates in clockwise direction, the motor 20 is not stopped immediately and continues to rotate for certain period of time. At this moment, the magnet 31 attached to the center of the motor shaft is also rotating.
The magnet 31, as shown in FIG. 11, comprises three pairs of magnetic pole the constant-voltage switching circuit 32 converts a change of magnetic pole into a electric signal.
Namely, as shown in FIG. 10, the output voltage of the hall sensor 32a is changed according to the change of magnetic pole, and the comparator 32b compares the reference voltage Vref with said output voltage of the hall sensor 32a and outputs the result. At this time, It is assumed that if N pole of the magnet 31 is indicating forward the hall sensor 32a, the output voltage of the hall sensor 32a is higher than the reference voltage Vref, but if S pole of the magnet 31 is indicating forward the hall sensor 32a, the reference voltage Vref is higher than the output voltage of the hall sensor 32a. Therefore, if N pole of the magnet 31 is indicating forward the hall sensor 32a, the comparator 32b outputs the high signal and if S pole of the magnet 31 is indicating forward the hall sensor 32a, the comparator 32b outputs the low signal. The switching element 32d repeats ON, OFF state according to the output of the comparator 32b and output the switched constant-voltage. The switched constant-voltage, which is outputted by the switching element 32d, is inputted to the waveform transforming circuit 34 and is shaped by the waveform transforming circuit 34 and the transformed waveform is inputted to the port P60 of the microcomputer 40 as the pulse signal. Therefore, the microcomputer 40 counts the pulse signal and detects the washings weight. Thus, the microcomputer can detect the washing weight by counting the number of the pulse. By rotating the wing in anticlockwise direction, the above-mentioned operation can be repeated.
In other words, the microcomputer 40 makes the motor 20 rotate two times in clockwise direction, then cuts off the power supply as shown in FIG. 12 (T1 period) and counts the residual rotation pulse. After the count is completed, the microcomputer 40 makes the motor 20 rotate two times in anticlockwise direction, then again cuts off the power supply as shown in FIG. 12 (T2 period) and counts the residual rotation pulse.
After that, the microcomputer 40 detects the washings weight (S2) by the number of the pulse being counted in said OFF period (T1+T2), determines a first water level W1 and displays the volume of the detergent (S3) being used.
At this time, the determined water level is not displayed and the volume of the detergents only displayed in the water level display means and detergent display means while the determined water level data is stored in internal memory.
Then, the microcomputer 40 determines a second water level W2 according to the first water level W1.
If the first water level is not less than level 4 which is medium low level, water is supplied until level 3 which is low level (S5-S6), the washings weight is detected by the above-mentioned method and the second water level W2 is determined (S7-S9).
Then, the microcomputer 40 compares the volume of the first water level with that of the second water level and calculates the water level difference. If the water level difference is not more than one level (for example, W1=level 6 which is medium high, W2=level 5 which is medium), the first water level W1 is determined to be the actual water level W1 (S11), the actual water level is displayed through a water level display means and detergent display means of FIG. 13 (S12). Then, the water is supplied corresponding to the determined actual water level (S13), the washing is continued (S15).
If the water level difference is not more than one level, the washings weight detection error rate, which results when the wet clothes is contained, is trivial. Generally, the washings weight detection before the supplying of water is more accurate than the washings weight detection after the supplying of water. But, when the washings weight is detected before the supplying of water, if the wet clothes is contained, the detection rate is lowered and the water level will be determined higher than actual volume of the clothing. Also, when the washings weight is detected after the supplying of water, the washings weight detection error, which results when the wet clothes is contained, may be decreased, but because the water supplying time is required, the washings weight detection time period takes lower.
When the water level difference W1-W2 is not less than two level, that is caused by wet clothing when the first water level is determined, the detected second water level after water supply to low level is determined to be the actual water level W2 (S16). The actual water level W2 is displayed through a water level display means and detergent display means of FIG. 13 (S12). Then, water is supplied to corresponding actual water level W2, the washing operating is processed (S13-S15).
On the other hand, in the above-mentioned step S4, if the first water level detected in step S4 is not more than level 3 which is low level, water is supplied until level 2 which is lower level (S17-S18), the washings weight is detected following the same method mentioned above and the third water level W3 is determined (S19-S21).
Then, the microcomputer 40 compares the volume of the first water level W1 with that of the third water level W3 (S22) and if the first water level W1 is higher than the third water level W3, the first water level W1 is determined to be the actual water level W1 (S23), the actual water level is displayed through the water level display means and the detergent display means of FIG. 13 (S12). Then, water is supplied corresponding to the determined first water level (S13), the washing operation is processed (S15).
If the first water level W1 is not higher than the third water level W3, the water level difference is calculated and if the water level difference is not more than one level, the first water level W1 is determined to be the actual water level W1 (S23-S24), the actual water level is displayed through a water level display means and detergent display means of FIG. 13 (S12). Then, water is supplied until the first water level (S13), the washing operation is processed (S15).
Also, if the water level difference is not less than two level, the third water level W3 is canceled (S25) and returned to the above-mentioned step (S5-S16) than the washing operation is continued.
In the type where the washings weight is detected after the supplying of water, the washings weight detecting rate is low when the water supply is low (in lower level) and the volume of clothing is large. Accordingly, if the water level difference is large, water is supplied until level 3 and the washings weight is detected. If the washings weight is not more than level 3 which is low level, it is preferred that water is supplied until level 2 which is lower level and the washings weight is detected. And if the washings weight is not less than level which is medium low level, it is preferred that water is supplied until level 3 and the washings weight is detected.
As above mentioned, the present invention detects the washings weight before and after the supplying of water. Therefore, the present invention is further accurate in the washings weight detection and decrease the entanglement of clothing. Even when a user set up the water level erroneously, the selection error can be corrected and the efficiency of washing machine can be improved.
While specific embodiments of the invention have been illustrated and described wherein, it is to realize that modifications and changes will occur to those skilled in the art. It is therefore to be understood that the appended claims are intended to cover all modifications and changes as fall within the true spirit and scope of the invention. | An apparatus for detecting a washing weight of washing machine has the rechecking function to detect the washings weight before and after the supplying of water and a microcomputer for determining the water level according to the detected washing weight. In a method for detecting washing weight of washing machine, if the washings weight is not larger than low level, water is supplied up to lower level and the washings weight is detected, thereby the water level is determined. And if the washings weight is not smaller than medium low level, the water is supplied up to low level and the washing weight is detected, thereby the water level is determined. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to convertible mobile, recreational and living vehicles and, more particularly, to a novel vehicle having extendable berth pods and top defining the living compartment area adapted to provide an interior having an overall width and height greater than when the berth pods and top are in their folded or stowed condition.
2. Description of the Prior Art
A variety of recreational vehicles are currently being employed by campers, hunters, sportsmen, vacationers or the like which combine mobility with living accommodations. A typical vehicle of this class is commonly referred to as a "camper" and utilizes a detachable living enclosure which occupies the open truck bed area of a conventional pick-up truck. Berthing areas extend outwardly over the truck bed sidewalls and an access door is generally provided at the rear of the enclosure. Another version of a camper vehicle or motor home employs a truck frame on which the living enclosure is erected.
However, difficulties have been encountered when employing conventional camper vehicles which largely stem from the fact that the vehicle employs a truck bed or frame which is of a predetermined length and width. The available living enclosure space rearward of the truck cab is relatively limited because of the restricted width and length of the truck frame so that the width of berthing areas are considerably more narrow than normally required to accommodate the full width of a reclining adult. Some attempts have been made to avoid this problem by extending the width of the living compartment or unit beyond the side limits of the truck frame or truck bed so that the entire width of the living enclosure is increased. Although such construction provides more width for berthing areas, the resulting overhang of the enclosure detracts from the off-the-road capabilities of the vehicle. Furthermore, great stresses are placed on the truck frame inasmuch as the conventional frames are loaded to an extent not compatible with their original design intent.
Other attempts have been made to provide living enclosures or units with full-width berthing areas that include an extendable side portion of the compartment which telescopes with respect to the main portion so that during travel, the overhang can be eliminated as the vehicle moves and when at rest, the side portion can be extended to increase the berthing space. Obviously, such extendable compartment portions are relatively complex, expensive and require periodic maintenance. Those conventional vehicles which employ a fixed living compartment or unit thereon, have limited utility in that the vehicles are generally restricted solely to the use thereof as a camper. Also, no means are provided for raising the top or roof of the compartment or enclosure so as to provide for standing room.
SUMMARY OF THE INVENTION
Accordingly, the convertible camper vehicle of the present invention obviates the aforementioned problems and difficulties by providing a camper vehicle having a living enclosure having width bunks or berths and a raisable top and still maintains the basic dimensional (envelope) characteristics of the carrier vehicle. The living compartment includes lateral, extendable berth pods which may be selectively extended outwardly to provide increased living space therebetween wherein an extendable or raisable top may be employed to achieve full-height or standing space.
In one form of the invention, the camper vehicle provides a vehicle body defining a living compartment having outwardly extendable lateral side pods adapted to form a pair of berths when extended. Each berth pod slidably mounts on a supporting frame carried on the bed of the vehicle. Cover means having pivotal side panels are employed to enclose each of the berthing pods while the vehicle is in its roadable condition and actuating means are employed to support the cover over the living compartment when the vehicle is in its parked condition. Means are employed to interconnect the support means with the frame and the berth pods so as to stabilize the berthing areas when the side panels are pivoted and pods are fully extended. Telescoping members are carried on the frame which serves to support the top cover when raised so that the height of the compartment is substantially increased.
Therefore, it is among the primary objects of the present invention to provide a lightweight mobile camper body or compartment capable of providing full-width sleeping accommodations with the advantage of little or no side overhang of the vehicle frame while the vehicle is in its roadable condition.
Another object of the present invention is to provide a novel mobile camper vehicle having a living enclosure defined by extendable side panels which, when extended, serve as full-length access areas leading into the interior of the compartment.
Another object of the present invention is to provide a novel mobile camper having a living compartment of relatively short height and width so that the overall vehicle dimensional envelope is substantially unaltered during its roadable configuration while incorporating laterally extending berth pods adapted to serve as berthing areas in one position. A compartment top having side closures serves to provide access to the interior and includes means for raising and lowering the top.
Yet another object of the present invention is to provide a convertible mobile camper having a first configuration substantially similar to a conventional panel-body truck and a second configuration wherein the sides of the compartment and the top of the compartment may be extended as a unitary structure to provide a full adult length, width and standing space.
A further object resides in the provision of a novel vehicle having pivoting side panels for access to the interior for storage of tools and supplys and adapted to receive berths, stove, basins, etc. so as to provide living quarters in another configuration.
Another object of the invention resides in a vehicle having an enclosure carried on the bed thereof suitable for usage as a store room for tools and the like or suitable for insertably receiving fixed units such as berths, basing and the like for use as an overnight camper.
BRIEF DESCRIPTION OF THE DRAWINGS
The features of the present invention which are believed to be novel are set forth with particularity in the appended claims. The present invention, both as to its organization and manner of operation, together with further objects and advantages thereof, may best be understood by reference to the following description, taken in connection with the accompanying drawings in which:
FIG. 1 is a rear perspective view of the novel convertible camper vehicle of the present invention illustrating the side portions thereof raised for side access to the interior;
FIG. 2 is a view similar to the view shown in FIG. 1 illustrating the camper living compartment occupied by parallel berths preparatory to lateral deployment;
FIG. 3 is a perspective view of the camper vehicle showing the top of the compartment raised and the berths laterally deplayed;
FIG. 4 is an enlarged transverse cross sectional view of the camper vehicle having the berths in their stowed position;
FIG. 5 is a view similar to the view of FIG. 4 showing the berths moved laterally and the top raised as illustrated in FIG. 3;
FIG. 6 is a perspective view of the berth and top supports defining the living enclosure of the camper vehicle;
FIG. 7 is an enlarged sectional view of the mechanism for raising the compartment top as taken in the direction of arrows 7--7 of FIG. 6; and
FIG. 8 is a transverse cross sectional view of the telescoping posts supporting the top of the compartment shown in FIG. 7 as taken in the direction of arrows 8--8 thereof.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a light-weight all-wheel drive vehicle is indicated bynumeral 10 which includes a rear body portion 11 adapted to mount a living compartment 12. The body 11 may include a rear tailgate 13 or may include an access door or panel 14. The living compartment 12 includes a forward portion 15 which is disposed adjacent the cab or driver's compartment of the vehicle and a rear portion 16 which fits into the open truck bed area of the vehicle defined by opposite side walls 17. As can be seen in the configuration of FIG. 1, the living compartment does not overhang the sidewalls 17 or the rear tailgate 13 so that the original vehicle envelopeis not changed. Furthermore, the length and width of the vehicle truck bed is conventional and is substantially narrower than is required to accommodate two single reclining adults lying between the sides 17 of the vehicle bed 11.
Each side of the living compartment 12 is defined by side panels 18 and 18'pivotally connected to the upper edge marginal regions of a central top panel 20. The panels 18 serve as sides for the compartment and enclose theinterior thereof when the vehicle is in its roadable or travelling condition. Suitable latch means may be provided to releasably secure the side panels to the compartment so that the panels will be retained in the closed position. Furthermore, the rear of the compartment 12 is enclosed by a pair of rear panels 21 and 22 representing half-doors which are pivotally connected to the respective rear ends of the compartment by means of hinges. Latch devices are included on each of the rear panels 21 and 22 so that the half-doors may be secured when desired to complete the enclosure of compartment 12. As indicated in FIG. 1, the side panels 18 and 18' may be pivoted outwardly and upwardly so as to provide access intothe interior of the compartment. When so extended, a brace or latching means 26 may be employed to support the side panel.
Referring now to FIG. 2, the side panels 18 and 18' have been deployed so as to extend upwardly and outwardly from the sides of compartment 12 exposing the interior thereof. To stabilize the extended side panels, a leg brace 26 pivotally attached to the underside of the side panel is positioned to support the panel in its open condition. It can clearly be seen that each of the panels 18 and 18' are composed of a pair of portionsthat are arranged substantially at 90° to each other so that one portion is coextensive with the top 15 and the other portion is coextensive with the sides of the vehicle when the panels are in their closed positions. A feature of this construction resides in the fact that when the panels are opened as shown in FIG. 2, ready access is available through the openings in the side of the compartment so that the user may have access to stored articles without having to remove other articles such as when access is solely from the rear of the vehicle. Furthermore, when the panels are so raised, the side portion of the panel provides a side overhang to protect the user and the side opening from rain or other inclimate weather.
FIG. 2 further illustrates the provisions for storing within the living compartment 12, a pair of berth pods indicated in general by numerals 30 and 31. When the vehicle is in its roadable condition, these pods are positioned as shown and are not generally available for use. However, whenthe vehicle has been parked and it is desired to use the interior for living purposes, the side panels 18 and 18' are lifted or raised and the elongated berth pods 30 and 31 may be laterally extended or slid outwardlythrough the side openings in the compartment as shown in FIG. 3. Also, as indicated in FIG. 3 the top of the compartment is raised and perferably, the berth pods are not slid out until the top has been fully extended upwardly as shown. In this condition, the panels 18 and 18' need not be pivoted about the top central panel 15.
As shown in FIG. 3, berth pod 31 is fully extended laterally from the compartment and berth pod 30 is still within the compartment preparatory to lateral extension as shown in broken lines. Once the top of the compartment has been fully raised, complete stand up room is available andonce the pods 30 and 31 have been laterally extended, substantial living space is available within the enclosure. It is to be understood that when the pods are extended and the top has been raised, the living space is fully enclosed since the adjacent edges of the panels 18 and 18' with the tops of the pods 30 and 31 are fully sealed. Also, a front panel (not shown) for the top is provided for additional enclosure of the living space.
It is to be understood that when the pods 30 and 31 are in their stowed condition, they are resting on parallel frame members 32 and 33 positionedadjacent the inside wall surface of the vehicle open bed sides 17 and that these frame members are in fixed based relationship with respect to each other so as to support the pods 30 and 31 and, to be described later, to support the top and its raising mechanism.
In further reference to FIG. 3, it can be seen that each of the berth pods,such as pods 30 for example, includes a peripheral flange 34 that extends about the opening of the pod. This flange engages with the underside of the top and with the supporting means thereof for effecting proper sealing. It is to be noted that the rear of the truck bed is provided withupright support 35 against which the flange 34 will seal at the rear of thecompartment. For clarification, these rear panels have been broken away in FIG. 3 to expose the support frame members 32 and 33.
In FIG. 4, which is a sectional view taken in the direction of arrow 4--4 in FIG. 2, the pod 30 is shown in its stowed position supporting on member32 and a convenient pin or rod 36 carried on the front of the compartment. In FIG. 5, the top of the compartment has been raised and compartment or pod 30 has been moved outwardly thereunder to a position where it rests onthe top of the truck bed integral with side 17. A notch 37 is provided adjacent the flange 34 so that a downwardly depending flange 38 may be positioned within the groove 37 to seal and retain the pod 30 in position.This same downwardly depending flange 38 is also used, as shown in FIG. 4, for securing the pod 30 in its position supported on frame 32 by interposing between the top of the truck bed side 17 and the compartment.
As shown more clearly in FIG. 5, a mechanism is provided for raising and lowering the compartment top which includes a telescoping member 40 at each corner thereof which is supported on the frame members 32 and 33. In FIG. 6, the four supporting telescoping members are illustrated as well astheir interconnection via a cable 41 which operatively moves one portion ofthe telescoping member with respect to the other for raising and lowering of the top. This latter mechanism is illustrated in FIG. 7 and may comprise a plurality of pulleys, such as pulleys 42 and 43 about which thecable 41 is suitable trained. It is to be understood that other mechanisms may be employed if desired. In FIG. 8, a transverse cross-sectional view of the telescoping members are shown wherein one portion thereof is slidably disposed within the other.
Therefore, it can be seen that the novel invention of the present embodiment illustrates and discloses a suitable camper vehicle or accessory vehicle for carrying a plurality of items through which access may be gained by lateral extension of panels 18. The living compartment may include berth pods which are laterally extended so as to increase the size of the vehicle when it is not in its moving condition. Both the top and the sides open up and suitable mechanism is shown for achieving and translating these movements.
While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes andmodifications may be made without departing from this invention in its broader aspects and, therefore, the aim in the appended claims is to coverall such changes and modifications as fall within the true spirit and scopeof this invention. | The camper vehicle disclosed herein provides a self-contained mobile body having a convertible enclosed living compartment defined by laterally extendable berth pods and a raisable top so that in a first roadable configuration, the berth pods and top serve as the opposite sides and top closures and when in a second configuration, the extended berth pods and raised top constitute a pair of berths separated by an interior compartment suitable for standing and moving about. Foldable side covers carried by the top are deployed over the length of each berth panel to enclose the interior compartment areas when in their second configuration. Raising mechanism for the top is employed to support the top and side covers over the berths which include telescoping supports. | 1 |
This is a continuation application of U.S. application Ser. No. 10/769,364, filed Jan. 30, 2004, now U.S. Pat. No. 7,340,865 the entirety of which being incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to adhesive-free, interlocking tiles and, more specifically, to an improved interlock structure for interlocking an assemblage of contiguous floor tiles with uniformly straight edges.
2. Background Discussion
Adhesive-free, interlocking floor tiles are typically molded of substantially resilient, plastic material and utilize interlock elements formed in the tile edges for effecting connections with adjacent, similar tiles. Typically, the interlock elements are pairs of substantially identical alternating projections and slots of substantially dovetail shapes. The projections and slots are supported by the tile edges to effect mating interlocks with inverted, substantially identical slots and projections, respectively, on other tiles to effect a mating interference fit between contiguous tiles of an assemblage, such as, an assemblage of floor tiles.
The projections serve as the male interlock elements and are typically dovetailed shaped; that is, shaped as truncated triangles with rounded corners in plan view and disposed in alignment along each tile. The male projections are alternately spaced by contiguous slots of substantially the same size and shape as the male projections, but inverted to form the female interlocking elements. Typically therefore, the slots are of identical dovetail shape and those on at least two exposed elements support edges of the tile are joined at right angles. The slots extend completely through these edges to provide female counterparts to the male elements. Interlocking of contiguous floor tiles on-site is effected by vertically aligning the male and female interlock elements of one tile with respective inverted female and male interlock elements of contiguous tiles and then driving the interlocks into resilient interference engagements by means of, for example, a mallet. The integrated installation, when thusly installed over flooring substrates, such as concrete or plywood, requires no adhesives or fasteners, and is therefore often referred to as “adhesive-free.” The male-female element pairs form one set each of the interlock structures disposed along the tile edges so that there is a series of contiguous pairs of projections and slots joined by a common dovetail-shaped sidewall.
For certain floor tile applications it is preferred that the tiles have four edges with one pair thereof joining at right angles to provide one corner of the tile and two uniformly solid, straight edges which define two of the four or more square or rectangular side edges of a multi-sided tile, depending on the particular overall tile shape. The pair of solid edge portions serves as straight, overlying support edges for downwardly facing interlock elements when the tile is installed horizontally. The edges have top surfaces as flush extensions of the top surface of the tile body and provide flat, top surfaces with a pair of solid, straight top edges, thereby simulating a conventional ceramic tile assemblage with linear grout lines or wood flooring with grooves and flush, coplanar top surfaces. An oppositely disposed, and second, pair of edges intersect at right angles to form a second opposite corner of the tile. The second pair of edges are likewise provided with a sequence of male-female interlocks defined by sidewalls which extend completely through the tile edges perpendicular to the plane of the tile to mate with the downwardly-projecting respective female and male interlocks of contiguous, substantially identical tiles. Examples of tiles having such interlock arrangements are disclosed by U.S. Pat. No. 4,287,693 issued on Sep. 8, 1981 to R. E. Collette; U.S. Pat. No. 6,526,705, issued on Mar. 4, 2003 to K. M. MacDonald; and, U.S. patent application Ser. No. 09/884,638, filed Jun. 19, 2001 by T. E. Ricciardelli and assigned to the same assignee as the present invention; all of the references referred to above being incorporated by reference herein and made part hereof.
The extent to which each essentially identical pair of interlock elements can effectively function to prevent tile separations during usage is a function of tile composition and the design of the interlocks with various considerations as to tile resilience and the extent of surface area available for inter-mating surface-to-surface engagement between interlocks, and other relevant factors known to those in the art. Thus, with certain of the prior art interlock structures, the two sides of the tile opposite those with solid edge portions utilize the full tile edge thickness for at least the female cavity sidewalls by molding dovetail slots as through-slots into the tile edges. The resulting tile has a pair of top linear edge portions and a pair of opposite or bottom edge portions with alternating non-linear or undulating edges. Advantageously, the latter may be hidden from view after tile assemblage by the overlying straight and solid top edge portions of contiguous tiles, and therefore, the top surfaces of the final tile assemblages have the desired uniformly straight edge lines and flush, top edge surfaces.
For a given thickness of tile, the pair of flush solid support edges forming the periphery of the top surface account for a portion of the overall tile thickness and consequently reduce the surface areas available for mating engagements between the identical pairs of interlock elements. This is because the female cavities have a reduced depth as a result of being dead-ended on-their underlying solid support edges. The male projections are also limited in height because they cannot extend beyond the planes of the top or bottom surfaces of the tile. As a result, the surface areas available to effect inter-element mating engagements is reduced, which is disadvantageous from a connective integrity standpoint. Conversely, this advantageously results in a reduction in the impact forces required to drive the downwardly-facing interlocks on the top tile edges into mating engagements with upwardly-facing interlocks of adjoining tiles, and consequently reduces the effort required for on-site tile installation.
It would be advantageous to provide a generally planar tile with multiple sides and a top surface having an underlying interlock structure that is adapted to facilitate on-site assemblage and removal of individual tiles with matable interlock structures on contiguous tiles, and yet is resistant to separation of the assemblage during usage.
An embodiment of this invention is to provide an interlocking tile with planar top and bottom surfaces and at least two linear edges extending at right angles to one another having different sets of interlock elements underlying the top edge surfaces which are specifically designed to facilitate on-site installation and removal and replacement, if required, of individual tiles without significantly degrading the resistance to tile edge separations during usage.
Yet another embodiment is to provide an adhesive-free tile assemblage with an interlock structure comprised of multiple pairs of differently constructed interlocks providing acceptable connective interlock integrity while facilitating the ease by which on-site installation assemblage and replacement of individual tiles can be effected with mating tiles having substantially identical, inverted interlock structures thereon.
Yet another embodiment is to provide an edge interlock system for a resilient tile that facilitates the initial connections and aligned orientations between the interlocks of that tile and the interlocks of similarly constructed contiguous tiles.
SUMMARY OF THE INVENTION
These embodiments are achieved by the instant invention which provides a multi-sided, interlocking tile with a corresponding multi-sided, substantially planar central portion with first, second, third and fourth elongated interlock element support edges disposed in end-wise relationship and cantilevered from different sides of the central portion. The inner edge portions of the support edges are formed integral with the central portion and extend laterally outwardly therefrom with the free, outer edge portions thereof defining the tile periphery. The first and second interlock support edges have longitudinal axes intersecting at substantially right angles to provide a first pair of adjoining interlock support edges on two sides of the central portion having interlock support surfaces that face toward the plane of the top tile surface or “upwardly.” Similarly, the third and fourth interlock support edges intersect at right angles to provide a second pair of adjoining interlock support edges on another two sides of the central tile portion having interlock support surfaces that face toward the plane of the bottom tile surface or “downwardly.” With this inverted arrangement of interlock support edges, a flat, uniformly solid, top tile, surface is available for the application of a square cornered laminate decorative and/or wear resistant layer applied during or after the tile molding process.
There are series of two sets each of different, male-female interlock elements on each support edge and the two sets are disposed in longitudinal alignment and project from one surface of each support edge. The two sets of interlock elements are joined by a common sidewall that traverses the surface of the underlying support edge from substantially one end to the other. The sidewalls on the first pair of support edges project upwardly and the sidewalls on the second pair of support edges project downwardly. Both sets of the interlock elements are comprised of male walled structures; one of the structures being a lug-like element and the other being a section of a rib-like element with substantially parallel inner and outer spaced-apart sidewalls. The lug and laterally opposite outer sidewall of a rib section are laterally spaced to form an essentially U-shaped channel therebetween that bottoms on its respective support edge surface. The channel forms a female interlock portion for the first of the two interlock sets, whereas the adjacent lug forms the male interlock portion of that first interlock set.
The inner sidewall of the rib section forms an open-ended cavity also bottoming on its enclosed support edge surface and this cavity forms the female interlock element for the second interlock set. Each of the rib sections projecting from its respective support surface is shaped to form the male interlock element for the second interlock set. The male and female elements of the two sets are shaped and sized as identical inverted counterparts of one another, so that adjacent tiles having substantially identical inverted first and second interlock sets can mesh and be matingly secured together without use of adhesives. The open-ended design of the interlocks and the tile resilience enables an installer to more readily replace individual tiles of the assembly by simply picking up one corner of the tile to effect initial separation between the interlocks. Additionally, the interlock sets on the corner ends of support edges are designed to mesh with less applied pressure and greater tolerances to initial misalignment than that required for other prior art sets of interlocks, thereby facilitating the initial interconnecting and alignments with similar interlocks of contiguous tiles and any subsequent removal of individual tiles.
The invention will now be described in more detail with reference to the accompanying drawings.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top plan view of a tile with edge interlocks constructed in accordance with the instant invention;
FIG. 2 is a bottom plan view of the tile shown in FIG. 1 ;
FIG. 3 is an isometric perspective of the left-hand corner of the tile shown in FIG. 1 ;
FIG. 3A is an enlargement of the right-hand corner of FIG. 3 , delineated by dash lines in FIG. 3 ;
FIG. 4 is an isometric perspective of the right-hand corner of the tile shown in FIG. 2 ; and,
FIG. 4A is an enlargement of the right-hand corner of FIG. 4 , delineated by dash lines in FIG. 4 and,
FIG. 5 is side view of a portion of the edge of an embodiment of the tile with a decorative and/or wear-resistant top surface thereon.
DETAILED DESCRIPTION
With reference to the drawings, FIG. 1 shows a top plan view of a tile 10 , constructed in accordance with this invention. The tile 10 is illustrated as having a substantially squared-shaped upper or top planar surface 13 and a lower or bottom planar surface 14 of substantially the same dimensions, the planes of the two surfaces 13 and 14 being essentially parallel and defining therebetween the “vertical” or perpendicular thickness of the tile 10 . The surfaces 13 and 14 are shown to be essentially of square shape, but may have other geometric shapes as well, for example rectangular, as disclosed in co-pending U.S. patent application Ser. No. 09/884,638, referred to hereinabove. Preferably, the top edges of the tile are uniformly solid and linear so that the tiles provide straight, solid edges with right-angled corners. The surfaces of the bottom 14 may be embossed or otherwise patterned (not shown) for slip-resistance enhancement.
The tile 10 is preferably composed of substantially resilient materials, such as; polyvinyl chloride (PVC), polypropylene, polyethylene, and natural or synthetic rubber or mixtures thereof that provide the molded products with a somewhat cushiony surface desirable for floor coverings and the substantially resilient interlock structures desirable for tight-fitting, essentially resilient interlocks. Advantageously, the tile 10 may be composed of recycled waste carpet scraps, as disclosed in U.S. Pat. No. 6,306,318 issued on Oct. 23, 2001, and assigned to the same assignee as the instant invention. As disclosed therein, a matrix of granulated waste polymeric carpet backing and carpet fibers and a suitable plasticizer, after being subjected to high heat and compressive forces in an injection molding machine, will produce a molded tile of PVC with embedded carpet fibers. As illustrated in FIG. 5 , to enhance the aesthetic appearance of a floor tile assemblage, a variety of decorative polymeric-based sheets, such as decorative vinyl sheets, may be laminated to the top surface of the tile 10 to provide a decorative top layer 11 to the tile 10 . The layer 11 may be covered by transparent wear-resistant layer, not shown, if required.
The tile 10 is shown in plan view in FIGS. 1 and 2 with a generally square-shaped central portion 12 of basic tile body thickness with two pairs of interlock edges; a first one of said pairs designated by numerals 14 A and 14 B in FIGS. 1 and 3 is comprised of two substantially identical elongated edge strips 19 A and 19 B, respectively, having substantially rectangular cross-sectional shapes. The strips 19 A, 19 B have respective flat top surfaces 20 A, 20 B, FIGS. 3 and 3A , that support interlock elements and face upwardly in the direction of a plane containing the top tile surface 13 . A pair of opposite bottom surfaces 14 A, 14 B, respectively, FIGS. 2 and 4 , extend as flush border edge continuations of the central region 12 of the bottom tile surface 14 . The longitudinal axes of the strips 19 A, 19 B, FIG. 3 , intersect at right angles to define one of the right-angled corners 24 of the tile 10 , and the strip surfaces 20 A, 20 B typically face upwardly when the tile is mounted with its bottom surface 14 against a floor substrate. The outermost first pair of tile 10 edges, FIG. 3 , is uniformly solid and substantially straight edges 22 A and 22 B, respectively, simulating linear grout or groove lines which typically result when conventional ceramic tiles or wood flooring planks are assembled in abutting relationships.
As best seen in FIGS. 3 and 3A , the strips 19 A and 19 B have a vertical thickness of approximately one-quarter the corresponding total thickness dimension of the tile 10 , including any additional decorative or wear layers 11 applied thereto. Typically, the portion 12 is about 15-20 inches and more specifically, about 17 inches on each side and the tile thickness with a decorative layer 11 is about 0.125-0.5 inch and more specifically, about 0.25 inch; although such dimension will vary depending upon the particular installation for weights, flexibility, and wear resistant requirements, as apparent. Flexibly cantilevered from their corresponding outer edges 21 A, 21 B of the central tile portion 12 the strips 19 A, 19 B intersect at right angles with those edges to form downwardly stepped corner edges at 21 A and 21 B, respectively, that extend parallel to support edges 20 A and 20 B, respectively, and intersect at right angles to one another at the left-hand corner of tile 10 , FIG. 3 . Typically, the strips 19 A and 19 B have exemplary width dimensions of about 0.5 inch to 1.0 inch and more specifically, about 0.75 inch. The dimensions of the strips are a function of the overall dimensions of the tile 10 and the size of the interlock elements molded into the strips. With the exemplary dimensions disclosed above, the top surface 13 has approximately a 15-20 inch border and more specifically about a 17.75 inch border edge. The depth or thickness of the edges 21 A, 21 B of the strips 19 A, 19 B respectively contiguous to and abutting the interlocks is determined by the vertical spacing required between the plane of top surface 13 and the interlock engaging surfaces of the interlock structures to provide flush edges with those of similar adjoining tiles. As will be apparent from FIG. 5 , for a predetermined height of interlock projections and depth of adjacent cavities described in greater detail hereinafter, this vertical spacing will be incrementally increased in the event additional single or composite material compatible and flexible layers 11 are applied by heat bonding or adhesives to the top tile surface by the amount that such layer or layers incrementally increase the thickness of the tile. To maintain a predetermined maximum tile thickness for desired flexibility, the thickness of the strips 19 A, 19 B may be reduced by an increment substantially equal to the height increase attributable to the addition of the layers 11 . Typically the layers 11 will have a thickness ranging from 0.002 inch to 0.004 inch in total thickness. Typically, the top layer 11 comprises a layer of 0.004 to 0.020 inch of flexible PVC to which may be applied a clear coating of 0.004 to 0.007 inch of either polyurethane, melamine or melamine in mixture with aluminum oxide (Al.sub.2O.sub.3) or similar material.
The second pair of interlock support edges, designated 30 A and 30 B in FIGS. 2 , 4 and 4 A, are also comprised of elongated strips 31 A, 31 B of rectangular cross-section and of substantially identical size and shape as the strips 19 A, 19 B. Strips 31 A and 31 B, intersect at right angles to form a second tile corner 34 opposite the corner 24 . The strips 31 A, 31 B extend from, and as continuations of the central portion 12 of top tile surface 13 to provide top border edges coplanar with the plane of the top surface 13 of the central region 10 A. The strips 31 A, 31 B are also cantilevered from edge portions of their respective outer adjoining edges of the bottom central portion 10 A and when installed on a substrate are stepped downwardly at right angles thereto to provide the perpendicular or vertical spacing for flush abutments with similar adjoining tiles with their inverted interlocks facing upwardly and their interlock support edges underlying the strips 31 A, 31 B for mating connections therebetween. The strips 31 A, 31 B, respectively, have flat, interlock elements support surfaces 40 A and 40 B, FIGS. 4 and 4A , facing the plane containing the bottom tile surface 14 , and hence, are downwardly facing when tile 10 is installed as a floor covering with the bottom surface 14 overlying the substrate. The width of the strips 31 A, 31 B is substantially the same throughout and substantially the same as that of the strips 19 A, 19 B. The ends of the strips 31 A, 31 B opposite the corner 34 , FIGS. 1 and 2 , may be spaced from the adjacent ends of the strips 19 A, 19 B, respectively, typically by the width of a strip to provide greater flexibility to both adjacent ends as indicated by numerals 35 A and 35 B in FIG. 2 . As seen in FIGS. 3A and 4A the strips 19 A and 19 B are substantially mirror images of those on the strips 31 A and 31 B, respectively, with a pair of interlocks at each end of the strips being especially designed to provide greater mating capability between superimposed interlocks than the intermediate sets of interlocks, as discussed hereinafter.
With reference to FIGS. 1 , 3 and 3 A, projecting upwardly from each of the surfaces 20 A, 20 B of their respective strips 19 A, 19 B are a series of longitudinally-aligned first and second sets of interlock elements molded into the tile, each set being comprised essentially of a differently designed pair of male and female structural types of interlock elements.
The first interlock set of the series, FIG. 3A , disposed along the mid-section of their supporting strip is comprised of a projecting male lug 40 and an adjacent female channel 42 ; the lug 40 , as viewed in plan, being shaped substantially as an equilateral triangle formed of adjoining sidewalls 40 - 1 , 40 - 2 and 40 - 3 with rounded corners and a flat upper end surface 40 - 4 . The lugs 40 typically project from their respective strip surfaces 20 A and 20 B a distance approximately equal to one-half the total thickness of the tile 10 , leaving a vertical space between their free end surfaces 40 - 4 and the top surface of the tile 10 substantially the vertical thickness of their respective corner edges 21 A and 21 B. The vertical spacing is substantially equal to the support edge thickness of other contiguous tiles substantially identical to the tile 10 with substantially identical interlocks plus any decorative and/or wear resistant layers 11 thereon. Thus, abutting tiles will meet with flush top surfaces and joint lines when edge-connected together by their respective mating interlocks. The end surfaces 40 - 4 , FIG. 3A , of at least one set of lugs 40 may have longitudinal, air venting slots 40 - 5 therein to facilitate the mold release of the tile 10 from, for example, an injection molding machine.
The sidewalls 40 - 1 , 40 - 2 and 40 - 3 of the lugs 40 and adjoining portions of their respective strip surfaces 20 A, 20 B, FIG. 3A , from one-half of the right-angled wall structure for a channel 40 ; the other half being formed by the surfaces 20 A, 20 B and the laterally opposed sidewalls of tandem connected rib sections 50 - 1 of a continuous male rib wall 50 which traverses the width and extends longitudinally for the major intermediate portion of the length of their respective tile support edges 21 A, 21 B, 30 A and 30 B. Each of the male rib sidewall sections 50 - 1 projects from its respective support edge surface 20 A, 20 B, FIGS. 3 and 3A , the same amount as the lug 40 and has an inner sidewall section 50 - 2 spaced laterally from and extending substantially parallel to an opposite one of the outer sidewall sections 50 - 1 . Thus, each traversing section of the wall 50 has a substantially rectangular cross-sectional shape for mating with U-shaped channels such as channels 42 . The two rib sections 50 - 1 define the two legs of each triangular locking structure and depend from a basewall section 50 - 3 , at approximately a 60-degree interior angle. The basewall sections 50 - 3 is molded flush with the corner edges 21 A, 21 B of the central region 10 A, thereby completing the cavity 60 enclosure.
Each male lug 40 , FIG. 3A , is disposed substantially equal distances from its laterally opposed outer sidewalls of sections 50 - 1 and substantially the same distances from their respective tile edges 22 A, 22 B. Thus, each male lug 40 is surrounded on three sides by a corresponding female channel 42 of slightly greater width than the width of laterally opposed rib wall sections 50 - 1 so as to tightly mate with similar but inverted rib wall sections of a contiguous tile. The inner sidewalls 50 - 2 of each rib 50 are also shaped in plan view as an equilateral triangle having rounded interior corners so as to have a substantially identical size and shape as a corresponding inverted lug 40 . The resulting open-ended cavities 60 , FIG. 3A , bottoming on their respective enclosed areas of the surfaces, 20 A, 20 B, have just slightly larger mating interiors than the lug 40 so as to receive inverted lug projections of adjoining tiles with an essentially interference fit.
The outer sidewalls of sections 50 - 1 of the ribs 50 , FIGS. 3 and 3A , are rounded adjacent the tile edges 22 A, 22 B and otherwise substantially follow the curvature of the lug 40 sidewalls 40 - 2 , 40 - 3 to facilitate mating therebetween. The spacing between the edges 22 A, 22 B and their laterally adjacent sidewalls 40 - 1 of lugs 40 is substantially the width of the channel 42 . Thus, each inverted one of the ribs 50 can be accommodated in a corresponding female channel 42 and since each inverted lug 40 can be accommodated in a rib cavity 60 , the second set of male-female interlocks is formed by a male rib section 50 - 1 and its adjoining female cavity 60 . As will be apparent, the rib 50 follows a substantially semisoidal course a substantial length of each support strip 19 A, 19 B. The rib merges into the central portion 10 adjacent the tile corners, and thus the two endmost lugs 40 A, 40 B do not have an intervening rib section.
The lugs 40 A and 40 B are inverted relative to one another and are laterally spaced by a channel section 42 A. The sections 42 A are typically designed to be somewhat wider than the intermediate channels 42 to correspond with the greater width of their respective vertically aligned inverted male rib sections 50 A, 50 B of greater width. This is done to assist an installer in making alignments and the initial engagements between the corners of contiguous tiles by providing wider interlocks for initial meshing. Typically, the end rib sections 50 A and 50 B encircling a respective one of the endmost cavities 61 and 62 are typically about twice as wide as the intermediate ribs 50 . Because the rib sections 50 A and 50 B are about twice as wide as the intervening rib sections 50 readily mesh with the correspondingly wider channels 42 A and 42 B by the installer aligning and then simply pressing and corner 24 or 34 of tile 10 with its rib sections 50 A and 50 B and cavities 61 and 62 facing downwards into the upwardly facing lugs 40 A, 40 B and wider channels 42 A, 42 B, respectively, of the inverted corresponding corner of a second and substantially identical tile. Once these initial engagements are made at the superimposed tile corners the remaining, intermediate interlocks of the overlapping tiles will be drawn into generally aligned in proper meshing relationships and their relatively tighter intermediate interlock engagements requiring greater forces may be affected by the installer with the use of a tool, such as a mallet. The wider and open-ended design of this initial pair of interlocks facilitates the ease by which individual tiles may be removed from the assemblage by the installer simply raising one corner of the tile to be removed to initiate separation of the contiguous interlocks.
The particular tile described herein is the preferred embodiment of the instant invention but it should be understood that modifications may be made therein without departing from the scope of the invention as defined in the following appended claims. This specification has disclosed all foreseeable equivalents. Terms such as “generally” and “substantially” and the like, as used herein, are to be accorded their ordinary and customary meaning. | A polymeric interlocking tile for an adhesive-free assemblage with adjacent tiles having substantially similar, but inverted, edge interlocks thereon. The interlocks on each edge of a tile include a row of first and second sets of male-female types of alternating interlocks. The first interlock set includes a male lug projection having sidewalls forming one sidewall of a channel of U-shaped cross-section. The channel forms a female interlock cavity for the first set. The second interlock set is contiguous to the first set and includes a male projecting rib having two parallel sidewalls, one sidewall faces the edge and forms an opposite sidewall of the channel and an opposite, inwardly facing sidewall forms an enclosure for a second female cavity of the next set. At the opposite ends of each interlock row, the U-shaped channel sidewalls are wider to facilitate an initial interlock meshing between contiguous tiles of the assemblage. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority from Argentina's Instituto Nacional de la Propiedad Industrial, patent application # 2013010338 1 , titled “CERRAMIENTO MULTIFUNCIONAL” (Multifunctional Enclosure, in English), filed on Sep. 20 , 2013 , based on the Paris Convention for the Protection of Industrial Property, subscribed by the Argentine Republic and the United States of America, the entire contents of which are herein incorporated by reference.
FEDERALLY SPONSORED RESEARCH
[0002] Not Applicable
SEQUENCE LISTING OR PROGRAM
[0003] Not Applicable
REFERENCES CITED
[0004] EP0253411A2
[0005] ES2063610A2
[0006] U.S. Pat. No. 3,845,591
[0007] U.S. Pat. No. 6,604,327
[0008] WO02072969A1
BACKGROUND OF INVENTION
[0009] 1. Field of the Invention
[0010] The present invention refers to a “MULTIFUNCTIONAL ENCLOSURE”, appropriate for any surface to be enclosed, both external and internal, in which it comprises a cross-linked structure containing a set of profiles that fits in the field of telescopic retractable roof structures, in particular structures composed primarily of profiles used in the field of architecture and construction.
[0011] 2. Background
[0012] Traditionally enclosure systems may be classified as those suitable for closed areas and outdoor areas. The first group comprises those enclosures that permit use and enjoyment every day of the year, regardless of weather conditions. The second group refers to all those enclosures that open wholly or partly to the open air. To this second group, the present invention is intended.
[0013] To make better use of the outdoor places, various enclosure systems were developed, generally consisting of roofs with partial openings that can be opened or closed in the manner of windows, fully or partially, that may be opened when weather conditions are favorable.
[0014] To this end, various systems have been developed and used, including:
Protective canvas or awnings; Tents, made of various materials such as canvas or plastic, with rigid or inflatable support structures (the whole tent is inflated, which requires monitoring its air leakage with the consequent continuous energy expenditure, or only the supporting structure is inflatable); Removable modules removable at will, which must be completely dismantled when not in use. Retractable module roofs that result in visible retracted structures at the ends of the area to be covered or have the need for providing a large enclosed space to hide them. Sliding covers that allow for a limited opening, always leaving a covered portion, since the entire structure (walls and/or roof) moves in modules, which are inserted one inside the other, to occupy one end portion thereof; being that in some cases the walls are fixed and only the corresponding portion of the roof moves leaving always a covered airspace.
[0020] All these solutions generally do not resolve the problem of dealing with the weight of the modules. Most sliding modules are difficult to move to a desired position because they employ mechanical means, pulleys and chains, which are used to manually move the modules. If the modules need to be moved by pushing there is a risk that they may lock.
[0021] As for pavilion type enclosures, there are a variety of models, fixed or telescopic, made of various materials, such as canvas or metal. Telescopic enclosures may be retracted and still occupy a fifth or a sixth of its original size.
[0022] In regards to the perimeter structures that support a sliding roof, they generally have multiple drawbacks. These structures have to bear the weight coupled with sliding modules' movements, thus they present a variety of construction issues such as tension, vibration, and possible deformation from buckling, all issues that require expensive systems because of materials used, resulting in increased weight and cost of the entire structure.
[0023] Enclosure systems that use rail tracks to displace themselves always have some possibility of locking on the tracks.
[0024] It must be noted that hereinafter when referring to a structure, module, or enclosure that it is closed, it implies that the modules are in position to total coverage of the surface, and when it is said to be open it implies that the modules are fully stored in underground chambers releasing all the space above ground.
[0025] The proposed invention solves all aforementioned problems, because there are no bearings circulating over rails and especially because once the structure is fully retracted it is hidden from view, freeing the space previously covered.
[0026] The process of opening and closing the enclosure may be effected mechanically. The use of counterweights for pivoting the structures makes manual operation of the enclosure possible. The simplicity of operation eliminates the need for trained personnel for their handling. It also allows for usage of the enclosure as often as desired.
[0027] Another possibility is the opening and closing of the enclosure by using a motor and a programmable computer that allows for scheduling and pre-defined frequencies of operation.
[0028] All the above mentioned problems can be solved by the present invention, whose opening and closing is accomplished telescopically, and may be used to cover areas such as: swimming pools, sports fields, greenhouses, gardens, patios, work areas, isolation areas, parking lots, and similar.
[0029] The following prior art is known to the inventor.
[0030] Spanish Patent ES2,063,610, discloses a fixed circular lattice structure, over which layered structures shaped as wedges are affixed to its perimeter, and pivot on it and lean to one side or the other causing the partial opening of the enclosure or its total closure. The problems presented by this invention are:
The segments tend to jam if they are not perfectly synchronized in their movement; Space around the enclosed area does become completely free; a portion of the structure is visible on the ground; The deformation of the segments due to temperature variations and use increases the chances of jamming; Its does not allow for placement of an enclosure in a small area.
[0035] U.S. Pat. No. 3,845,591 discloses a telescopic enclosure that extends horizontally. It consists of segments of different sizes such that upon retraction each segment is contained underneath the previous segment. The structure moves over side rails. The problems presented are:
The segments tend to jam while circulating over rails; Rails must be periodically maintained to prevent the bearings from locking; Not all space is liberated upon opening the enclosure, part of the structure remains visible and above ground; The structure is usable to enclose small areas since its configuration limits its elements to exceed certain size because of weight and maneuverability.
[0040] WIPO application WO0/2072969 discloses a telescopic rectangular enclosure that can be extended horizontally. It consists of segments of different sizes that may be retracted and stored below the previous segment. The segments move by rolling over side rails on the floor. The ends of the enclosure may be closed by means of a retractable semicircular dome formed by U-shaped modules united together at their pivoting points. The problems presented by this invention are:
The modules in movement tend to lock while circulating on the rails; Space above ground is not free, part of the structure remains visible; The structure is usable to enclose small areas.
[0044] U.S. Pat. No. 6,604,327 B1 discloses a telescopic enclosure that can extend horizontally. It consists of segments of different sizes that may be retracted and stored below the previous segment. The segments move by rolling over wheels over the floor. The problems presented by this invention are:
The modules in movement tend to lock easily since there is no guide to keep all wheels aligned; Space above ground is not free, part of the structure remains visible; Applicable only to small areas.
[0048] European Patent EP 0253411 discloses several enclosure options. Focusing on a relevant option, a telescopic rectangular enclosure may be extended horizontally and consist of segments of different sizes that may be retracted and stored below the previous segment. The structure circulates over wheels and its ends are retractable, closable by semicircular dome modules formed by inverted U shape wedges. The problems presented by this invention are:
The modules tend to lock while circulating on the rails; Space above ground is not free; part of the structure remains visible; The structure is usable to enclose small areas.
SUMMARY OF THE INVENTION
[0052] The object of the present invention is a to provide for a multifunctional enclosure, for covering outdoor and indoor areas, which comprises a set of components operatively linked together, forming an enclosure that can be retracted completely and be hidden out of sight; having features that solve the previously mentioned problems.
When the enclosure is retracted, it frees completely the area above ground as the entire structure is stored below ground level and out of sight; When the enclosure is deployed it covers the entire desired area, being suitable for large areas; The component modules do not travel over the ground, either on rails or wheels, rather the modules pivot on their axis, thereby eliminating the inconvenience caused by wear and jamming of wheels caused by the horizontal displacement of the modules; Module's movement is not hindered by obstacles as bearings maintain separation between modules and ensure smooth and fluid movements; Each half of the enclosure pivots on its own axis, therefore the total load is divided; It allows for the placing of openings, such as access doors and windows; The enclosure modular structure makes it ideal for manufacturing, transport, and installation at different locations.
[0060] The inventive enclosure is composed of a series of modules arranged in two parallel halves facing each other. Each one of the modules has a section of parabolic profile shape and the length of the area to be covered, and it is connected to an axis upon it rotates.
[0061] The number of modules in each half of the enclosure can vary according to the dimensions of the area to be covered. All modules in each half share the same horizontal axis; both axes are located below ground level, in parallel to each other.
[0062] The size of the modules varies from one another due to construction requirements, such as the location of an access door or opening, that requires certain modules to have an angle greater than others, whereby the wedge of the modules of each half does not always have the same angle as the opposite module. This means that each half module has different length and diameter that range from larger on the outside to smaller on the inside, also one side may have more modules than the other side.
[0063] The radius and length difference between modules is such that allows for a proper fit between them to open and close, while determining the clearance or gap light needed to allow for deformations provided in each case and the smooth functioning without trouble.
[0064] The rotational movement of the modules around their axes allows for a proper fit between each other in the perimetral underground housing, reducing the space required and at the same time offering the possibility for the total deployment of the structure to the deployed position.
[0065] Each module consists of two wedge-shaped panels, one in front and one on the rear, connected by its wider end (the side opposite the axis) through multiple beams, two of which connect the inside corners facing each other (hereinafter upper and lower beams) and the rest connecting the middle part (hereinafter middle beam) giving it structural stiffness and support to the laminar material that will be used to close the resulting intermediate spaces. On the inner facing sides of the beams, multiple perpendicular ribs are affixed thereto and spaced at equal distances, and upon which the laminar material mentioned above is interspersed, these ribs converging on at least one axis associated with a motor.
[0066] Each panel shaped wedge will consist of two radial profiles or studs attached at one end (the apex of the wedge), with another profile that will unite them at the other end giving the characteristic wedge shape to the whole module and can present in its middle part a section of arch or curved profile affixed to the internal face of the studs. The radial profile or attack stud of each module, which is the one closer to the middle of the deck to be deployed, or that remains at ground level when retracted, may present an extension to the opposite side of the axis to facilitate the rotation of the panel about its axis on the following ways:
By placing counterweights on the extension. These counterweights are located interspersed and sized not to interfere with their movement or with other modules in the opposite side; or by applying the necessary force to the end thereof to the lever advantage (such as by steel cables, gears, mechanical, elastic, or hydraulic devices).
[0069] By using a counterweight extension, it allows for the rotation of the modules by applying a small force on said extensions, which requires using a smaller motor and therefore less energy or the possibility to use manual force.
[0070] A bracket may be affixed to some joints between two profiles to ensure its squareness and to further strengthen the joints and the whole structure. Optionally, the brackets may be placed on internal corners or only on those unions that bear a higher load, to reduce the overall weight of the module.
[0071] Near the apex of the wedge-shaped panels is the opening where the axis is located. The external module, hereinafter drag module, may rest at 90 degrees to the ground, when in its deployed position, will be firmly fixed to said axis. The remaining modules will turn freely around said axis, linked to it through bearings to reduce the friction, so that turning the axis will turn the drag module and the module will drag the next module by a pulling action exerted by an abutment flange or stop. The flange runs through the longitudinal extension of the module and is disposed on the inner side of each lower beam (except for the lower module that does not having such a flange). The flange abuts against another like flange located on the outer side of each upper beam (except for the upper module that does not have such a flange).
[0072] The lower module that remains in contact with the ground surface may contain apertures, such as a door or a window.
[0073] The modules, which connect with each other in the deployed position, form a half cylinder that conforms the roof and sides of an enclosure, and the semicircular sections of each module complete the front and back faces of semicircular cover.
[0074] Each module is formed by cross-linking said beams and ribs with the resulting spaces in between them filled with foil material, either translucent or opaque.
[0075] Since modules are loaded on the same horizontal axis, each one can be moved from an angle that positions it below the ground line within underground housing (open or rest position when the cover is not in use) to a deployed position, in which the modules are located so that they connect to each other through their upper and/or lower edges by flanges or tabs above mentioned, completing each half an arch of 90 degrees.
[0076] As mentioned, there are three attack/contact beams in each module, that are positioned upside when the structure is opened.
[0077] The beams corresponding to the profile of the upper module are designed and positioned so as to ensure the tightness of the enclosure when, in the deployed position, makes contact with the other module. The beams corresponding to the profiles of the remaining modules are designed and positioned in such a way to ensure the tightness of the enclosure when deployed and to make contact with the studs and lower beams of the adjacent upper module through the said flange.
[0078] The design of the joints between different modules and the semicircular shaped enclosure guarantees a free water runoff adjacent to the lower module and the tightness of the joints of the profiles with laminar sealing material. In turn, the upper module has a slanting in the last part (the top) that facilitates the disposal of water, snow, ice, or other liquids.
[0079] The process of opening and closing the enclosure may be performed mechanically with the help of motors, but the use of counterweights for pivotal structures makes opening manually feasible. This simplicity of operation eliminates the need for trained personnel with special skills. It also allows the utilization as frequent as desired.
[0080] The deployment of the enclosure may be performed with the help of one or two synchronized motors, pulleys, or hydraulic pistons applied to the modules or beams.
[0081] If motors are used, the opening and closing of the structure may be automated, so it is possible to schedule and pre-defined operating frequencies.
[0082] In order to reduce structural stress caused by the operation of the enclosure, it is possible to apply forces to the end of the extensions designed to partially offset the weight of the modules, which can be static, linear, hydraulic, spring loaded, mechanical, or elastic, such as counterweights.
[0083] In a preferred embodiment shown, counterweights consist of a radial extension to the main radius of each module, with the radial development required (in the opposite direction to the module).
[0084] The dimensions of the counterweights, as shown in the embodiment, may vary depending on the soil type and the topography since it will determine the depth of the excavation.
[0085] The axes that serve for rotation of the modules (and corresponding counterweights) include bearings supported by a rigid structure affixed on a firm base on each side at the ends of each drag module.
[0086] Access to the interior of the structure, when deployed, is made through one or more openings located on the lower module of one or both principal sections.
[0087] In order to reduce any rubbing or friction, avoid obstacles, and maintain the necessary gap between the modules for the smooth running of the enclosure, bearings are disposed on the inner and outer faces.
[0088] The underground storage or housing is located on the perimeter of the area to be covered. It consists of a compartment closed on all sides except the necessary opening gap for the entry and exit of the modules and the maintenance access that may be required.
[0089] The sealing, total or partial, of the housing is achieved with the use of a perimeter rain cover and collector. In the embodiment, both elements, rain cover and rain collector, are part of the movable structure with the first connected to the upper beam of the main module and the second connected to the lower beam of the module, this greatly simplifies the operation of the structure.
[0090] In the case of covering large areas, a series of arches, fixed or telescopic, may be added to the enclosure structure to provide the necessary support while matching the curvature of the modules. For this, each module in the underside of the beams may have bearings to match and position the supporting arches used.
BRIEF DESCRIPTION OF THE DRAWINGS
[0091] FIG. 1 is a perspective view of the enclosure in the closed position.
[0092] FIG. 2 is a perspective view of the enclosure in open condition.
[0093] FIG. 3 is a top view of the enclosure in the closed condition.
[0094] FIGS. 4A, 4B, 4C, and 4D are a sequence of perspective views of the operational condition of the enclosure.
[0095] FIG. 5 is a longitudinal cross sectional view through the middle of the enclosure in a closed position, where the modules making up one half of the enclosure may be observed.
[0096] FIG. 6 is a cross sectional view of the enclosure in closed position and of the underground storage.
[0097] FIG. 7 is a view of a cross section of the enclosure retracted inside the lateral underground storage.
[0098] FIG. 8 is a top view of the retracted enclosure with the covers and the upper slabs of the underground storage removed.
[0099] FIG. 9 is a schematic view of the modules in cross section of an alternative enclosure of four modules where the arrangement of the modules can be seen in closed position.
[0100] FIG. 10 is a schematic view of the modules in cross section of an alternative enclosure of four modules where the arrangement of modules can be seen in open position.
[0101] FIG. 11 is a schematic view of the modules in cross section of an alternative enclosure of eight modules where the arrangement of modules can be seen in closed position.
[0102] FIG. 12 is a schematic view of the modules in cross section of an alternative enclosure of eight modules where the arrangement of modules can be seen in open position.
[0103] FIG. 13 is a top schematic view of an horizontal section of the back panels of the modules showing the location and of the axial profiles related modules being in open position.
[0104] FIG. 14 is an internal cross-sectional view of the upper module.
[0105] FIG. 15 is a cross sectional view of the front panel of the upper module.
[0106] FIG. 16 is a cross sectional view of the middle module.
[0107] FIG. 17 is a cross sectional view of the front of the middle module.
[0108] FIG. 18 is an internal cross sectional view of the lower module.
[0109] FIG. 19 is a cross sectional view of the lower front panel module.
[0110] FIG. 20 is a view of a cross section of the enclosure in an open position and the lateral underground storage.
[0111] FIG. 21 is an internal view of a cross section of the enclosure in closed condition with side underground chambers.
[0112] FIG. 22 is a schematic view of a cross section of half of the enclosure in closed position.
[0113] FIG. 23 is a schematic view of an approach of a cross section of half of the enclosure that shows how the beams of the modules are related in closed position.
[0114] FIG. 24 is a schematic view of an approach of a cross section of the axial profiles of the envelope in closed position showing how the axial sections of the panels of the modules are related.
[0115] FIG. 25 is a view of a cross section of one underground storage and the structure in open position.
[0116] FIG. 26 is a side view of an approach one to a bearing.
[0117] FIG. 27 is a lower view of one of the bearings.
[0118] FIG. 28 is a front view of the bearing hole through which passes one of the axes.
[0119] FIG. 29 is a perspective view showing the arrangement of the closed halves of the enclosure and a traverse cut for a better appreciation of the underground storage.
DETAILED DESCRIPTION OF THE INVENTION
[0120] In order that the present invention may be clearly understood and implemented the preferred embodiment is disclosed hereinafter. An accurate description of a preferred embodiment with reference to the same to the accompanying schematic drawings, given that in all figures the same reference numerals that indicate like or corresponding elements; the preferred embodiment is one of many and it is purely illustrative and in no way limiting of the invention.
[0121] FIG. 1 is a perspective view of the inventive enclosure in the deployed position where it may be observed that each half of the enclosure is made of upper module ( 1 ), medium module ( 2 ), and lower module ( 3 ). Each of the modules consist of a plurality of longitudinal beams, herein shown an upper beam ( 4 ), a middle beam ( 5 ), and a lower beam ( 6 ), and a plurality of transversal ribs ( 7 ). The spaces delimited by the beams and ribs are filled by foil material covering ( 8 ). A wedge-type front and rear panels are formed by an upper profile beam ( 9 ) and two lateral or axial profiles beams ( 10 , 11 ), a middle a curved profile rib ( 12 ) is used to strengthen the panels. Foil material covering ( 13 , 14 ) fills the spaces delimited by the various beams and ribs. Brackets ( 15 ) may be used to strengthen the enclosure structure. One or more modules or panels may have an opening, such as a door ( 16 ), shown at the lower module ( 3 ). The upper module ( 1 ) on each half of the enclosure is framed by a closing or attack beam ( 17 , 17 ′) that together function as underground housing covers, and the rainwater collectors ( 18 , 19 ) of the lower module ( 3 ).
[0122] FIG. 2 is a perspective view of the enclosure in the open position showing the underground housing covers ( 17 and 17 ′). FIG. 3 is a top view of the inventive enclosure in the deployed position showing that each half of it is made by the upper module ( 1 ), middle module ( 2 ), and lower module ( 3 ). Each module consists of an upper beam ( 4 ), a middle beam ( 5 ), a bottom beam ( 6 ), a plurality of ribs or intermediate sections ( 7 ), foil material covering the spaces delimited by the beams and ribs ( 8 ), and two wedge type panels of which it can be seen the upper profile beam ( 9 , 9 ′). The attack beam of the upper module ( 1 ) forms the underground cover ( 17 ). Shown also are the rainwater collector ( 18 ) of the lower module ( 3 ), the front rain collector ( 19 ), the underground engine compartments ( 20 and 20 ′), and the structural supporting brackets ( 21 ). This figure shows clearly how the modules of one half are offset with respect to the modules of the other half, so that they may be interposed half on the modules of the other half, to allow proper rotation without interfering with its extensions or counterweights. In the event that counterweight extensions are not used, it is not necessary to maintain an offset of the modules.
[0123] FIG. 4 shows a sequence of perspective views of the evolution of the enclosure. Looking from top to bottom: 4 A: Enclosure completely deployed; 4 B: Partial opening; 4 C: Partial opening; 4 D: Enclosure fully open.
[0124] FIG. 5 shows a longitudinal sectional view of the deployed enclosure, so that the modules which make one half of the enclosure are observable. The upper module framed by underground cover ( 17 ) is appreciated, as are middle module ( 2 ), and lower module ( 3 ). The front and rear covers ( 19 and 19 ′), which are retractable, and the lower ( 22 ) and middle ( 23 ) beam from the middle module ( 2 ), as well as ribs or intermediate sections ( 24 ), and the foil material covering the space delimited by the beams and ribs ( 25 ). Counterweights ( 26 , 27 , 28 and 26 ′, 27 ′, 28 ′) used in this embodiment are observed as are the front and rear axles ( 29 and 29 ′) for this half of the enclosure and the front and back underground housing ( 30 and 30 ′).
[0125] FIG. 6 is a transversal cross-sectional view of the deployed enclosure and underground housing, where it can be observed: Upper modules ( 1 , 1 ′), middle modules ( 2 , 2 ′), and lower modules ( 3 , 3 ′) with its storm sewers ( 18 , 18 ′), the axes ( 29 , 29 ″), underground housing compartments ( 31 , 31 ′), and the group of counterweights ( 32 ) for each module.
[0126] FIG. 7 is a cross sectional view of an open enclosure where all modules are retracted into the lateral underground housings, appreciating: upper modules ( 1 , 1 ′), middle modules ( 2 , 2 ′), lower modules ( 3 , 3 ′) with its attached storm gutters ( 18 , 18 ′), covers ( 17 , 17 ′) for the upper modules ( 1 , 1 ′) of each half, the axes ( 29 , 29 ″), side underground housing ( 31 , 31 ′), and a group of counterweights ( 32 ) for each module.
[0127] FIG. 8 is a top view of the inventive enclosure in the open position with its covers removed to appreciate the disposition of the modules ( 1 , 2 , 3 , 1 ′, 2 ′, 3 ′) in the underground housing, engine compartments ( 20 , 20 ′), motors ( 33 , 33 ′), axis of each motor ( 34 , 34 ′), affixing and supporting structures ( 35 , 36 , 35 ′, 36 ′) for the axes corresponding to each side of the enclosure ( 29 , 29 ″, 29 ″′, 29 ″″), gearbox reductions for each motor ( 37 , 38 ), and frontal extensions of each module with its counterweights ( 26 , 27 , 28 , 26 ′, 27 ′, 28 ′).
[0128] FIG. 9 is a schematic cross sectional view an alternative embodiment of the inventive enclosure comprising four modules in a deployed mode.
[0129] FIG. 10 is a schematic cross sectional view an alternative embodiment of the inventive enclosure comprising four modules in an open mode.
[0130] FIG. 11 is a schematic cross sectional view yet another alternative embodiment of the inventive enclosure comprising eight modules in a deployed mode.
[0131] FIG. 12 is a schematic cross sectional view yet another alternative embodiment of the inventive enclosure comprising eight modules in an open mode.
[0132] FIG. 13 is a top schematic view of the horizontal section of the back panels of the modules showing, in the deployed position, the location and relationship amongst the axial panels of the modules. It can be appreciated the upper modules ( 1 , 1 ′), each with its two axial profiles or lateral beams ( 10 ′, 11 ′, 10 ″′, 11 ″′); middle modules ( 2 , 2 ′), each with its two axial profiles or lateral beams ( 39 ′, 40 ′, 39 ′″, 40 ′″), and lower modules ( 3 , 3 ′), each with its two axial profiles or lateral beams ( 41 ′, 42 ′, 41 ″′, 42 ′″).
[0133] FIG. 14 is an internal cross sectional view of the upper module where it can be observed the upper beam ( 4 ), middle beam ( 5 ), lower beam ( 6 ), foil material covering ( 43 ), and the wedge formed by an upper profile beam ( 9 ), two lateral or axial profiles beams ( 10 , 11 ), a middle curved profile rib ( 12 ), foil material covering ( 13 , 14 ), and supporting brackets ( 15 , 15 ′). The axis passage ( 44 ) and the counterweight ( 28 ) are shown.
[0134] FIG. 15 is a cross sectional view of the front panel of the upper module where it can be observed the internal face of one of the panels and the arrangement of the beams ( 10 , 11 ), the curved profile ( 12 ), the foil material covering ( 13 ), and the counterweight ( 28 ).
[0135] FIG. 16 is an internal cross sectional view of the middle module where it can be observed an upper beam ( 45 ), a middle beam ( 23 ), a lower beam ( 22 ), the foil material ( 46 ), and the wedge-type panel formed by a top rib or profile ( 47 ) and two lateral studs or profiles ( 48 , 49 ), a curved profile ( 50 ), foil material covering ( 51 , 52 ), and supporting brackets ( 53 , 53 ′). The axis passage ( 54 ) and the counterweight ( 59 ) are shown.
[0136] FIG. 17 is a cross sectional view of the front panel of the middle module where it is shown the arrangement of the studs ( 48 , 49 ), curved profile ( 50 ), foil material covering ( 51 ), and counterweight ( 27 ).
[0137] FIG. 18 is an internal cross sectional view of the lower module where it can be observed an upper beam ( 55 ), a middle beam ( 56 ), a lower beam ( 57 ), the foil material covering ( 58 ), and the wedge-type panel formed by a top rib or profile ( 59 ), two lateral studs or profiles ( 60 , 61 ), a curved profile ( 62 ), foil material covering ( 63 , 64 ). The axis passage ( 65 ), the counterweight ( 26 ), an opening represented by a door ( 16 ), and a gutter ( 18 ) are shown.
[0138] FIG. 19 is a cross sectional view of the lower module where it is shown the internal face of one panel and the arrangement of studs ( 60 , 61 ), the curved middle section ( 62 ), the foil material covering ( 63 ), and the counterweight ( 26 ).
[0139] FIG. 20 is a cross sectional view of the deployed enclosure showing the lateral underground housings ( 31 , 31 ′), the axes ( 29 , 29 ″), the group of counterweights ( 32 ), an internal reinforcement arch ( 66 ), and the sets of modules ( 67 , 67 ′) in their respective underground housing ( 31 , 31 ′), and gutters ( 18 , 18 ′).
[0140] FIG. 21 is an internal view of a cross section of the enclosure in the deployed position showing side underground housings ( 31 , 31 ′), a group of counterweights ( 32 ), one of the internal reinforcement arches ( 66 ) shown to appreciate the relative position with reference to the upper ( 1 , 1 ′), middle ( 2 , 2 ′) and lower ( 3 , 3 ′) modules for each half of the enclosure with their gutters ( 18 , 18 ′), and bearings ( 67 , 68 , 69 , 67 ′, 68 ′, 69 ′) located on the inside of the beams corresponding to each half modules and rolling on the upper face of the arch ( 66 ).
[0141] FIG. 22 is a schematic rear view of a cross section of one half of the deployed enclosure showing the upper beam ( 4 ), middle beam ( 5 ), and lower beam ( 6 ) of the upper module, the last one ( 6 ) having bearings ( 70 ) on its lower side; the middle module with an upper beam ( 45 ) presenting a bearing ( 71 ) on its upper side, a middle beam ( 23 ), and lower beam ( 22 ) presenting a bearing ( 72 ) on its lower side; lower module, presenting gutters ( 18 ), an upper beam ( 55 ) presenting a bearing ( 73 ) on its upper face, a middle beam ( 56 ), and lower beam ( 57 ); said bearings permit the modules to roll over the matching faces of the ribs or profiles that are perpendicular to the beams.
[0142] FIG. 23 is a detailed schematic view of a cross section of a joint of two modules showing how the beams of the modules, in this example the middle module's lower beam ( 22 ) with its flange or stop ( 74 ) and bearing ( 72 ) from the lower module with his upper beam ( 55 ) with its flange or cap ( 75 ) and bearing ( 73 ), and the respective foil material covering ( 46 , 58 ).
[0143] FIG. 24 is a schematic view of a cross section of the axial profiles of the deployed enclosure showing how the axial sections of the panels of the modules are related when deployed. In this case, the upper module with its lower beam ( 11 ) and its flange or cap ( 76 ) meet middle module's upper beam ( 48 ) and its flange or cap ( 77 ) and the respective foil material coverings ( 13 , 51 ).
[0144] FIG. 25 is a view of a cross section of one underground housing ( 31 ) showing the upper module with an upper beam ( 4 ), a middle beam ( 5 ), a lower beam ( 6 ), the foil material covering ( 43 ), and an upper profile beam ( 9 ); the middle module with an upper beam ( 45 ), a middle beam ( 23 ), a lower beam ( 22 ), the foil material covering ( 46 ), and an upper profile beam ( 47 ); the lower module with an upper beam ( 55 ), a middle beam ( 56 ), a lower beam ( 57 ), the foil material covering ( 58 ), upper profile beam ( 59 ), and gutters ( 18 ).
[0145] FIG. 26 is a side view, in this case of the middle module's lower beam ( 22 ) with its flange or stop ( 74 ), in contact with lower module's upper beam ( 55 ) with its flange or cap ( 75 ), bearing ( 73 ), and the retaining bearing plate ( 78 ).
[0146] FIG. 27 is a bottom view of one of the bearings in which the bearing ( 73 ) and the retaining plate of the bearing ( 78 ) are shown.
[0147] FIG. 28 is a front view showing a bearing ( 79 ) in the axis passage ( 54 ) in the middle module, also shown two lateral studs or profiles ( 48 , 49 ).
[0148] FIG. 29 is a perspective view showing half of the enclosure deployed showing a transversal cut to the soil for better appreciation of the underground housings. It can be appreciated the upper module ( 1 ′) with its counterweight ( 28 ′), the middle module ( 2 ′) with its counterweight ( 27 ′), and the lower module ( 3 ′) with its counterweight ( 26 ′), the closure or attack beam ( 17 ′) corresponding to this half of the enclosure formed by the attack profiles, the engine compartment ( 20 ′) where a motor may be housed, the lateral underground housing ( 31 , 31 ′), the axis ( 29 ″), shown extended for a better visualization.
[0149] It is logical to assume that this invention may be implemented with modifications insofar as construction materials and number of modules, but without departing from the basic principles that are clearly specified in claims bellow. | A manual or motor activated enclosure, appropriate for any surface to be enclosed, comprising matching opposite cross-linked structures containing a set of profiles that fits in the field of telescopic modular pivoting roof structures, that upon retraction it is housed underground such that none of its components are visible above ground, and upon deployment it achieves complete enclosure of the area while proving for openings. | 4 |
[0001] The present invention relates to organic light emitting diodes (OLEDs) and methods for fabricating OLEDs, and particularly to an OLED with a fluorinion-doped anode and a method for fabricating the OLED.
BACKGROUND
[0002] OLED devices have begun to gradually replace cathode ray tube displays (CRTs) and liquid crystal displays (LCDs) in the marketplace. This is because OLED devices not only have a thinner profile, wider viewing angle, and less weight, but they also have faster response times and lower power consumption. Another advantage is the relatively simple structure of an OLED device, which typically includes an anode, a cathode, and an organic emission stack positioned therebetween. The simple structure permits the OLED device to be easily fabricated using relatively inexpensive manufacturing processes.
[0003] Referring to FIG. 3 , a conventional OLED 10 includes a transparent substrate 11 , an anode 12 , an organic emission stack 19 , and a cathode 18 arranged in that order from bottom to top. The organic emission stack 19 includes several layers depending on its functions. The organic emission stack 19 usually includes a hole injection layer 13 , a hole transporting layer 14 , an emitting layer 15 , an electron transporting layer 16 , and an electron injection layer 17 arranged in that order from the anode 12 to the cathode 18 .
[0004] In operation, a positive electrical potential is applied between the anode 12 and the cathode 18 . Holes from the anode 12 are injected into the emitting layer 15 through the hole injection layer 13 and the hole transporting layer 14 . Electrons from the cathode are injected into the emitting layer 15 through the electron injection layer 17 and the electron transporting layer 16 . Accordingly, light beams are generated from the emitting layer 15 as a result of hole-electron recombination within the emitting layer 15 .
[0005] Generally, the anode 12 is made of a transparent conductive material with a high work function. For example, the anode 12 may be an indium tin oxide (ITO) layer. The hole injection layer 13 is made of organic material. However, a pure ITO layer has a hydrophilic property, and an organic layer has a lipophilic property. Because of these inconsistent properties, the anode 12 and the hole injection layer 13 cannot be combined together firmly. Furthermore, impurities, such as oxygen and water, are liable to be introduced between the anode 12 and hole injection layer 13 . These impurities can greatly impair the operability of the OLED 10 and reduce the working lifetime of the OLED 10 .
[0006] Accordingly, what is needed is an OLED and a method for fabricating the OLED which can overcome the above-described deficiencies.
SUMMARY
[0007] In one aspect, an organic light emitting diode includes a substrate, a first electrode with a plurality of fluorinions therein, an organic emission stack, and a second electrode sequentially stacked in that order.
[0008] In another aspect, a method for fabricating an organic light emitting diode includes steps: providing a substrate, and forming a first electrode on the substrate; doping a plurality of fluorinions into the first electrode; forming an organic emission stack on the first electrode; and forming a second electrode on the organic emission stack.
[0009] Other novel features and advantages will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is a schematic, isometric view of an OLED according to a preferred embodiment of the present invention.
[0011] FIG. 2 is a flowchart summarizing an exemplary method for fabricating the OLED of FIG. 1 .
[0012] FIG. 3 is a schematic, side cross-sectional view of a conventional OLED.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0013] FIG. 1 is a schematic, isometric view of an OLED according to a preferred embodiment of the present invention. The OLED 20 includes a transparent substrate 21 , an anode 22 , an organic emission stack 29 , and a cathode 28 arranged in that order from bottom to top.
[0014] The transparent substrate 21 may for example be made of glass, quartz, sapphire or plastic. The anode 22 is made of transparent conductive material selected from indium tin oxide (ITO), indium zinc oxide (IZO), and indium cerium oxide (ICO). A plurality of fluorinions (not shown) are doped in the anode 22 , so as to reduce a hydrophilic property and enhance a hydrophobic property of the anode 22 .
[0015] The organic emission stack 29 includes several layers depending on its functions. In the illustrated embodiment, the organic emission stack 29 includes a hole injection layer 23 , a hole transporting layer 24 , an emitting layer 25 , an electron transporting layer 26 , and an electron injection layer 27 arranged in that order from the anode 22 to the cathode 28 .
[0016] The cathode 27 is made of a metal or metal alloy. Illustrative metals and metal alloys include, but are not limited to, aluminum (Al), silver (Ag), yttrium (Yt), calcium (Ca), magnesium/silver (Mg/Ag), and the like.
[0017] FIG. 2 is a flowchart summarizing an exemplary method for fabricating the OLED 20 . The method includes: step S 1 , providing a substrate; step S 2 , forming an anode; step S 3 , doping fluorinions; step S 4 , forming a hole injection layer and a hole transporting layer; step S 5 , forming an emitting layer; step S 6 , forming an electron transporting layer and an electron injection layer; and step S 7 , forming a cathode.
[0018] In step S 1 , the substrate 21 is provided. The substrate 21 is made of transparent material such as glass, quartz, sapphire or plastic.
[0019] In step S 2 , a transparent conductive film, such as an ITO film, an IZO film, or an ICO film, is formed on the substrate 21 , thereby obtaining the anode 22 . The anode 22 can be formed through any one of a deposition process, a sputtering process, a vacuum vapor deposition process, and the like.
[0020] In step S 3 , a plurality of fluorinions (not shown) are doped into the anode 22 . The fluorinions can be doped into the anode by an ion diffusion method or ion implantation method in a vacuum environment. Then a thermal activation process is performed on the anode 22 , in order to cure defects formed during the doping process.
[0021] After the fluorinions are doped into the anode 22 , a solvent cleaning process is performed on the anode 22 . The cleaning process can be one or more of an ultrasonic cleaning process, a heat treatment process, a plasma treatment process using hydrogen, oxygen, ozone, etc., an ultraviolet-ozone (UV-ozone) treatment process, and/or a silane treatment process. Such cleaning processes clean impurities from the anode 22 , and lower an electronic energy level of the anode 22 . This facilitates electron injection into an ionization energy level of an upper organic layer formed in a subsequent step. Such cleaning processes also improve the interface properties between the anode 22 and an organic layer subsequently formed on the anode 22 .
[0022] In step S 4 , the hole injection layer 23 and the hole transporting layer 24 are sequentially formed on the anode 22 . The hole injection layer 23 is made of a material selected from copper phthalocyanine (CuPc) and 4,4′,4″-tris(N-(3-methylphenyl)-N-phenylamino)triphenylamine (MTDATA). The hole transporting layer 25 is made of N,N′-di(1-naphthyl)-N,N′-diphenyl-benzidine (NPD), or the like. The hole injection layer 23 and the hole transporting layer 24 helpful to provide the OLED 20 with a low starting voltage, and enhance a stability of the OLED 20 .
[0023] In step 5 , an organic layer (not labeled) is formed on the hole transporting layer 24 . The organic layer can for example be made of an organic polymer material, or a non-polymer material, or the like. The organic layer is formed by a method selected from a spin coating method, a vacuum vapor deposition method, a laser-induced thermal imaging method, and the like. The organic layer is then patterned, thereby forming the emitting layer 25 .
[0024] In step S 6 , the electron transporting layer 26 and the electron injection layer 27 are sequentially formed on the emitting layer 25 . The electron transporting layer 26 can for example be made of a material selected from a polycyclic hydrocarbon-based derivative, a heterocyclic compound, an aluminum complex, a gallium complex, any derivative of the foregoing, and the like. The electron injection layer 27 can for example be made of a material selected from alkali metals and alkali compounds with low work function, such as calcium, magnesium or lithium fluoride.
[0025] In step S 7 , a transparent conductive layer with low work function is formed on the electron injection layer 27 , thereby obtaining the cathode 28 . A thickness of the cathode 28 is in a range of 5 nm (nanometers) to 30 nm. The cathode 28 can for example be made of metals and metal alloys, such as Al, Ag, Yt, Ca, Mg/Ag, and the like.
[0026] In the above-described described OLED 20 and method for fabricating the OLED 20 , a plurality of fluorinions are doped into the anode 22 . The fluorinons enable the anode 22 to have a hydrophobic property. Accordingly, the anode 22 has an improved surface property. In particular, the anode 22 can be firmly combined with the organic emission stack 29 , and few or even no impurities are liable to be introduced between the anode 22 and the hole injection layer 23 . The fluorinion-doped anode 22 enhances the operability and prolongs a working lifetime of the OLED 20 .
[0027] It is to be understood, however, that even though numerous characteristics and advantages of the present embodiments have been set out in the foregoing description, together with details of the structures and functions of the embodiments, the disclosure is illustrative only; and that changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the invention to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed. | An exemplary organic light emitting diode ( 20 ) includes a substrate ( 21 ), a first electrode ( 22 ) with a plurality of fluorinions therein, an organic emission stack ( 29 ), and a second electrode ( 28 ) sequentially stacked in that order. A related method for fabricating the organic emitting diode is also provided. | 7 |
FIELD OF THE INVENTION
[0001] The invention relates to a novel process, novel process steps and novel intermediates useful in the synthesis of pharmaceutically active compounds, in particular neutral endopeptidase (NEP) inhibitors.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a method to prepare N-acyl derivatives of biphenyl alanine. N-acyl derivatives of biphenyl alanine are key intermediates in the synthesis of pharmaceutically active compounds, in particular neutral endopeptidase (NEP) inhibitors, such as those described in U.S. Pat. No. 4,722,810, U.S. Pat. No. 5,223,516, U.S. Pat. No. 4,610,816, U.S. Pat. No. 4,929,641, South African Patent Application 84/0670, UK 69578, U.S. Pat. No. 5,217,996, EP 00342850, GB 02218983, WO 92/14706, EP 00343911, JP 06234754, EP 00361365, WO 90/09374, JP 07157459, WO 94/15908, U.S. Pat. No. 5,273,990, U.S. Pat. No. 5,294,632, U.S. Pat. No. 5,250,522, EP 00636621, WO 93/09101, EP 00590442, WO 93/10773, WO2008/031567 and U.S. Pat. No. 5,217,996.
[0003] Typically, synthetic methods to prepare biphenyl alanine derivatives use expensive starting materials such as non-natural D-tyrosine. Moreover, said methods require the use of trifluoromethanesulfonic anhydride, which is also expensive, to activate the phenolic hydroxyl in order to carry out the aryl coupling reaction leading to the desired biphenyl structure. One example of such a synthetic approach is described in the Journal of Medicinal Chemistry 1995, Vol. 38 No. 10. 1689-1700. Scheme 1 illustrates one of these methods:
[0000]
[0004] A method for preparing 2-acetylamino-3-biphenyl propanoic acid is reported in Chemical and Pharmaceutical Bulletin, 1976, 24 (12), 3149-57. Said method comprises the steps i) and ii) outlined below:
[0000]
[0005] A drawback of this process is that the acetyl group is removed under the reaction conditions of the first step and thus a further chemical step is necessary in order to reinstall it. Such an undesired acetyl removal makes thus the process unattractive both from the atom economic point of view and from the reagent cost perspective. Moreover, this process does not provide means to obtain enantiomerically pure 2-acylamino-3-biphenyl propanoic acid, in particular it does not allow for the preparation of (S)-2 acylamino-3-biphenyl acid, which is, as above mentioned, a key intermediate in the synthesis of pharmaceutically active compounds, in particular neutral endopeptidase (NEP) inhibitors.
[0006] Therefore, there is a strong need to develop inexpensive methods to prepare biphenyl alanine derivatives. It is found that the present invention meets this objective and thus provides a process that is industrially advantageous.
SUMMARY OF THE INVENTION
[0007] This invention provides a method for preparing a N-acylbiphenyl alanine of formula (I), as defined herein. The new process, according to the present invention, for producing a chiral compound according to formula (I), is summarized in Scheme 2, wherein
steps a), b) and c) are as defined herein; compounds of formula (I), (II), (III) and (IV) are as defined herein; and “*” means a chiral center with absolute stereochemistry (R) or (S),
[0000]
[0011] In one embodiment, the process of the present invention provides a compound of formula (Ia), as summarized in Scheme 3, wherein
steps a), b) and c) are as defined herein; and compounds of formula (Ia), (IIa), (III) and (IV) are as defined herein.
[0000]
[0014] In another embodiment, the process of the present invention provides a compound of formula (Ib), as summarized in Scheme 4, wherein
steps a), b) and c) are as defined herein; and compounds of formula (Ib), (IIb), (III) and (IV) are as defined herein.
[0000]
[0017] A chiral compound of formula (I) can be converted into a neutral endopeptidase (NEP) inhibitors, for example, as described in the Journal of Medicinal Chemistry, 1995, Vol. 38, No. 10, 1691, and the patent documents cited hereinbefore, the disclosure for each of which is incorporated by reference
DETAILED DESCRIPTION OF THE INVENTION
Step a:
[0018] In a first embodiment the present invention relates to a method for preparing a compound of formula (III), or salt thereof,
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
comprising
reacting a compound of formula (IV), or salt thereof,
[0000]
[0000] wherein R1 is as defined for the compound of formula (III)
under decarboxylation reaction conditions
to provide the compound of formula (III).
[0019] Step a) may be carried out in solvents generally known in the art, for example, in the presence of a solvent, (named solvent 1), selected from water, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, N,N-dimethyl formamide (DMF) and 1-methyl-2-pyrrolidone (NMP). The amount of said solvent 1 is, for example, 0 to 50 times the feed amount (by weight) of the compound of formula IV, as defined herein.
[0020] Typically, decarboxylation reaction conditions are achieved by heating, in particular, step a is carried out at a reaction temperature of from 80 deg C. to 250 deg C. In one embodiment, step a) is carried out at the reflux temperature of solvent 1, as defined herein.
[0021] In one embodiment, the reaction time for step a) is of from 2 to 48 hours.
Step b:
[0022] In a further embodiment, the present invention relates to a method for preparing a chiral compound of formula (II),
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
R2 is C 1-7 alkyl, such as methyl; or is R3R4NC(═O)— or R5OC(═O)—, wherein R3 and R4 are independently selected from hydrogen or C 1-7 alkyl; and R5 is C 1-7 alkyl;
R6 is C 6-10 aryl, such as phenyl, and
“*” means a chiral center with absolute stereochemistry (R) or (S),
comprising
reacting
a compound of formula (III), or salt thereof,
[0000]
[0000] wherein R1 is as defined for the compound of formula (II),
with a chiral amine of formula (V)
[0000]
[0000] wherein R2 and R6 are as defined for the compound of formula (II), and
“*” means a chiral center with absolute stereochemistry (R) or (S);
and resolving the resulting diastereomeric mixture via crystallization
to provide the compound of formula (II).
[0023] A chiral compound of formula (II), as defined herein, means a compound having the formula
[0000]
[0000]
[0000] wherein R1, R2 and R6 are as defined for the compound of formula (II).
[0024] In a further embodiment, the present invention relates to a method for preparing a chiral compound of formula (IIa),
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
R2 is C 1-7 alkyl, such as methyl; or is R3R4NC(═O)— or R5OC(═O)—, wherein R3 and R4 are independently selected from hydrogen or C 1-7 alkyl; and R5 is C 1-7 alkyl; and
R6 is C 6-10 aryl, such as phenyl;
comprising
reacting
a compound of formula (III), or salt thereof,
[0000]
[0000] wherein R1 is as defined for the compound of formula (IIa),
with a chiral amine of formula (Va)
[0000]
[0000] wherein R2 and R6 are as defined for the compound of formula (IIa);
and resolving the resulting diastereomeric mixture via crystallization
to provide the compound of formula (II).
[0025] In a further embodiment, the present invention relates to a method for preparing a chiral compound of formula (IIb),
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
R2 is C 1-7 alkyl, such as methyl; or is R3R4NC(═O)— or R5OC(═O)—, wherein R3 and R4 are independently selected from hydrogen or C 1-7 alkyl; and R5 is C 1-7 alkyl;
R6 is C 6-10 aryl, such as phenyl;
comprising
reacting
a compound of formula (III), or salt thereof,
[0000]
[0000] wherein R1 is as defined for the compound of formula (IIb),
with a chiral amine of formula (Vb)
[0000]
[0000] wherein R2 and R6 are as defined for the compound of formula (IIb);
and resolving the resulting diastereomeric mixture via crystallization
to provide the compound of formula (IIb).
[0026] The reactions described above are carried out in solvents generally known in the art, for example, a solvent (named solvent 2) selected from methanol, ethanol, isopropanol and aqueous solutions thereof. And the solvent added for the crystallization can be different from that added in the preparation of a compound of formula (III). The feed amount (by weight) of solvent 2 is for example, 10 to 50 times the amount of the compound of formula (III), as defined herein.
[0027] In particular, step b is carried out at a reaction temperature of from −10 deg C. to 40 deg C. In particular the crystallization is carried out at a temperature of from 0 to 40 deg C.
[0028] Typically, in step b) the molar ratio of the 2-acylamino-3-biphenyl propanoic acid compound of formula (III), as defined herein, to the compound of formula (V), (Va) or (Vb) as defined herein, is 1.0:(0.5 to 3.0).
Step c:
[0029] In a further embodiment, the present invention relates to a method for preparing a chiral compound of formula (I), or salt thereof,
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl; and
“*” means a chiral center with absolute stereochemistry (R) or (S),
comprising
treating a chiral compound of formula (II),
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
R2 is C 1-7 alkyl, such as methyl; or is R3R4NC(═O)— or R5OC(═O)—, wherein R3 and R4 are independently selected from hydrogen or C 1-7 alkyl; and R5 is C 1-7 alkyl;
R6 is C 6-10 aryl, such as phenyl, and
“*” means a chiral center with absolute stereochemistry (R) or (S),
with an acidic reagent
to provide the compound of formula (I).
[0030] In a still further embodiment, the present invention relates to a method for preparing a compound of formula (Ia), or salt thereof,
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
comprising
treating a compound of formula (IIa),
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
R2 is C 1-7 alkyl, such as methyl; or is R3R4NC(═O)— or R5OC(═O)—, wherein R3 and R4 are independently selected from hydrogen or C 1-7 alkyl; and R5 is C 1-7 alkyl, and
R6 is C 6-10 aryl, such as phenyl;
with an acidic reagent
to provide the compound of formula (I).
[0031] In a still further embodiment, the present invention relates to a method for preparing a compound of formula (Ib), or salt thereof,
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
comprising
treating a compound of formula (IIb),
[0000]
[0000] wherein
R1 is C 1-7 alkyl, such as methyl or ethyl; or is substituted or unsubstituted C 6-10 aryl, such as phenyl or para-chlorophenyl;
R2 is C 1-7 alkyl, such as methyl; or is R3R4NC(═O)— or R5OC(═O)—, wherein R3 and R4 are independently selected from hydrogen or C 1-7 alkyl; and R5 is C 1-7 alkyl, and
R6 is C 6-10 aryl, such as phenyl;
with an acidic reagent
to provide the compound of formula (Ib).
[0032] Typically, the acidic reagent is an inorganic acid or an organic acid, such as hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, citric acid, formic acid or acetic acid.
[0033] Typically, step c) is carried out in solvents generally known in the art, for example, a solvent, (named solvent 3), selected from water, methanol, ethanol, isopropanol and tetrahydrofuran. The amount of said solvent 3 is, for example, 2 to 20 times the feed amount (by weight) of the compound of formula II, as defined herein.
[0034] In particular, step c is carried out at a reaction temperature of from 10 deg C. to 95 deg C.
[0035] In one embodiment, the reaction time for step c) is of from 10 min to 5 hours.
[0036] Typically, in step c) the molar ratio of the compound of formula (II), as defined herein, to the acidic reagent is 1.0:(1.0 to 4.0).
Further Embodiments
[0037] In a further aspect, the present invention relates to a method for preparing a compound of formula (I), (Ia) or (Ib), as defined herein, or salt thereof, comprising
i) step a), as described above; ii) step b), as described above; and iii) step c) as described above.
[0041] In a still further aspect, the present invention relates to a method for preparing a compound of formula (I), (Ia) or (Ib), as defined herein, or salt thereof, comprising
iv) step b), as described above; and v) step c) as described above.
Preferred Embodiments
Embodiment 1
[0044] A process for preparing and resolving a 2-acylamino-3-biphenyl propanoic acid compound of formula III, which is characterized in that it is comprised of the following steps:
[0000]
[0000] wherein
R1 is an alkyl group, a phenyl, or phenyl containing substituting group;
R2 is methyl or a group featuring the following structure:
[0000]
[0000] wherein R3, R4 are H or an alkyl group; and
R5 is an alkyl group.
Embodiment 2
[0045] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 1, which is characterized in that said alkyl is preferably methyl, ethyl, propyl or isopropyl; said phenyl containing substituting group is preferably para-chlorophenyl.
Embodiment 3
[0046] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 1 or 2, which is characterized in that step a is carried out by heating to a temperature of from 80 deg C. to 250 deg C.
Embodiment 4
[0047] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 1 or 2, which is characterized in that during step a, the compound of formula IV reacts at reflux temperature a in solvent 1 to provide said 2-acylamino-3-biphenyl propanoic acid compound.
Embodiment 5
[0048] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 4, which is characterized in that said solvent 1 is selected from water, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, N,N-dimethyl formamide and 1-methyl-2-pyrrolidone.
Embodiment 6
[0049] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 1, which is characterized in that during step b said 2-acylamino-3-biphenyl propanoic acid compound is reacted with a compound of formula Va or Vb in solvent 2 to obtain the crude wet compound of formula IIa or IIb.
Embodiment 7
[0050] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 1, which is characterized in that during step b, said 2-acylamino-3-biphenyl propanoic acid compound reacts with a compound of formula Va or Vb in solvent 2 at a specific temperature to obtain the crude wet compound of formula IIa or IIb.
Embodiment 8
[0051] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid according to embodiment 7, which is characterized in that the said reaction takes place at a temperature of from −10 deg C. to 40 deg C.
Embodiment 9
[0052] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 7, which is characterized in that the crude wet compound of formula IIa or IIb is added with solvent 2 to make it crystallize at a specific temperature and obtain the solid compound of formula IIa or IIb.
Embodiment 10
[0053] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 9, characterized in that the said crystallization takes place at a temperature of from 0 deg C. to 40 deg C.
Embodiment 11
[0054] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to any one of embodiments 6, 7, 8, 9 or 10, which is characterized in that said solvent 2 can be methanol, ethanol, isopropanol, or their respective aqueous solutions.
Embodiment 12
[0055] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiments 1 or 2, which is characterized in that during step b, the molar ratio of the 2-acylamino-3-biphenyl propanoic acid compound to the compound of formula Va or Vb is 1.0:(0.5 to 3.0).
Embodiment 13
[0056] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiments 1 or 2, which is characterized in that the step c is carried out by adding an acidic reagent to obtain the compound of formula Ia or Ib.
Embodiment 14
[0057] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 13, which is characterized in that the acidic reagent is selected from hydrochloric acid, sulphuric acid, phosphoric acid, oxalic acid, citric acid, formic acid and acetic acid.
Embodiment 15
[0058] A process for preparing and resolving the 2-acylamino-3-biphenyl propanoic acid compound according to embodiment 14, which is characterized in that the molar ratio of the compound of formula IIa or IIb to the acidic reagent is 1.0:(1.0 to 4.0).
General Terms:
[0059] Listed below are definitions of various terms used to describe the present invention. These definitions, either by replacing one, more than one or all general expressions or symbols used in the present disclosure and thus yielding preferred embodiments of the invention, preferably apply to the terms as they are used throughout the specification unless they are otherwise limited in specific instances either individually or as part of a larger group.
[0060] Alkyl being a radical or part of a radical is a straight or branched (one or, if desired and possible, more times) carbon chain, and is especially C 1 -C 7 -alkyl, such as C 1 -C 4 -alkyl, in particular branched C 1 -C 4 -alkyl, such as isopropyl. The term “lower” or “C 1 -C 7 -” defines a moiety with up to and including maximally 7, especially up to and including maximally 4, carbon atoms, said moiety being branched (one or more times) or straight-chained and bound via a terminal or a non-terminal carbon. Lower or C 1 -C 7 -alkyl, for example, is n-pentyl, n-hexyl or n-heptyl or preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, sec-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, in particular methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl. In particular, C 1 -C 7 -alkyl is methyl, ethyl, propyl, or isopropyl. In one embodiment C 1 -C 7 -alkyl is methyl or ethyl.
[0061] Aryl, as a radical or part of a radical, for example is a mono- or bicyclic aryl with 6 to 22 carbon atoms, such as phenyl, indenyl, indanyl or naphthyl, in particular phenyl. Substituted C 6-10 aryl is, for example, C 6-10 aryl substituted by one or more substituents (for example one to three substituents) independently selected from, for example, C 1 -C 7 -alkyl, C 1 -C 7 -alkoxy-C 1 -C 7 -alkyl, C 1 -C 7 -alkoxy and halo. In one embodiment, substituted C 6-10 aryl is C 6-10 aryl substituted by halo, such as para-chlorophenyl.
[0062] Alkoxy, as a radical or part of a radical, is, for example, C 1 -C 7 -alkoxy and is, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy and also includes corresponding pentyloxy, hexyloxy and heptyloxy radicals. C 1 -C 4 alkoxy is preferred.
[0063] Halo or halogen is preferably fluoro, chloro, bromo or iodo, most preferably chloro.
[0064] In the formulae of the present application the term
[0000]
[0000] on a C-sp 3 indicates the absolute stereochemistry, either (R) or (S).
[0065] In the formulae of the present application the term
[0000]
[0000] on a C-sp 3 indicates the absolute stereochemistry, either (R) or (S).
[0066] In the formulae of the present application the term on a C-sp 3 represents a racemic mixture, thus it means a chiral center wherein the (S) stereoisomer and the (R) stereoisomer are in a 50:50 ratio.
[0067] In the formulae of the present application the term “Ph” means phenyl.
[0068] The term “chiral”, as used herein, refers to molecules which have the property of non-superimposability on their mirror image partner, while the term “achiral” refers to molecules which are superimposable on their mirror image partner. Any possible pure enantiomer or mixture of enantiomers, pure diastereoisomer or mixture of diasteromer are encompassed by the present invention. In one embodiment the term chiral refers to an entiomerically enriched mixture of enantiomers. The term “enantiomerically enriched”, as used herein, refers to a mixture of enantiomers wherein the amount of one enantiomer is higher than 50%. In another embodiment the term chiral refers to a diasteromerically enriched mixture of diasteromers. The term “diasteromerically enriched”, as used herein, refers to a mixture of diasteromers wherein the amount of one diasteromer is higher than 50%.
[0069] In a further embodiment the term chiral, as used herein, refers to a “diastereomeric mixture”, in particular, a mixture of diastereoisomers (R,R*) and (S,R*) or (R,S*) and (S,S*), wherein R and S refer to the absolute configuration of the asymmetric carbon of a carboxyl group containing molecule and R* and S* refer to the absolute configuration of the asymmetric carbon of an amine containing molecule. A compound of formula (II) may thus be a diasteromeric mixture as defined herein.
[0070] The term “crystallization”, as used herein, refers to a process by which a single diastereoisomer is preferentially crystallized out from a diastereoisomeric mixture, as defined herein. Thus, crystallization refers, in one embodiment, to the process of preferentially crystallizing out the diastereoisomer (R,R*) or (S,R*) from the mixture (R,R*) and (S,R*), as defined above. In another embodiment, crystallization refers to the process of preferentially crystallizing out the diastereoisomer (R,S*) or (S,S*) from the mixture (R,S*) and (S,S*), as defined above.
[0071] The term “resolving”, as employed herein, refers to converting a 50:50 mixture of diastereoisomers (R,R*) and (S,R*) or (R,S*) and (S,S*), as defined above, in a mixture enriched in either one of the diastereoisomers. An enriched mixture is thus one that contains a higher abundance or proportion of one diastereoisomer over the other.
[0072] The term “reflux” refers to the temperature at which the reaction mixture boils, preferably a temperature up to 180° C., preferably up to 140° C.
[0073] As used herein, the term “room temperature” or “ambient temperature” means a temperature of from 20 to 35° C., such as of from 20 to 25° C.
[0074] In view of the close relationship between the compounds and intermediates in free form and in the form of their salts, including those salts that can be used as intermediates, for example in the purification or identification of the compounds or salts thereof, any reference to “compounds”, “starting materials” and “intermediates” hereinbefore and hereinafter, is to be understood as referring also to one or more salts thereof or a mixture of a corresponding free compound, intermediate or starting material and one or more salts thereof, each of which is intended to include also any solvate, metabolic precursor such as ester or amide, or salt of any one or more of these, as appropriate and expedient and if not explicitly mentioned otherwise. Different crystal forms may be obtainable and then are also included. Salts can be formed where salt forming groups, such as basic or acidic groups, are present that can exist in dissociated form at least partially, e.g. in a pH range from 4 to 10 in aqueous solutions, or can be isolated especially in solid, especially crystalline, form. In the presence of basic groups (e.g. imino or amino), salts may be formed preferably with organic or inorganic acids. Suitable inorganic acids are, for example, halogen acids, such as hydrochloric acid, sulfuric acid, or phosphoric acid. Suitable organic acids are, for example, carboxylic, phosphonic, sulfonic or sulfamic acids, for example acetic acid, propionic acid, lactic acid, fumaric acid, succinic acid, citric acid, amino acids, such as glutamic acid or aspartic acid, maleic acid, hydroxymaleic acid, methylmaleic acid, benzoic acid, methane- or ethane-sulfonic acid, ethane-1,2-disulfonic acid, benzenesulfonic acid, 2-naphthalenesulfonic acid, 1,5-naphthalenedisulfonic acid, N-cyclohexylsulfamic acid, N-methyl-, N-ethyl- or N-propyl-sulfamic acid, or other organic protonic acids, such as ascorbic acid. In the presence of negatively charged radicals, such as carboxy or sulfo, salts may be formed with bases, e.g. metal or ammonium salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium, magnesium or calcium salts, or ammonium salts with ammonia or suitable organic amines, such as tertiary monoamines, for example triethylamine or tri(2-hydroxyethyl)amine, or heterocyclic bases, for example N-ethyl-piperidine or N,N′-dimethylpiperazine. When a basic group and an acid group are present in the same molecule, internal salts may also be formed. Particularly useful salts include the hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric, lactic acid, fumaric acid, succinic acid, oxalic acid, malic acid, malonic acid, tartaric acid, tolyltartaric acid, benzoyltartaric acid, orotic acid, nicotinic acid, methane-sulfonic acid or 4-methylbenzenesulfonic acid salts of compounds of formula (I), (III) or (IV) and the like formed from reaction with the above reagents. Methods to prepare acid addition salts are described in the literature, for example, in the relevant chapters of “CRC Handbook of Optical Resolutions via Diasteromeric Salt Formation”, D. Kozma, CRC Press 2002, in Acta Cryst, 2006, B62, 498-505 and in Synthesis, 2003, 13, 1965-1967.
[0075] Where the plural form is used for compounds, starting materials, intermediates, salts, pharmaceutical preparations, diseases, disorders and the like, this is intended to mean one (preferred) or more single compound(s), salt(s), pharmaceutical preparation(s), disease(s), disorder(s) or the like, where the singular or the indefinite article (“a”, “an”) is used, this is not intended to exclude the plural, but only preferably means “one”.
[0076] Particular embodiments of the invention are provided in the following Examples. These Examples serve to illustrate the invention without limiting the scope thereof, while they on the other hand represent preferred embodiments of the reaction steps, intermediates and/or the process of the present invention.
Example 1
Preparation of 2-acetylamino-3-biphenyl propanoic acid
[0077]
[0078] In a dry and clean reaction bottle, add 40 g of 2-acetylamino-2-(4-phenyl benzyl) malonic acid. Add 1000 ml of water and maintain at reflux temperature for 48 hours. Test for completion of reaction with HPLC. Cool down to room temperature and vacuum filtrate it. Dry in an oven at 90 to 100 deg C. and normal pressure. After drying, obtain 31.1 g of 2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 89.9%. 1H NMR (500 MHz, DMSO-d6): 1.82, 2.89-2.93, 3.08-3.12, 4.45-4.50, 7.33-7.37, 7.44-7.47, 7.58-7.60, 7.64-7.66, 8.26˜8.28, 12.75; MS (m/z): 224.07 (100), 167.14 (56), 165.16 (26), 282.94 ([MH+], 1).
Example 2
Preparation of 2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid
[0079]
[0080] Take 20 g of 2-(N-para-chlorobenzoyl)amino-2-(4-phenyl benzyl) malonic acid, and place in a drying oven at 105 deg C. and normal pressure for 12 hours. Test for completion of reaction with HPLC. Obtain 16.4 g of the dry product, 2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid. Yield ratio: 94.8%. 1H NMR (500 MHz, DMSO-d6): 3.12-3.17, 3.25-3.29, 4.66-4.71, 7.32-7.35, 7.42-7.45, 7.54-7.57, 7.58-7.60, 7.62-7.64, 7.86-7.88, 8.89-8.91, 12.963; MS (m/z): 224.0 (100), 167.1 (55), 165.1 (21), 139.1 (10), 111.1 (5), 378.8 ([MH+], 1).
Example 3
Preparation of 2-acetylamino-3-biphenyl propanoic acid
[0081]
[0082] In a dry and clean reaction bottle, add 20 g of 2-acetylamino-2-(4-phenyl benzyl) malonic acid. Add 100 ml of xylene and maintain at reflux temperature for 3 hours. Test for completion of reaction with HPLC. Cool down to room temperature and vacuum filtrate it. Dry in an oven at 90 to 100 deg C. and normal pressure. After drying, obtain 15.6 g of 2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 90.2%. Spectroscopic data as Example 1.
Example 4
Preparation of 2-(N-formyl phenyl)amino-3-biphenyl propanoic acid
[0083]
[0084] In a clean and dry reaction bottle, add 40 g of 2-(N-formyl phenyl)amino-2 (phenyl benzyl) malonic acid. Add 2100 ml of N,N-dimethyl formamide (DMF) and maintain at reflux temperature for 40 hours. Test for completion of reaction with HPLC. Cool down to room temperature and vacuum filtrate it. Dry in an oven at 90 to 100 deg C. and normal pressure. After drying, obtain 32.8 g of 2-(N-formyl phenyl)amino-3-biphenyl propanoic acid. Yield ratio: 92.8%. 1H NMR (500 MHz, DMSO-d6): 3.12-3.17, 3.23-3.27, 4.65-4.70, 7.31-7.33, 7.34-7.45, 7.46-7.48, 7.58-7.60, 7.62-7.64, 7.83-7.84, 8.77-8.79, 12.85; MS (m/z): 224.0 (100), 167.1 (34), 165.1 (15), 105.1 (10), 77.2 (18), 344.8 ([MH+], 1).
Example 5
Preparation of 2-(N-isopropyl formyl)amino-3-biphenyl propanoic acid
[0085]
[0086] In a clean and dry reaction bottle, add 20 g of (2-(N-isopropyl formyl)amino-2 (phenyl benzyl) malonic acid. Add 200 ml of 1,3-dichlorobenzene, heat to reflux temperature and maintain temperature for 25 hours. Test for completion of reaction with HPLC. Cool down to room temperature and vacuum filtrate it. Dry in an oven at 90 to 100 deg C. and normal pressure. After drying, obtain 16.3 g of 2-(N-isopropyl formyl)amino-3-biphenyl propanoic acid. Yield ratio: 94.2%. 1H NMR (500 MHz, DMSO-d6): 0.87-0.88, 2.37-2.43, 2.89-2.94, 3.09-3.13, 4.44-4.48, 7.31-7.36, 7.43-7.46, 7.57-7.59, 7.63-7.65, 8.01-8.08, 12.71; MS (m/z): 224.0 (100), 167.1 (38), 165.2 (16), 310.9 ([MH+], 1).
Example 6
Preparation of 2-propionyl amino-3-biphenyl propanoic acid
[0087]
[0088] In a dry and clean reaction bottle, add 20 g of 2-propionyl amino-2-(4-benzyphenyl) malonic acid. Add 100 ml of nitrobenzene, heat to reflux temperature, and maintain temperature for 2 hours. Test for completion of reaction with HPLC. Cool down to room temperature and vacuum filtrate it. Dry in an oven at 90 to 100 deg C. and normal pressure. After drying, obtain 15.8 g of 2-propionyl amino-3-biphenyl propanoic acid. Yield ratio: 92.1%. 1H NMR (500 MHz, DMSO-d6): 0.93, 2.06-2.11, 2.88-2.93, 3.08-3.12, 4.44-4.49, 7.32-7.36, 7.44-7.47, 7.58-7.59, 7.64-7.66, 8.15-8.16, 12.72; MS (m/z): 224.0 (100), 167.1 (45), 165.1 (20), 296.9 ([MH+], 1).
Example 7
Preparation of 2-butyryl amino-3-biphenyl propanoic acid
[0089]
[0090] In a dry and clean reaction bottle, add 20 g of 2-butyryl amino-2-(4-benzyphenyl) malonic acid. Add 100 ml of 1-methyl-2-pyrrolidone (NMP), heat to reflux temperature, maintain temperature for 15 hours. Test for completion of reaction with HPLC. Cool down to room temperature and vacuum filtrate it. Dry in an oven at 90 to 100 deg C. and normal pressure. After drying, obtain 16.0 g of 2-butyryl amino-3-biphenyl propanoic acid. Yield ratio: 93.5%. 1H NMR (500 MHz, DMSO-d6): 0.74-0.77, 1.42-1.46, 2.03-2.06, 2.87-2.92, 3.09-3.12, 4.46-4.51, 7.32-7.36, 7.43-7.47, 7.56-7.59, 7.63-7.65, 8.16-8.18, 12.70; MS (m/z): 224.0 (100), 167.1 (39), 165.2 (16), 310.9 ([MH+], 1).
Example 8
Preparation of 2-acetylamino-3-biphenyl propanoic acid
[0091]
[0092] In a dry and clean reaction bottle, add 40 g of 2-acetylamino-2-(4-benzyphenyl) malonic acid. Add 5 ml of ethylbenzene and maintain temperature at 80 deg C. for 48 hours. Test for completion of reaction with HPLC. Cool down to room temperature and vacuum filtrate it. Dry in an oven at 90 to 100 deg C. and normal pressure. After drying, obtain 30.5 g of 2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 87.6%. Spectroscopic data as Example 1.
Example 9
Preparation of 2-butyryl amino-3-biphenyl propanoic acid
[0093]
[0094] Take 20 g of 2-butyryl amino-2-(4-phenyl benzyl) malonic acid, and place in a drying oven at 165 deg C. and normal pressure for 18 hours. Test for completion of reaction with HPLC. Obtain 14.3 g of dry product of 2-butyryl amino-3-biphenyl propanoic acid. Yield ratio: 90.3%. Spectroscopic data as Example 7.
Example 10
Preparation of 2-(N-formyl phenyl)amino-3-biphenyl propanoic acid
[0095]
[0096] Take 20 g of 2-(N-formyl phenyl)amino-2-(4-phenyl benzyl) malonic acid, and place in a drying oven at 80 deg C. and normal pressure for 12 hours. Test for completion of reaction with HPLC. Obtain 12.7 g of the product, 2-(N-formyl phenyl)amino-3-biphenyl propanoic acid. Yield ratio: 91.7%. Spectroscopic data as Example 4.
Example 11
Preparation of 2-propionyl amino-3-biphenyl propanoic acid
[0097]
[0098] Take 20 g of 2-propionyl amino-2-(4-phenyl benzyl) malonic acid, and place in a drying oven at 250 deg C. and normal pressure for 12 hours. Test for completion of reaction with HPLC. Obtain 15.4 g of dry product of 2-propionyl amino-3-biphenyl propanoic acid. Yield ratio: 89.8%. Spectroscopic data as Example 6.
[0099] The products from the examples above (1˜11) are used as reactants in the subsequent reaction step (step b).
Example 12
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt
[0100] In a dry and clean reaction bottle, add 300 ml of ethanol and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 4 g of S-1-phenethylamine. Slowly cool down to 10 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt.
[0101] Then, add the crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 0 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 5.7 g of the product. Yield ratio: 39.9%.
Example 13
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt
[0102] In a dry and clean reaction bottle, add 300 ml of methanol and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 3 g of S-1-phenethylamine. Slowly cool down to 30 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt.
[0103] Then, add the crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt to a dry and clean reaction bottle. Add 100 ml of methanol. Heat to increase temperature to reflux. Slowly cool down to 30 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 5.5 g of the product. Yield ratio: 38.5%.
Example 14
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt
[0104] In a dry and clean reaction bottle, add 300 ml of ethanol, 30 ml of tap water, and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 3 g of S-1-phenethylamine. Slowly cool down to 35 deg C. Maintain temperature for 1 hours. Vacuum filtrate it. Obtain crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt.
[0105] Then, add the crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 35 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 5.8 g of the product. Yield ratio: 40.6%.
Example 15
Preparation of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-1-phenethylamine salt
[0106] In a dry and clean reaction bottle, add 634 ml of ethanol and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 12.7 g of R-1-phenethylamine. Slowly cool down to 15 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-1-phenethylamine salt.
[0107] Then, add the crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-1-phenethylamine salt to a dry and clean reaction bottle. Add 200 ml of methanol. Heat to increase temperature to reflux. Slowly cool down to 20 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 6.0 g of the product. Yield ratio: 42.0%.
Example 16
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-2-amino-2-phenyl acetamide salt
[0108] In a dry and clean reaction bottle, add 380 ml of methanol and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 9.2 g of S-2-amino 2-phenyl acetamide. Slowly cool down to 40 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-2-amino 2-phenyl acetamide salt.
[0109] Then, add the crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-2-amino 2-phenyl acetamide salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 30 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 5.7 g of the product. Yield ratio: 39.8%.
Example 17
Preparation of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-2-amino N-methyl 2-phenyl acetamide salt
[0110] In a dry and clean reaction bottle, add 127 ml of isopropanol, and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 2.9 g of R-2-amino N-methyl 2-phenyl acetamide. Slowly cool down to −10 deg C. Maintain temperature for 1 hour. Vacuum filtrate it. Obtain crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-2-amino N-methyl 2-phenyl acetamide salt.
[0111] Then, add the crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-2-amino N-methyl 2-phenyl acetamide salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 40 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 6.1 g of the product. Yield ratio: 42.7%.
Example 18
Preparation of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-2-amino N,N-dimethyl-2-phenyl acetamide salt
[0112] In a dry and clean reaction bottle, add 400 ml of ethanol and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 5 g of R-2-amino N,N-dimethyl-2-phenyl acetamide. Slowly cool down to 25 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-2-amino N,N-dimethyl-2-phenyl acetamide salt.
[0113] Then, add the crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-2-amino N,N-dimethyl-2-phenyl acetamide salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 0 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 4.9 g of the product. Yield ratio: 38.7%.
Example 19
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-amino-phenyl-ethyl acetate amine salt
[0114] In a dry and clean reaction bottle, add 300 ml of isopropanol, 100 ml of tap water, and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 3.5 g of S-amino-phenyl-acetic ether. Slowly cool down to 0 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-amino-phenyl-ethyl acetate amine salt.
[0115] Then, add the crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-amino-phenyl-ethyl acetate amine salt to a dry and clean reaction bottle. Add 100 ml of methanol. Heat to increase temperature to reflux. Slowly cool down to 30 deg C. Vacuum filtrate it. Dry in a drying oven for 8 h at 50 to 60 deg C. Obtain 5.6 g of the product. Yield ratio: 39.0%.
Example 20
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-amino-phenyl-methyl acetate amine salt
[0116] In a dry and clean reaction bottle, add 300 ml of methanol, 30 ml of tap water, and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 10 g of S-amino-phenyl-methyl acetate. Slowly cool down to −5 deg C. Maintain temperature for 1 hours. Vacuum filtrate it. Obtain crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-amino-phenyl-methyl acetate amine salt.
[0117] Then, add the crude wet product of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-amino-phenyl-methyl acetate amine salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 35 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 6.0 g of the product. Yield ratio: 41.5%.
Example 21
Preparation of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-amino-phenyl-isopropyl acetate amine salt
[0118] In a dry and clean reaction bottle, add 300 ml of ethanol and 10 g of 2-acetylamino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 15 g of R-amino-phenyl-isopropyl acetate amine. Slowly cool down to 20 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-amino-phenyl-isopropyl acetate amine salt.
[0119] Then, add the crude wet product of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-amino-phenyl-isopropyl acetate amine salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 20 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 5.2 g of the product. Yield ratio: 36.5%.
Example 22
Preparation of (L)-2-propionyl amino-3-biphenyl propanoic acid-(R)-2-amino N,N-dimethyl-2-phenyl-acetamide salt
[0120] In a dry and clean reaction bottle, add 400 ml of ethanol and 10 g of 2-propionyl amino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 5 g of R-2-amino N,N-dimethyl-2-phenyl acetamide. Slowly cool down to 25 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (L)-2-propionyl amino-3-biphenyl propanoic acid-(R)-2-amino N,N-dimethyl-2-phenyl-acetamide salt.
[0121] Then, add the crude wet product of (L)-2-propionyl amino-3-biphenyl propanoic acid-(R)-2-amino N,N-dimethyl-2-phenyl-acetamide salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 0 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 4.8 g of the product. Yield ratio: 32.7%.
Example 23
Preparation of (D)-2-butyryl amino-3-biphenyl propanoic acid-(S)-amino-phenyl-ethyl acetate amine salt
[0122] In a dry and clean reaction bottle, add 300 ml of isopropanol, 100 ml of tap water, and 10 g of 2-butyryl amino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 3.5 g of S-amino-phenyl-ethyl acetate. Slowly cool down to 0 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (D)-2-butyryl amino-3-biphenyl propanoic acid-(S)-amino-phenyl-ethyl acetate amine salt.
[0123] Then, add the crude wet product of (D)-2-butyryl amino-3-biphenyl propanoic acid-(S)-amino-phenyl-ethyl acetate amine salt to a dry and clean reaction bottle. Add 100 ml of methanol. Heat to increase temperature to reflux. Slowly cool down to 30 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 4.3 g of the product. Yield ratio: 31.5%.
Example 24
Preparation of (D)-2-(N-formyl phenyl)amino-3-biphenyl propanoic acid-(S)-amino-phenyl-methyl acetate amine salt
[0124] In a dry and clean reaction bottle, add 300 ml of methanol, 30 ml of tap water, and 10 g of 2-(N-formyl phenyl)amino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 10 g of S-amino-phenyl-methyl acetate. Slowly cool down to −5 deg C. Maintain temperature for 1 hour. Vacuum filtrate it. Obtain crude wet product of (D)-2-(N-formyl phenyl)amino-3-biphenyl propanoic acid-(S)-amino-phenyl-methyl acetate amine salt.
[0125] Then, add the crude wet product of (D)-2-(N-formyl phenyl)amino-3-biphenyl propanoic acid-(S)-amino-phenyl-methyl acetate amine salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 35 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 5.0 g of the product. Yield ratio: 38.6%.
Example 25
Preparation of (L)-2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid-(R)-amino-phenyl-isopropyl acetate amine salt
[0126] In a dry and clean reaction bottle, add 300 ml of ethanol and 10 g of 2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid. Heat to increase temperature and dissolve the compound. Add 15 g of R-amino-phenyl-isopropyl acetate amine. Slowly cool down to 20 deg C. Maintain temperature for 0.5 hours. Vacuum filtrate it. Obtain crude wet product of (L)-2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid-(R)-amino-phenyl-isopropyl acetate amine salt.
[0127] Then, add the crude wet product of (L)-2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid-(R)-amino-phenyl-isopropyl acetate amine salt to a dry and clean reaction bottle. Add 100 ml of ethanol. Heat to increase temperature to reflux. Slowly cool down to 20 deg C. Vacuum filtrate it. Dry in a drying oven for 8 hours at 50 to 60 deg C. Obtain 4.5 g of the product. Yield ratio: 30.5%.
[0128] The products from the Examples above (12˜25) are used as reactants in subsequential reaction step (step c).
Example 26
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid
[0129]
[0130] In a dry and clean reaction bottle, add 200 ml of ethanol and 10 g of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt. Elevate temperature to 50 deg C. Instill 3.5 g of hydrochloric acid. Maintain temperature for 1 hour. Cool down to 0 to 5 deg C. Vacuum filtrate it. Obtain 6.5 g of the product (D)-2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 93.7%. 1H NMR (500 MHz, DMSO-d6): 1.81, 2.87-2.92, 3.07-3.11, 4.43-4.48, 7.32-7.36, 7.44-7.47, 7.58-7.60, 7.64-7.66, 8.25-8.26, 12.74; MS (m/z): 224.0 (100), 167.1 (56), 165.2 (26), 282.9 ([MH+], 1).
Example 27
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid
[0131]
[0132] In a dry and clean reaction bottle, add 100 ml of tap water and 10 g of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt. Elevate temperature to 60 deg C. Instill 2.5 g of sulfuric acid. Maintain temperature for 10 min. Slowly cool reaction solution down to 0 to 5 deg C. Vacuum filtrate it. Obtain 6.5 g of the product (D)-2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 92.9%. Spectroscopic data as Example 26.
Example 28
Preparation of (L)-2-acetylamino-3-biphenyl propanoic acid
[0133]
[0134] In a dry and clean reaction bottle, add 50 ml of tetrahydrofuran and 10 g of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-1-phenethylamine salt. Elevate temperature to 40 deg C. Instill 3.5 g of hydrochloric acid. Maintain temperature for 1 hour. Cool down to 10 to 20 deg C. Vacuum filtrate it. Obtain 6.4 g of the product (L)-2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 91.4%. 1H NMR (500 MHz, DMSO-d6): 1.82, 2.88-2.93, 3.08-3.12, 4.45-4.50, 7.33-7.36, 7.44-7.47, 7.58-7.60, 7.65-7.66, 8.26-8.28, 12.76; MS (m/z): 224.0 (100), 167.1 (54), 165.1 (26), 282.9 ([MH+], 1).
Example 29
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid
[0135]
[0136] In a dry and clean reaction bottle, add 253 ml of methanol and 10 g of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt. Elevate temperature to 95 deg C. Instill 9.8 g of phosphoric acid. Maintain temperature for 5 hours. Cool down to 0 to 5 deg C. Vacuum filtrate it. Obtain 6.3 g of the product (D)-2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 90.7%. Spectroscopic data as Example 26.
Example 30
Preparation of (D)-2-acetylamino-3-biphenyl propanoic acid
[0137]
[0138] In a dry and clean reaction bottle, add 25 ml of isopropanol and 10 g of (D)-2-acetylamino-3-biphenyl propanoic acid-(S)-1-phenethylamine salt. Elevate temperature to 10 deg C. Instill 4.5 g of oxalic acid. Maintain temperature for 10 min. Slowly cool reaction solution down to 0 to 5 deg C. Vacuum filtrate it. Obtain 6.7 g of the product (D)-2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 95.7%. Spectroscopic data as Example 26.
Example 31
Preparation of (L)-2-acetylamino-3-biphenyl propanoic acid
[0139]
[0140] In a dry and clean reaction bottle, add 100 ml of tetrahydrofuran and 10 g of (L)-2-acetylamino-3-biphenyl propanoic acid-(R)-1-phenethylamine salt. Elevate temperature to 40 deg C. Instill 3.5 g of hydrochloric acid. Maintain temperature for 4 hours. Cool down to 10 to 20 deg C. Vacuum filtrate it. Obtain 6.6 g of the product (L)-2-acetylamino-3-biphenyl propanoic acid. Yield ratio: 94.3%. Spectroscopic data as Example 28.
Example 32
Preparation of (L)-2-propionyl amino-3-biphenyl propanoic acid
[0141]
[0142] In a dry and clean reaction bottle, add 200 ml of methanol and 10 g of (L)-2-propionyl amino-3-biphenyl propanoic acid-(R)-2-amino N,N-dimethyl-2-phenyl-acetamide salt. Elevate temperature to 90 deg C. Instill 15 g of citric acid. Maintain temperature for 5 hours. Cool down to 0 to 5 deg C. Vacuum filtrate it. Obtain 6.4 g of the product (L)-2-propionyl amino-3-biphenyl propanoic acid. Yield ratio: 91.8%. 1H NMR (500 MHz, DMSO-d6): 0.91-0.94, 2.06-2.11, 2.88-2.93, 3.08-3.12, 4.44-4.49, 7.32-7.36, 7.44-7.47, 7.57-7.59, 7.64-7.66, 8.15-8.16, 12.72; MS (m/z): 224.1 (100), 167.1 (46), 165.1 (20), 296.9 ([MH+], 1).
Example 33
Preparation of (D)-2-(N-formyl phenyl)amino-3-biphenylpropionic acid
[0143]
[0144] In a dry and clean reaction bottle, add 25 ml of isopropanol and 10 g of (D)-2-(N-formyl phenyl)amino-3-biphenyl propanoic acid-(S)-amino-phenyl-methyl acetate amine salt. Elevate temperature to 10 deg C. Instill 4 g of acetic acid. Maintain temperature for 30 min. Slowly cool reaction solution down to 0 to 5 deg C. Vacuum filtrate it. Obtain 6.0 g of the product (D)-2-(N-formyl phenyl)amino-3-biphenylpropionic acid. Yield ratio: 89.7%. 1H NMR (500 MHz, DMSO-d6): 3.11-3.16, 3.23-3.26, 4.64-4.69, 7.31-7.33, 7.34-7.45, 7.46-7.48, 7.58-7.60, 7.62-7.64, 7.82-7.84, 8.77-8.78, 12.83; MS (m/z): 224.0 (100), 167.1 (30), 165.1 (16), 105.1 (7), 77.1 (15), 344.8 ([MH+], 1).
Example 34
Preparation of (L)-2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid
[0145]
[0146] In a dry and clean reaction bottle, add 100 ml of tetrahydrofuran and 10 g of (L)-2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid-(R)-amino-phenyl-isopropyl acetate amine. Elevate temperature to 40 deg C. Instill 5 g of formic acid. Maintain temperature for 2.5 hours. Cool down to 10 to 20 deg C. Vacuum filtrate it. Obtain 5.3 g of the product, (L)-2-(N-para-chlorobenzoyl)amino-3-biphenyl propanoic acid. Yield ratio: 87.6%. 1H NMR (500 MHz, DMSO-d6): 3.10-3.14, 3.26-3.30, 4.61-4.66, 7.13-7.34, 7.39-7.44, 7.52-7.56, 7.61-7.63, 7.84-7.86, 8.75-8.77; MS (m/z): 224.1 (100), 167.1 (40), 165.1 (15), 139.1 (5), 111.1 (6), 378.9 ([MH+], 1). | The invention relates to a novel process, novel process steps and novel intermediates useful in the synthesis of pharmaceutically active compounds, in particular neutral endopeptidase (NEP) inhibitors. | 2 |
FIELD OF THE INVENTION
The present invention relates to a method of producing well-defined polycrystalline silicon areas, in particular for producing electrically conducting regions.
BACKGROUND INFORMATION
Electrically conducting regions may be defined in an amorphous silicon layer by controlled production of polycrystalline silicon regions. Such polycrystalline silicon regions may be characterized by a good electric conductivity, which may optionally be adjusted by introducing suitable dopants. Furthermore, polycrystalline silicon has a high piezoresistivity, so it may be suitable for use of wire strain gauges. Such wire strain gauges may be used in pressure sensors, for example. An electric resistance, which may be determined via a corresponding analyzer circuit, changes due to the acting pressure.
Polycrystalline silicon may be produced by a LPCVD method (low-pressure chemical vapor deposition), where the deposition rate may be determined by the process temperature. The process temperatures may vary in ranges between 400° C. and 900° C., depending on the layer of polycrystalline silicon to be deposited.
If such polycrystalline silicon layers are deposited on heat-sensitive substrates, e.g., stainless steel substrates, to produce high-pressure sensors, the high thermal stress associated with such deposition may constitute a high process risk. To define geometrically the electrically conducting regions, they may be well-defined by photolithographic process steps. This may require that a masking layer be applied to the polysilicon layer and exposed, then the exposed or unexposed regions be removed selectively and next the polysilicon layer may be plasma etched, for example. Such methods may be relatively complicated to control and may allow only a limited structural fidelity.
SUMMARY OF THE INVENTION
An exemplary method according to the present invention may reduce a thermal load in production of polycrystalline silicon regions. Furthermore, an exact structural definition may be achieved so that process reliability and yield may be increased. In situ high resolution structuring of the polycrystalline silicon regions in the submicrometer range may be possible because a substrate may be provided with a layer of a doped amorphous silicon, the amorphous silicon may be irradiated using a laser source to produce the electrically conducting regions, a shadow mask being positioned between the substrate and the laser source to provide definition of the electrically conducting regions. Irradiation of the doped amorphous silicon using a laser source, in particular an excimer laser, may permit a controlled breakup of the bond structure of the amorphous silicon through direct electronic energization and production of a polycrystalline lattice structure as a function of the wavelength used and the duration of the laser treatment. Polycrystalline silicon having a high electric conductivity, a low temperature dependence of the resistance, and a marked piezoresistivity may be obtained by previously doping the amorphous silicon. Use of the shadow masks in laser treatment may also eliminate a requirement for photolithographic process steps. This may reduce manufacturing costs on the whole.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 a through 1 e show manufacturing steps in the production of polycrystalline silicon regions in a first exemplary embodiment.
FIGS. 2 a through 2 f show process steps for production of polycrystalline silicon regions in a second exemplary embodiment.
DETAILED DESCRIPTION
FIGS. 1 a through 1 e show schematically individual process steps in the production of well-defined polycrystalline silicon regions by an exemplary method according to the present invention. A silicon oxide (SiO 2 ) layer 12 is first applied to a substrate 10 , e.g., a stainless steel substrate. Then as illustrated in FIG. 1 b , a layer 14 of doped amorphous silicon is deposited on this layer 12 . Then as illustrated in FIG. 1 c , a passivation layer 16 , e.g., of silicon dioxide (SiO 2 ) or silicon nitride (Si 3 N 4 ) is applied.
In a next step illustrated in FIG. 1 d , the composite of layers 10 , 12 , 14 , 16 is irradiated with a laser source 18 , e.g., an excimer laser, using electromagnetic radiation 20 . A shadow mask 22 having at least one mask opening 24 is arranged between laser source 18 and the composite of layers 10 , 12 , 14 , 16 . In the area of mask opening 24 , electromagnetic radiation 20 strikes the composite of layers 10 , 12 , 14 , 16 . Passivation layer 16 is transparent to electromagnetic radiation 20 . Crystallization occurs in the area of amorphous silicon layer 14 —well-defined geometrically by the mask opening—due to irradiation with electromagnetic radiation 20 , so that a polycrystalline silicon region 26 develops there. According to the contour of mask opening 24 , region 26 of the polycrystalline silicon is defined and is embedded in layer 14 of amorphous silicon. Due to the doping of amorphous silicon 14 , an electrically highly conductive polycrystalline silicon region 26 is formed. Since amorphous silicon 14 has a relatively high resistance and polycrystalline region 26 has a high electric conductivity, the electrically conductive regions are well-defined by region 26 .
Then as illustrated in FIG. 1 e , contact windows 28 are opened in passivation layer 16 , and a metallic coating (not shown here) is subsequently deposited in these windows. This metallic coating provides contacting of electrically conducting region 26 .
Contact windows 28 may likewise be opened by irradiation with a laser light. In this manner, contact windows 28 may be selectively opened by changing the wavelength of the laser light, for example, and/or increasing the power of laser source 18 and providing a suitable shadow mask.
Photolithographic process steps may not be required for production of well-defined electrically conductive regions 26 of polycrystalline silicon. Furthermore, irradiation with laser light may not be critical thermally, so that substrate 10 is not exposed to an excessive thermal load. In this manner, electrically conducting regions 26 may be produced with a high process reliability and a high process rate.
The exemplary method according to the present invention may be used, for example, in the production of high-pressure sensors in which substrate 10 is made of a stainless steel and electrically conducting regions 26 form wire strain gauges in a bridge circuit (e.g., a Wheatstone bridge). This may require only an appropriately adapted configuration of shadow mask 22 , which has an appropriate number of mask openings 4 (e.g., four in this case) for definition of the bridge resistors and corresponding openings to form the feeder lines (printed conductors). In the case of high-pressure sensors having stainless steel substrates or other structural components having non-silicon wafer substrates, the exemplary method according to the present invention may be desirable because it may eliminate the use of conventional photolithography which with these components may be a yield-limiting process that may be difficult to control.
FIGS. 2 a through 2 f illustrate another exemplary method according to the present invention. The same parts as in FIG. 1 are provided here with the same reference numbers and will not be explained again here, so that only the differences will be discussed.
In contrast with the exemplary embodiment illustrated in FIGS. 1 a through 1 e , polycrystalline silicon region 26 is structured before deposition of passivation layer 16 . This may make it possible, as illustrated in FIG. 2 d , to selectively remove the regions of amorphous silicon (former layer 14 ) surrounding polycrystalline silicon regions 26 produced then. Because of the prevailing etching selectivity between amorphous silicon and polycrystalline silicon, which may be particularly pronounced in the case of strong boron doping, this may be implemented by an etching attack, e.g., through the use of plasmas containing hydrogen or halogen, in a simple manner without a photolithography step. Following this, as illustrated in FIG. 2 e , passivation layer 16 is deposited and then ( FIG. 2 f ) contact windows 28 are structured therein. These windows are then metal plated again so that polycrystalline silicon regions 26 may be connected to an electric circuit.
In the first exemplary embodiment, the process steps illustrated in FIGS. 1 a , 1 b and 1 c , and in the second exemplary embodiment, the steps illustrated in FIGS. 2 a and 2 b may be performed immediately in succession in one recipient without any negative effect on the vacuum atmosphere required in the meantime, or at least having to release the vacuum. This may yield on the whole a shorter process running time. Also, a thermal stress on substrate 10 may be greatly reduced in comparison with the conventional LPCVD deposition method for polycrystalline silicon. In addition, due to the prior doping of amorphous silicon in layer 14 and the subsequent well-defined exposure of regions 26 to electromagnetic radiation 20 , very homogeneous polycrystalline silicon regions 26 may be obtained, resulting in a considerable reduction in asymmetry in the entire bridge when used as wire strain gauges in a Wheatstone resistance bridge, so that high-precision piezoresistive pressure sensors may be produced through this exemplary method according to the present invention. | A method of producing well-defined polycrystalline silicon regions is described, in particular for producing electrically conducting regions, in which a substrate is provided with an insulating layer and a layer of doped amorphous silicon, electromagnetic irradiation is performed using a laser source to produce the electrically conducting regions, and a shadow mask is positioned between the laser source and the substrate having the layer for definition of the contours of the electrically conducting regions. | 7 |
This is a continuation of application Ser. No. 08/106,149, filed Aug. 13, 1993, now abandoned, which is a continuation of application Ser. No. 07/485,376, filed Feb. 26, 1990, now abandoned.
REFERENCE TO MICROFICHE APPENDIX
The application includes a microfiche appendix pursuant to 37 CFR §1.96(b) containing 34 microfiche having 1729 frames.
BACKGROUND OF THE INVENTION
The invention relates to the physical design of a database.
Database systems are typically not self-optimizing in terms of their physical design. That is, they do not automatically alter the particular layout and storage characteristics of their data and operations. Most systems do include features that allow a user to specify certain settings, such as a choice of indexed or sequential keys for data records, the expected size of data files, or the storage locations of the data and program files. However, the appropriate settings of these and other features usually requires unique expertise that a general user does not possess.
A human database expert, therefore, is usually required to fine tune the physical design of a database in order to provide better runtime performance. For example, the expert can make some improvements that yield a higher application throughput (i.e., a greater number of transactions processed) by reducing the number of necessary input/output operations (I/Os) and conducting more efficient buffering of data in memory. Other improvements include providing more efficient utilization of the central processing unit (CPU) and disk storage units by partitioning data across multiple disks, calculating optimal data density (i.e., providing large enough storage areas to contain each section of data), and calculating optimal placement of data within the data files.
As noted, the physical structure of a database can be defined as the particular storage characteristics of a collection of interrelated data stored as one or more stored records. A stored record is the basic unit of storage which corresponds to one logical record and contains all pointers, record lengths, and other identifiers necessary to represent pieces of data. Aspects of the physical structure of a database include, for example, the location and size of files, the access methods and keys to database records, and the placement of records within the database. Not surprisingly, the design of the physical structure has a significant impact on performance of the database as a whole. This impact, however, can differ from database to database (even among databases having the same physical structure). For example, the physical structure's impact on performance can vary depending on the amount of data in the database (i.e., the "data volume"). The impact can also vary depending on the "physical constraints" of the system, e.g., the number of storage devices available, the amount of space available on the storage devices, the amount of I/O taking place, and the amount of random access memory (RAM) available. And finally, the impact can vary depending on the "workload" of the database, e.g., the type, frequency, priority, and sequence of database operations.
SUMMARY OF THE INVENTION
In general, the invention features a physical database designer which is embodied in computer software that generates a physical database design. The designer follows a process which includes the steps of (a) entering a logical schema representing the database to be designed; (b) entering a hierarchial definition of the workload experienced by the database, which includes, for each level of a hierarchy of operations, a separate specification of workload; and (c) applying expert rules to the logical schema and the workload definition to generate the physical database design.
In preferred embodiments, the physical database design generated by the designer can be a relational database or a codasyl database. Another feature of the preferred embodiment provides that the designer compares the workload's different operations on the database by normalizing the hierarchical workload definition so that the operations are treated uniformly when creating the physical database design. Also, the workload hierarchy includes at least three levels: programs, transactions within programs, and requests within transactions. A fourth level, applications, is possible as well and denotes groupings of related programs. In the embodiment discussed below, the information contained in the workload definition includes the importance of operations at different levels of the hierarchy, the frequency of operations at different levels of the hierarchy, and the access mode and lock mode of transactions. Other types of information might likewise be stored. Finally, one element of the improved physical database design generated by the designer is a definition of record placement, i.e., a particularly efficient storage layout for the data based on the workload and other inputs. For example, the designer can use the following as inputs, (a) a volume definition for the database which includes information on the number of occurrences of the operation such as the volatility, the minimum and maximum number of occurrences; and (b) a physical constraints definition for the database which indicates the size of main memory available to the database, the size of disk memories on which records in the database are stored, and the maximum number of concurrent users of the database.
The invention automates the design of the physical structure of a database and allows users to improve the performance of the database and any applications that rely on it. To do this, the system applies information regarding the data volume, physical constraints, and workload of the database to the design of the physical structure of the database. The information regarding the data volume and physical constraints can be generated by hand or input from various database dumps. Likewise, the workload analysis can be generated by hand or by an application event-based data collector such as that described in a copending application by Philip K. Royal, entitled SYSTEM AND METHOD FOR APPLICATION EVENT COLLECTION, filed on even date with this application.
The invention can be used to design databases that use storage space efficiently and that partition data across the available storage space to reduce the I/O overhead of database operations. For example, if the workload analysis indicates that operations on two particular objects (i.e., pieces of data) often occur in sequence, the invention recommends that objects be placed in proximity to one another on the storage device to minimize the number of I/O operations necessary to access the objects. In addition, the system can also size data according to the workload of the database and indicate how to arrange the data in "clusters" or groups within a database file. That is, the system stores related record types, e.g., all records processed by a particular database request or transaction, in the same area of the database. This technique helps to prevent excessive disk head movement that slows response time.
Other advantages and features will become apparent from the following description, and from the claims.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 is a block diagram of the components of a physical database design system according to the present invention.
FIG. 2 is a flow chart which illustrates the steps necessary to enter design inputs, i.e., logical schema, workload, volume, and constraints.
FIG. 3 is a flow chart which illustrates the steps necessary to generate the physical structure.
FIG. 4 is a flow chart which illustrates the steps necessary to output the creation parameters and runtime parameters to implement the physical structure.
Table 1 is a sample logical database design (logical schema) used by the system.
Table 2 is a sample workload definition used by the system.
Table 3 is a sample data volume definition used by the system.
Table 4 is a sample physical constraints definition used by the system.
Table 5 (supplied in Appendix A) is a sample output of creation parameters and runtime parameters necessary to create the physical structure produced by the system.
Shown in block diagram form in FIG. 1, the present invention is a physical database design system 10 which assists a user in the fine tuning of a database by applying a set of rules to a logical database structure 14 (also referred to as a "logical schema"). For example, the rule shown below determines whether a database table should be placed according to its type and index structure. Other example rules are supplied in Appendix A attached hereto. Generally, records of the same type and their associated index structure are stored on the same database page so that a retrieval of an index key at the particular page also retrieves the data associated with that key. Thus, the number of I/O operations caused by page retrievals is reduced and the performance of the database is improved.
______________________________________Domain: VAX Rdb/VMSContext: Table placementSource: VAX Rdb/VMS DocumentationRule #: 1______________________________________"If a table has an index, and is accessed by a direct key, andand its importance is higher than sequential importancethen this table ia a candidate for placement."Rule:If --> table has a hash index as its best index, and the index importance > sequential importance for the object and there is no instance in pdd$placeThen --> place the table via its hash index and set the placement type to direct.______________________________________
Referring again to FIG. 1, the logical schema 14 can be derived from several sources, including a database rootfile 16 or a database utility output 20. The database utility output is a language file, e.g., Data Definition Language (DDL), that is parsed via a YET Compiler Compiler (YACC) parser to create a generic internal representation, i.e., the logical schema 14. Thus, the system 10 can accept and improve the design of any type of database, e.g., a CODASYL or a relational database.
To improve the logical schema 14 described above, the system 10 relies upon the rules and also upon the following: a database workload definition 22, which can be generated by a human user 24 or derived from the output of an event performance collector 26; a data volume definition 28, which can be generated by the user or derived from a database rootfile 30 or database utility output such as the "database analyze output" 32 shown in FIG. 1; and a design constraints definition 34 which can be generated by the user.
A physical database designer 36 also shown in FIG. 1 applies the information of the workload 22, the data volume 28, the design constraints 34, and the rules to the logical schema 14. The results of this application include a storage schema 38, i.e., a physical database structure which defines the on-disk structure of the logical schema 14. This physical structure is accompanied by a set of runtime parameters 42 and a set of creation parameters 44.
The user can use the creation parameters 44 to implement the physical database structure 38, and use the runtime parameters 42 to unload data from an old database and reload it in the new database. A detailed description of each of the components described in connection with FIG. 1, beginning with the logical schema 14, is provided below in connection with FIGS. 2-7.
Structure of the Logical Schema
The logical schema 14 of FIG. 1 can be thought of as defining record and field structures with which data entities are associated. An example of a logical schema 14 for a personnel database is shown below in Table 1. As shown, the schema includes a number of tables, i.e., COLLEGES, DEGREES, DEPARTMENTS, EMPLOYEES, JOBS, JOB -- HISTORY, RESUMES, SALARY -- HISTORY, and WORK -- STATUS. Each table can be thought of as the definition of a record data structure. Each table also has a number of column elements which can be thought of as fields in the record. For example, the COLLEGES table includes the column elements COLLEGE -- CODE, COLLEGE -- NAME, CITY, STATE, and POSTAL CODE. Each column element has associated with it a data type, e.g., character, integer, or date. The data entities which later fill the "rows" under the column elements can be related by their data type, but can also form relationships to one another by their appearance in multiple tables. For example, the COLLEGE -- CODE column element appears in the COLLEGES table and the DEGREES table.
TABLE 1______________________________________Tables in shema PersonnelCOLLEGESDEGREESDEPARTMENTSEMPLOYEESJOBSJOB.sub.-- HISTORYRESUMESSALARY.sub.-- HISTORYWORK.sub.-- STATUSColumns in table COLLEGESColumn Name Data TypeCOLLEGE.sub.-- CODE CHAR (4)COLLEGE.sub.-- NAME CHAR (25)CITY CHAR (20)STATE CHAR (2)POSTAL.sub.-- CODE CHAR (5)Columns in table DEGREESColumn Name Data TypeEMPLOYEE.sub.-- ID CHAR (5)COLLEGE.sub.-- CODE CHAR (4)YEAR.sub.-- GIVEN SMALLINTDEGREE CHAR (4)DEGREE.sub.-- FIELD CHAR (20)Columns in table DEPARTMENTSColumn Name Data TypeDEPARTMENT.sub.-- CODE CHAR (4)DEPARTMENT.sub.-- NAME CHAR (30)MANAGER.sub.-- ID CHAR (5)BUDGET.sub.-- PROJECTED INTEGERBUDGET.sub.-- ACTUAL INTEGERColumns in Table EMPLOYEESColumn Name Data TypeEMPLOYEE.sub.-- ID CHAR (5)LAST.sub.-- NAME CHAR (14)FIRST.sub.-- NAME CHAR (10)MIDDLE.sub.-- INITIAL CHAR (1)ADDRESS.sub.-- DATA.sub.-- 1 CHAR (25)ADDRESS.sub.-- DATA.sub.-- 2 CHAR (25)CITY CHAR (20)STATE CHAR (2)POSTAL.sub.-- CODE CHAR (5)SEX CHAR (1)BIRTHDAY DATESTATUS.sub.-- CODE CHAR (1)Columns in table JOBSColumn Name Data TypeJOB.sub.-- CODE CHAR (4)WAGE.sub.-- CLASS CHAR (1)JOB.sub.-- TITLE CHAR (20)MINIMUM.sub.-- SALARY INTEGERMAXIMUM.sub.-- SALARY INTEGERColumns in table JOB.sub.-- HISTORYColumn Name Data TypeEMPLOYEE.sub.-- ID CHAR (5)JOB.sub.-- CODE CHAR (4)JOB.sub.-- START DATEJOB.sub.-- END DATEDEPARTMENT.sub.-- CODE CHAR (4)SUPERVISOR.sub.-- ID CHAR (5)Column in table RESUMESColumn Name Data TypeEMPLOYEE.sub.-- ID CHAR (5)Column in table SALARY.sub.-- HISTORYColumn Name Data TypeEMPLIYEE.sub.-- ID CHAR (5)SALARY.sub.-- AMOUNT INTEGERSALARY.sub.-- START DATESALARY.sub.-- END DATEColumns in table WORK.sub.-- STATUSColumn Name Data TypeSTATUS.sub.-- CODE CHAR (1)STATUS.sub.-- NAME CHAR (8)STATUS.sub.-- TYPE CHAR (14)______________________________________
The database workload 22 defines database transactions performed on the data entities in the tables and column elements shown above and is described next in connection with an example workload for the personnel database.
Structure of the Database Workload
The database workload definition 22, an example of which is shown below in Table 2, describes the expected database operations on the data entities in the tables and column elements defined in the logical schema 14. In the workload 22, the operations on the logical schema 14 (i.e., applications, programs, transactions, and requests) are arranged in a hierarchical fashion. That is, an application includes one or more programs; a program includes one or more transactions; and a transaction includes one or more requests. Briefly, then, within this hierarchical structure, the workload 22 defines which tables of the logical schema 14 are accessed, how the tables are accessed (access mode, lock mode, and operation), how frequently they are accessed (frequency and cycle), and how important it is that a operation complete in the shortest time possible importance ) .
TABLE 2______________________________________Workload for Schema Personnel;Application EMPLOYEESImportance 10;Program JOBINFOCycle DAILYFrequency 80.00Importance 10;Transaction CHECK.sub.-- DEPT.sub.-- INFOAccess.sub.-- mode READ ONLYLock.sub.-- mode SHAREDFrequency 1.00Importance 10;Request DEPTCODE.sub.-- 1 Frequency 1.00SELECT column.sub.-- list FROM JOB.sub.-- HISTORY WHERE DEPARTMENT CODE = "literal";Request DEPTCODE.sub.-- 2 Frequency 1.00SELECT column.sub.-- list FROM JOB.sub.-- HISTORY WHERE DEPARTMENT.sub.-- CODE = "literal" AND JOB.sub.-- END > "literal";Transaction CHECK.sub.-- EMPLOYEE.sub.-- EXISTANCEAccess.sub.-- mode READ ONLYlock.sub.-- mode SHAREDFrequency 1.00Importance 10;Request EMPIDCHK.sub.-- 1 Frequency 1.00SELECT column.sub.-- list FROM EMPLOYEES WHERE EMPLOYEE.sub.-- ID = "literal";Request EMPIDCHK.sub.-- 2 Frequency 1.00SELECT column.sub.-- list FROM JOB.sub.-- HISTORY WHERE EMPLOYEE.sub.-- ID = "literal";Transaction CHECK.sub.-- JOB.sub.-- INFOAccess.sub.-- mode READ ONLYLock.sub.-- mode SHAREDFrequency 1.00Importance 10Request JOBCODE.sub.-- 1 Frequency 1.00SELECT column.sub.-- list FROM JOBS WHERE JOB.sub.-- CODE = "literal";Request JOBCODE.sub.-- 2 Frequency 1.0SELECT column.sub.-- list FROM JOBS.sub.-- HISTORY WHERE JOB.sub.-- CODE = "literal";Transaction MODIFY.sub.-- EMP.sub.-- STATUSAccess.sub.-- mode READ WRITELock.sub.-- mode PROTECTEDFrequency 1.00Importance 10;Request MODEMP1 Frequency 1.00UPDATE EMPLOYEES SET EMPLOYEE.sub.-- ID ="literal" WHERE EMPLOYEE.sub.-- ID = "literal";Request MODEMP2 Frequency 1.00UPDATE JOB.sub.-- HISTORY SET EMPLOYEE.sub.-- ID ="literal" WHERE EMPLOYEE.sub.-- ID = "literal";Request MODEMP3 Frequency 1.00UPDATE SALARY.sub.-- HISTORY SET SALARY.sub.-- END ="literal" WHERE EMPLOYEE.sub.-- ID = "literal";Transaction MODIFY.sub.-- JOBEND.sub.-- DATEAccess.sub.-- mode READ WRITELock.sub.-- mode EXCLUSIVEFrequency 1.00Importance 10;Request JOBEND Frequency 1.00UPDATE JOB.sub.-- HISTORY SET EMPLOYEE.sub.-- ID ="literal" WHERE EMPLOYEE.sub.-- ID = "literal" AND JOB.sub.-- END > "literal";Transaction MODIFY.sub.-- SALEND.sub.-- DATEAccess.sub.-- mode READ WRITELock.sub.-- mode PROTECTEDRequest SALEND Frequency 1.00UPDATE SALARY.sub.-- HISTORY SET SALARY.sub.-- END ="literal" WHERE EMPLOYEE.sub.-- ID = "literal" AND SALARY.sub.-- END > "literal" AND SALARY.sub.-- END <> "literal" AND SALARY.sub.-- END >= "literal" AND SALARY.sub.-- END <= "literal"Request STORESAL Frequency 1.00INSERT INTO SALARY.sub.-- HISTORY (column.sub.-- list)VALUES (value.sub.-- list);Transaction STORE.sub.-- JOBDEPTAccess.sub.-- mode READ WRITELock.sub.-- mode EXCLUSIVEFrequency 1.00Importance 10Request JOBSTORE Frequency 1.00INSERT INTO JOB.sub.-- HISTORY (column.sub.-- list)VALUES (value.sub.-- list);______________________________________
Access to data entities in a table is defined by several conditions. First, an access mode statement defines the type of operation that a particular column element is the object of, e.g., a READ, WRITE, or UPDATE operation. Second, a lock mode statement defines whether the data entity can be accessed simultaneously by more than one operation, e.g., whether the column element allows SHARED, EXCLUSIVE, or PROTECTED access. For example, data entities in the EMPLOYEES table shown above are accessed by a CHECK -- DEPT -- INFO transaction which defines all requests for operations on the table as READ ONLY and SHARED. Finally, the column elements by which data entities in a table are usually accessed are specified in requests. For example, in the request DEPTCODE -- 1 shown in Table 2 the data entities in the table DEPARTMENTS are accessed by the DEPARTMENT -- CODE column element.
The frequency of access to a table is defined by the number of times the data entities in a table are accessed in a particular cycle of time, i.e., the number of times per hour, day, week, month, quarter, or year. If a table is usually accessed by a particular column element, the frequency of access via that element can be very high in a single cycle. For example, the EMPLOYEES table might be accessed by the EMPLOYEE -- ID column element 50 or 100 times a day. On the other hand, if an table is seldom accessed by the contents of a different column element, the frequency of access can be very low in a single cycle. For example, the EMPLOYEE table might be accessed by the ADDRESS -- DATA -- 1 column element only once a week.
The importance of an application, program, or transaction is a ranking on a scale of one to ten which corresponds to how important it is that the operation complete in the shortest time possible. For example, an application might be considered fairly important and rank a score of 8, while a program within the application might be very important and rank a score of 10. In some specific cases, rankings may seem to conflict with one another. For example, a transaction that looks up an employee's phone number and is performed many times a day, may seem at first to outrank a transaction which looks up an employee's address for payroll processing once a week. However, the payroll processing is likely considered a transaction which outranks other transactions and so requires a higher rating.
Generally, the importance ratings determine several details of the final storage schema 38, e.g., the critical access paths in the schema. Thus, by carefully selecting an importance for each application, program, and transaction, a user can create a workload definition 22 that identifies which aspects of the database design to optimize. A description of each type of operation on the logical schema, i.e., application, program, transaction, and request, follows.
An application is a collection of programs that perform a distinct business function. For example, the "EMPLOYEES" application shown in Table 2 above retrieves and updates information about a company's employees, via individual programs such as "JOBINFO." Note that applications are typically not defined by an access mode, lock mode, frequency, or cycle since they are merely a means for grouping related programs. However, the importance of the application is defined, specifically, as a function of the importance of the programs within the application. For example, the EMPLOYEES application is rated at 8.
Next, a program, e.g., JOBINFO, is a collection of transactions which performs a specific function or task. The workload 22 defines a separate program for each executable image or command procedure that accesses the database, e.g., application programs, or VAX Datatrieve, SQL, or DBQ procedures. Within each application, the frequency, cycle, and importance for each program is defined. For example, the cycle of the JOBINFO program is defined as DAILY, its frequency is 80.00, and its importance is 10.
Next, a transaction is a recoverable unit of database activity. For example, JOBINFO includes the transactions CHECK -- DEPT -- INFO, CHECK -- EMPLOYEE -- EXISTENCE, and CHECK -- JOB -- INFO. The access mode for the CHECK -- DEPT -- INFO transaction is defined as READ ONLY, the lock mode is SHARED, the frequency is 1.00, and the importance is 10. Note that all transactions have the same cycle, i.e., one execution of the program.
Finally, each transaction is a collection of requests, i.e., single database accesses. Each access is written in a database language such as SQL or DML. For example, referring again to Table 2, the first request in the CHECK -- DEPT -- INFO transaction is the "DEPTCODE -- 1" request which is defined by the SQL statement: "SELECT column -- list FROM DEPARTMENTS WHERE DEPARTMENT -- CODE="literal" AND JOB -- END>"literal".
The workload definition 22 as defined above is input to the physical database designer 36 and analyzed by an expert system to create an optimal physical design. A description of the analysis done by the expert system on the workload 22 is presented below.
Analysis of Workload Definition (KB -- ANALYSIS)
The analysis and characterization of the workload 22 is the first step in the design process once all of the design inputs have been obtained. The analysis includes the steps of annualizing the frequencies based on processing cycle, normalizing the frequencies for the transactions and requests, and creating an absolute importance for each request.
The expert system within the physical database designer 36 contains a module KB ANALYSIS which performs several operations on the workload data in order to determine certain details of "the improved database design, i.e., the final storage structure 38. First, KB -- ANALYSIS "annualizes" the occurrences of each request in the workload definition 22. That is, it converts the number of occurrences from the number of occurrences per cycle to the number of occurrences per year. For example, if the cycle is hourly, KB -- ANALYSIS annualizes the number of occurrences by multiplying hours per day * days per week , weeks per month , months per quarter * quarters per year.
Second, KB -- ANALYSIS "normalizes" the occurrences of transactions and requests so that the execution counts can be accurately compared. To do this, KB -- ANALYSIS first updates the absolute count of transactions by multiplying the execution count of transactions by the execution count of programs and assigning the result to the absolute count of transactions. Then, KB -- ANALYSIS updates the absolute number of requests by multiplying the absolute count of transactions by the execution count of requests and assigning the result to the absolute number of requests.
Third, KB -- ANALYSIS normalizes the importance rating of the requests so that the ratings of all requests in the workload can be accurately compared. That is, the importance of each request is calculated based on the importance of the application, program, and transaction in which the request occurs. To calculate the relative importance of each request, KB -- ANALYSIS uses the following algorithm:
request importance=request absolute frequency/(importance high bound-request importance) 2
Where:
______________________________________importance high bound = application multiplier +program multiplier +transaction multiplier +request multiplier + 1request importance = application importance * application multiplier + program importance * program multiplier + transaction importance * transaction multiplier + request importance * request multiplier______________________________________
And where any multiplier=10**(level-1). For example,
______________________________________application multiplier = 10**3 = 1000program multiplier = 10**2 = 100transaction multiplier = 10**1 = 10request multiplier = 10**0 = 1______________________________________
Finally, KB -- ANALYSIS combines the requests of all transactions in the workload definition 22 into one access path to each data entity for every type of access defined in the workload. To do this, KB -- ANALYSIS sorts all requests in a particular order, e.g., by each "break" in the sort order, i.e., by design, retrieval -- mode, verb, adverb, object, select -- type, or select -- object. KB -- ANALYSIS also sums the importance at each break in the sort order.
Structure of the Data Volume Definition
The data volume definition 28 of FIG. 1 describes the amount of data in the database. The system 10 uses this information in several ways, e.g., to optimize the size and number of database files, areas within the files. Briefly, the data volume is defined as the minimum, average, and maximum number of occurrences of each table and column element, as well as the volatility of the tables and elements. For example, an employee database might contain one EMPLOYEES table for all employees in a company. Therefore, the minimum number of occurrences of data entities in the EMPLOYEES table is equal to the number of employees. Over time, however, the number of employees can vary. This variance is accounted for in the average and maximum number of occurrences of data entities in the EMPLOYEES table. For example, if the company expects to double its number of employees, the average and maximum numbers of entities in the EMPLOYEES table is increased in the data volume definition.
Further, because few databases contain static data, i.e., unchanging data, the system allows users to rate the volatility of each table and column element on a scale of one to ten (one for very stable and ten for very volatile). For example, the number of entities in the EMPLOYEES table can be somewhat volatile, e.g., subject to many additions and deletions, and receive a rating of 8. On the other hand, the number of entities in the COLLEGES table, for example, may be quite stable and receive a rating of 2. If the number of entities in a table is likely to change no more or no less than the number of other entities in the database, the table is or column element is typically assigned a volatility rating of 5.
Table 3 below shows an example volume definition for the personnel database. The overall definition is assigned values of zero occurrences and a middle range volatility rating of 5. Likewise, each table and column entry is assigned values to indicate the number of occurrences of entities in the table or column and its volatility. For example, the number of occurrences of data entities in the COLLEGES table has a minimum, average, and maximum value of 16, and a volatility of 5.
TABLE 3______________________________________Volume for Schema Personnel Default Minimum is 0.00 Average is 0.00 Maximum is 0.00 Volatility is 5; Table COLLEGES Minimum is 16.00 Average is 16.00 Maximum is 16.00 Volatility is 5 Column COLLEGE.sub.-- CODE Minimum is 16.00 Average is 16.00 Maximum is 16.00 Volatility is 5 Column COLLEGE.sub.-- NAME Minimum is 16.00 Average is 16.00 Maximum is 16.00 Volatility is 5 Column CITY Minimum is 16.00 Average is 16.00 Maximum is 16.00 Volatility is 5 Column STATE Minimum is 16.00 Average is 16.00 Maximum is 16.00 Volatility is 5 Column POSTAL.sub.-- CODE Minimum is 16.00 Average is 16.00 Maximum is 16.00 Volatility is 5Table DEGREES Minimum is 664.00 Average is 664.00 Maximum is 664.00 Volatility is 5; Column EMPLOYEE.sub.-- ID Minimum is 664.00 Average is 664.00 Maximum is 664.00 Volatility is 5; Column COLLEGE.sub.-- CODE Minimum is 664.00 Average is 664.00 Maximum is 664.00 Volatility is 5; Column YEAR.sub.-- GIVEN Minimum is 664.00 Average is 664.00 Maximum is 664.00 Volatility is 5; Column DEGREE Minimum is 664.00 Average is 664.00 Maximum is 664.00 Volatility is 5; Column DEGREE.sub.-- FIELD Minimum is 664.00 Average is 664.00 Maximum is 664.00 Volatility is 5;Table DEPARTMENTS Minimum is 26.00 Average is 26.00 Maximum is 26.00 Volatility is 5; Column DEPARTMENT.sub.-- CODE Minimum is 26.00 Average is 26.00 Maximum is 26.00 Volatility is 5; Column DEPARTMENT.sub.-- NAME Minimum is 26.00 Average is 26.00 Maximum is 26.00 Volatility is 5; Column MANAGER.sub.-- ID Minimum is 26.00 Average is 26.00 Maximum is 26.00 Volatility is 5; Column BUDGET.sub.-- PROJECTED Minimum is 26.00 Average is 26.00 Maximum is 26.00 Volatility is 5; Column BUDGET.sub.-- ACTUAL Minimum is 26.00 Average is 26.00 Maximum is 26.00 Volatility is 5;TABLE EMPLOYEES Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column EMPLOYEE.sub.-- ID Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column LAST.sub.-- NAME Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column FIRST.sub. -- NAME Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column MIDDLE.sub.-- INITIAL Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column ADDRESS.sub.-- DATA.sub.-- 1 Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column ADDRESS.sub.-- DATA.sub.-- 2 Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column CITY Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column STATE Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column POSTAL.sub.-- CODE Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column SEX Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column BIRTHDAY Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5; Column STATUS.sub.-- CODE Minimum is 100.00 Average is 100.00 Maximum is 100.00 Volatility is 5;Table JOBS Minimum is 60.00 Average is 60.00 Maximum is 60.00 Volatility is 5; Column JOB.sub.-- CODE Minimum is 60.00 Average is 60.00 Maximum is 60.00 Volatility is 5; Column WAGE.sub.-- CLASS Minimum is 60.00 Average is 60.00 Maximum is 60.00 Volatility is 5; Column JOB.sub.-- TITLE Minimum is 60.00 Average is 60.00 Maximum is 60.00 Volatility is 5; Column MINIMUM.sub.-- SALARY Minimum is 60.00 Average is 60.00 Maximum is 60.00 Volatility is 5; Column MAXIMUM.sub.-- SALARY Minimum is 60.00 Average is 60.00 Maximum is 60.00 Volatility is 5;Table JOB.sub.-- HISTORY Minimum is 1096.00 Average is 1096.00 Maximum is 1096.00 Volatility is 5; Column EMPLOYEE.sub.-- ID Minimum is 1096.00 Average is 1096.00 Maximum is 1096.00 Volatility is 5; Column JOB.sub.-- CODE Minimum is 1096.00 Average is 1096.00 Maximum is 1096.00 Volatility is 5; Column JOB.sub.-- START Minimum is 1096.00 Average is 1096.00 Maximum is 1096.00 Volatility is 5; Column JOB.sub.-- END Minimum is 1096.00 Average is 1096.00 Maximum is 1096.00 Volatility is 5; Column DEPARTMENT.sub.-- CODE Minimum is 1096.00 Average is 1096.00 Maximum is 1096.00 Volatility is 5; Column SUPERVISOR.sub.-- ID Minimum is 1096.00 Average is 1096.00 Maximum is 1096.00 Volatility is 5;Table RESUMES Minimum is 0.00 Average is 0.00 Maximum is 0.00 Volatility is 5; Column EMPLOYEE.sub.-- ID Minimum is 0.00 Average is 0.00 Maximum is 0.00 Volatility is 5; Segmented.sub.-- string RESUME Minimum is 0.00 Average is 0.00 Maximum is 0.00 Volatility is 5;Table SALARY.sub.-- HISTORY Minimum is 2916.00 Average is 2916.00 Maximum is 2916.00 Volatility is 5; Column EMPLOYEE.sub.-- ID Minimum is 2916.00 Average is 2916.00 Maximum is 2916.00 Volatility is 5; Column SALARY.sub.-- AMOUNT Minimum is 2916.00 Average is 2916.00 Maximum is 2916.00 Volatility is 5; Column SALARY.sub.-- START Minimum is 2916.00 Average is 2916.00 Maximum is 2916.00 Volatility is 5; Column SALARY.sub.-- END Minimum is 2916.00 Average is 2916.00 Maximum is 2916.00 Volatility is 5;Table WORK.sub.-- STATUS Minimum is 12.00 Average is 12.00 Maximum is 12.00 Volatility is 5; Colum STATUS.sub.-- CODE Minimum is 12.00 Average is 12.00 Maximum is 12.00 Volatility is 5; Column STATUS.sub.-- NAME Minimum is 12.00 Average is 12.00 Maximum is 12.00 Volatility is 5; Column STATUS.sub.-- TYPE Minimum is 12.00 Average is 12.00 Maximum is 12.00 Volatility is 5;______________________________________
The final input to the physical database designer 36, i.e., the design constraints definition 34 is described below.
Structure of the Design Constraints The design constraints definition 34 of FIG. 1 describes the constraints on the physical resources used by the database, and is used to help create the storage schema 38. Briefly, the constraints include the maximum number of users permitted to access the database at one time, the number of storage devices available to store files associated with the database, the maximum amount of space available on any one of the devices, the maximum amount of memory available to applications using the database (roughly half the amount of free memory), and the percentage of available memory to be used by applications. For example, if two thirds of the available system memory is to be used by the database applications, the available memory is 67%.
As an example, Table 4 below shows design constraint definition for the personnel database. The number of storage devices, i.e., disks, is 10 and provides 100,000 blocks of disk storage for 50 users. The maximum amount of memory available to applications is 64 megabytes, and the applications actually use 96% of the available memory.
TABLE 4______________________________________Environment for physical.sub.-- design physical; Disks is 10; Area.sub.-- size is 100000 blocks; Users is 50; Maximum.sub.-- memory is 64 megabytes; Available.sub.-- memory is 96 percent;______________________________________
General Operation: Inputs to the Physical Database Designer
FIG. 2 is a flow chart which illustrates the steps of entering the design inputs, i.e., the logical schema 14, the workload 22, the constraints, 34, and the data volume 28. First, the physical database designer 36, creates a physical design into which it will store the results of its work. To initiate this process, the designer 36 prompts the user for the file name of a logical schema 14 and workload 22 to use as inputs to the design process (step 100). Next, the designer 36 creates an instance of the logical schema 14 (step 102) and checks to see that the schema is unique (step 104), i.e., that there are no other instances of the same logical schema and only one logical schema for the physical design. If the schema 14 is not unique, the designer 36 returns an error (step 106). Otherwise, i.e., if the schema 14 is unique, the designer 36 creates instances for each table and column element in the schema (step 108).
In the next processing phase, the designer 36 creates volume instances for each table and column element in the logical schema (step 112). The designer 36 next creates a instance of the workload 22 (step 114) and checks to see that the workload is unique (step 116), i.e., that there is one workload only for the physical design. If the workload 22 is not unique, the designer 36 returns an error (step 118). Otherwise, i.e., if the workload 22 is unique, the designer 36 creates an instance for each request, transaction, program, and application in the workload 22 (step 120). Finally, the designer 36 validates each request instance against the table and column element instances for the logical schema and prompts the user to resolve any inconsistencies (step 122).
Having described the inputs to the designer 36, we next describe the outputs from the designer 36.
Structure of the Runtime Parameters and Creation Parameters
The runtime parameters 42 and creation parameters 44 of FIG. 1 are contained in a command procedure, e.g., a series of Digital Command Language (DCL) commands, which the user can use to implement the improved database. That is, when the command procedure is run, it unloads the data entities from an existing database, optimizes the physical design of the database, and reloads the data entities into a new database built upon the optimized design. Table 5 below shows an example file of a command procedure used to optimize the personnel database.
Briefly, the command procedure shown in Table 5 (supplied in Appendix B) provides the user with information regarding the optimization process it is undertaking and allows the user an opportunity to change the input to various steps in the process. For example, if the database has tables of data entities which depend upon one another, i.e., have matching records in them, then the procedure prompts the user to edit a load sequence so that the tables are loaded in the proper order. Next, the procedure instructs the user as to what is necessary to implement the new database, e.g., a logical schema and enough space to temporarily store the data found in the tables of the existing database. And finally, the procedure informs the user as to how the storage of the data entities has been optimized and offers the user an opportunity to change the optimization.
Once the procedure has provided the user with a description of how the database will be changed, it proceeds to unload the data entities from the existing database. After the data entities are unloaded, the procedure defines the new database, creates storage areas according to the storage schema 38, and creates storage maps for tables, i.e., mapping of the tables to areas of the database. Once the new database is complete, the procedure sorts the unloaded data entities from the old database, and loads the sorted data entities into the new database. The process followed by the command procedure in the runtime parameters 42 and the creation parameters 44 can be further documented in various textual reports.
General Operation: Physical Database Designer Creates Design
FIG. 3 is a flow chart illustrating steps which an expert system in concert with the designer 36 takes in order to generate an optimal physical design. First, the designer 36 analyzes the applications, programs, transactions and requests to determine the access entries to each data entity (step 302). Having analyzed the necessary aspects of each data entity, the designer 36 next retrieves the importance for each request in the transaction and program (step 304) and determines the critical access-to each data entity (step 306) .
In the next phase of processing, the designer 36 analyzes the critical access methods entries to determine the desired access mode and access field for each data entity (step 308). Having completed its analysis, the designer 36, then creates access method instances for each unique critical access and data entity combination (step 310). Following step 310, the designer 36 analyzes the critical access entries to determine placement instance for each data entity (step 312). The designer also analyzes transaction instances (for relational databases) or relationship instances (for CODASYL databases) and request instances to determine the interrelationships between data entities (step 314). Once the analysis is complete, the designer 36, generates clusters for interrelated data entities (step 316).
Then, in the final phase of processing, the designer 36 analyzes clusters to determine the mapping of entities to storage areas and storage maps (step 318) and creates instances of storage areas, storage maps, storage partitions, and storage indices (step 320). Once the instances are created, the designer 36 uses the access methods to determine storage index (step 322) and also uses the clusters and placements to determine storage area and storage map (step 324). Finally, the designer 36 prompts the user to determine the storage partitions (step 326) and creates load sequence instances using the volume, request, cluster, and storage map instances (step 328).
General Operation: Physical Database Designer Outputs Design
FIG. 4 is a flow chart illustrating the steps of producing the logical schema 40, the storage schema 38, and the creation parameters 44 and runtime parameters 42. First, the designer 36 creates the-new logical schema 40. To do this, the designer accesses instances of the logical schema, data entities, attributes, and relationships to create model specific Data Definition Language (DDL) file (step 400). Second, the designer 36 creates the storage schema 38. To do this, the designer 36 accesses instances of the record format, storage schema, storage area, storage map, storage index, and storage partition to create model specific DDL file (step 402). Third, the designer 36 creates the creation parameters 44. To do this, the designer 36 accesses instances of the storage area, implementation product, and design constraints to create model specific creation commands (step 404). Fourth, the designer creates the runtime parameters 42. To do this, the designer 36 accesses instances of the implementation product, design constraints, storage area, and storage map to create model specific runtime commands (step 406).
And finally, the designer 36 creates various textual reports such as a design report. To do this, the designer 36 accesses instances of logical schema, access method, placement, cluster, storage schema, storage area, storage map, and load sequence and writes descriptions of each to the report (step 410). The design report 48, is useful, for example, in explaining to a user why the system 10 chose the parameters and schema characteristics it did. The report is also useful in determining if the system used the appropriate inputs to generate the storage schema 38.
The source code for the physical database designer (supplied in Microfiche form in Appendix C and incorporated herein by reference) embodies the software modules described above. The programming languages used are VAX C version 3.0-031. The computer used is a VAX 8820 and the operating system used is VAX/VMS version 5.2. The modules are intended to run under DECwindows, but can also run under a DCL command line interface. Also a list of database design rules and heuristics coded in the relational data manipulation language, e.g., VAX SQL, is included in Appendix A.
This disclosure contains material which is subject to copyright protection. The copyright owner does not object to the facsimile reproduction of the patent document as it appears in the Patent and Trademark Office files, but reserves all other copyright rights.
Other embodiments are within the following claims. | A physical database designer which is embodied in computer software that generates a physical database design. The designer follows a process which includes the steps of (a) entering a logical schema representing the database to be designed; (b) entering a hierarchial definition of the workload experienced by the database, which includes, for each level of a hierarchy of operations, a separate specification of workload; and (c) applying expert rules to the logical schema and the workload definition to generate the physical database design. | 6 |
TECHNICAL FIELD
The illustrative embodiments generally relate to a method and apparatus for vehicle hardware theft prevention.
BACKGROUND
Vehicle security is a constant source of concern to owners of vehicles. From vehicle alarms, to vehicle tracking systems, numerous security measures have been developed over the years to provide protection to owners and to prevent theft.
Vehicle security systems often will produce a loud noise or alarm if the vehicle is compromised or tampered with. These alarms are designed as a deterrent, and can alert bystanders to the presence of a thief, and may serve to scare the thief away before a crime is completed. Such systems can also help reduce insurance rates and may be required to obtain the most desirable rates.
Some security systems can even alert an owner of a potential theft, or alert authorities. Due to the fact that an alerted party may take some time to arrive at the vehicle, however, theft may be complete by the time the notified party has arrived.
In some instances, theft deterrent systems may even track the location of a vehicle. This can assist in capture of a thief, and recovery of the vehicle if the vehicle itself has been stolen. If vehicle components, such as a stereo, navigation system, entertainment system, etc. are stolen, however, the tracking device may be unable to provide a vehicle location.
These components, once they have been taken from the vehicle, stand very little chance of recovery unless the thief is captured or a storehouse is found. Once they have been sold and installed into different vehicles, it may almost be impossible to discover the components and recover them. As such, if the thief acts quickly enough the thief may be able to remove some or all of the valuable components and escape. If an alarm system did not provide sufficient deterrent, there may be little else that can be done to deter a determined thief from stealing a component.
SUMMARY
In a first illustrative embodiment, a computer-implemented method includes determining that an infotainment system has been activated. The illustrative method further includes accessing a vehicle network containing at least a unique vehicle identifier.
In this embodiment, the illustrative method additionally includes comparing the unique vehicle identifier to a stored vehicle identifier. The illustrative method further includes permitting access to the infotainment system only if the unique vehicle identifier matches the stored vehicle identifier.
In a second illustrative embodiment, a computer readable storage medium, stores instructions that, when executed, cause a processor of a vehicle computing system to perform the method including determining that an infotainment system has been activated.
The illustrative method further includes accessing a vehicle network containing at least a unique vehicle identifier and comparing the unique vehicle identifier to a stored vehicle identifier. Also, the illustrative method includes permitting access to the infotainment system only if the unique vehicle identifier matches the stored vehicle identifier.
In a third illustrative embodiment, a system includes a vehicle computing system and at least one module running on the vehicle computing system. In this embodiment, the module is operable to access a vehicle network to determine if a unique vehicle identifier is present. The module is further operable to compare the unique vehicle identifier to a stored vehicle identifier. Also, the module is operable to permit access to the infotainment system only if the unique vehicle identifier matches the stored vehicle identifier.
In a fourth illustrative embodiment, a computer-implemented method includes determining that a requested upload corresponds to a procedure for unlocking a locked vehicle infotainment system. In this illustrative embodiment, the method includes verifying the authenticity of the requested upload. The illustrative method also includes activating a verified upload to unlock the locked vehicle infotainment system.
Also, in this embodiment, the method includes, responsive to the unlocking, deleting a VIN associated with the locked vehicle infotainment system. The method further includes obtaining a new VIN for association with the vehicle infotainment system, the new VIN being available on a vehicle bus in which the infotainment system is installed, and corresponding to the vehicle's VIN. Further, the method includes saving the new VIN as a VIN which must be detected upon system startup to prevent relocking of the vehicle infotainment system.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an illustrative example of a vehicle computing system;
FIG. 2 shows an illustrative example of a verification process;
FIG. 3 shows an illustrative example of an unlock process;
FIG. 4 shows an illustrative example of VIN pairing process; and
FIG. 5 shows an illustrative example of a VIN recording process.
DETAILED DESCRIPTION
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. The figures are not necessarily to scale; some features may be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
FIG. 1 illustrates an example block topology for a vehicle based computing system 1 (VCS) for a vehicle 31 . An example of such a vehicle-based computing system 1 is the SYNC system manufactured by THE FORD MOTOR COMPANY. A vehicle enabled with a vehicle-based computing system may contain a visual front end interface 4 located in the vehicle. The user may also be able to interact with the interface if it is provided, for example, with a touch sensitive screen. In another illustrative embodiment, the interaction occurs through, button presses, audible speech and speech synthesis.
In the illustrative embodiment 1 shown in FIG. 1 , a processor 3 controls at least some portion of the operation of the vehicle-based computing system. Provided within the vehicle, the processor allows onboard processing of commands and routines. Further, the processor is connected to both non-persistent 5 and persistent storage 7 . In this illustrative embodiment, the non-persistent storage is random access memory (RAM) and the persistent storage is a hard disk drive (HDD) or flash memory.
The processor is also provided with a number of different inputs allowing the user to interface with the processor. In this illustrative embodiment, a microphone 29 , an auxiliary input 25 (for input 33 ), a USB input 23 , a GPS input 24 and a BLUETOOTH input 15 are all provided. An input selector 51 is also provided, to allow a user to swap between various inputs. Input to both the microphone and the auxiliary connector is converted from analog to digital by a converter 27 before being passed to the processor. Although not shown, numerous of the vehicle components and auxiliary components in communication with the VCS may use a vehicle network (such as, but not limited to, a CAN bus) to pass data to and from the VCS (or components thereof).
Outputs to the system can include, but are not limited to, a visual display 4 and a speaker 13 or stereo system output. The speaker is connected to an amplifier 11 and receives its signal from the processor 3 through a digital-to-analog converter 9 . Output can also be made to a remote BLUETOOTH device such as PND 54 or a USB device such as vehicle navigation device 60 along the bi-directional data streams shown at 19 and 21 respectively.
In one illustrative embodiment, the system 1 uses the BLUETOOTH transceiver 15 to communicate 17 with a user's nomadic device 53 (e.g., cell phone, smart phone, PDA, or any other device having wireless remote network connectivity). The nomadic device can then be used to communicate 59 with a network 61 outside the vehicle 31 through, for example, communication 55 with a cellular tower 57 . In some embodiments, tower 57 may be a WiFi access point.
Exemplary communication between the nomadic device and the BLUETOOTH transceiver is represented by signal 14 .
Pairing a nomadic device 53 and the BLUETOOTH transceiver 15 can be instructed through a button 52 or similar input. Accordingly, the CPU is instructed that the onboard BLUETOOTH transceiver will be paired with a BLUETOOTH transceiver in a nomadic device.
Data may be communicated between CPU 3 and network 61 utilizing, for example, a data-plan, data over voice, or DTMF tones associated with nomadic device 53 . Alternatively, it may be desirable to include an onboard modem 63 having antenna 18 in order to communicate 16 data between CPU 3 and network 61 over the voice band. The nomadic device 53 can then be used to communicate 59 with a network 61 outside the vehicle 31 through, for example, communication 55 with a cellular tower 57 . In some embodiments, the modem 63 may establish communication 20 with the tower 57 for communicating with network 61 . As a non-limiting example, modem 63 may be a USB cellular modem and communication 20 may be cellular communication.
In one illustrative embodiment, the processor is provided with an operating system including an API to communicate with modem application software. The modem application software may access an embedded module or firmware on the BLUETOOTH transceiver to complete wireless communication with a remote BLUETOOTH transceiver (such as that found in a nomadic device). Bluetooth is a subset of the IEEE 802 PAN (personal area network) protocols. IEEE 802 LAN (local area network) protocols include WiFi and have considerable cross-functionality with IEEE 802 PAN. Both are suitable for wireless communication within a vehicle. Another communication means that can be used in this realm is free-space optical communication (such as IrDA) and non-standardized consumer IR protocols.
In another embodiment, nomadic device 53 includes a modem for voice band or broadband data communication. In the data-over-voice embodiment, a technique known as frequency division multiplexing may be implemented when the owner of the nomadic device can talk over the device while data is being transferred. At other times, when the owner is not using the device, the data transfer can use the whole bandwidth (300 Hz to 3.4 kHz in one example). While frequency division multiplexing may be common for analog cellular communication between the vehicle and the internet, and is still used, it has been largely replaced by hybrids of with Code Domain Multiple Access (CDMA), Time Domain Multiple Access (TDMA), Space-Domain Multiple Access (SDMA) for digital cellular communication. These are all ITU IMT-2000 (3G) compliant standards and offer data rates up to 2 mbs for stationary or walking users and 385 kbs for users in a moving vehicle. 3G standards are now being replaced by IMT-Advanced (4G) which offers 100 mbs for users in a vehicle and 1 gbs for stationary users. If the user has a data-plan associated with the nomadic device, it is possible that the data-plan allows for broad-band transmission and the system could use a much wider bandwidth (speeding up data transfer). In still another embodiment, nomadic device 53 is replaced with a cellular communication device (not shown) that is installed to vehicle 31 . In yet another embodiment, the ND 53 may be a wireless local area network (LAN) device capable of communication over, for example (and without limitation), an 802.11g network (i.e., WiFi) or a WiMax network.
In one embodiment, incoming data can be passed through the nomadic device via a data-over-voice or data-plan, through the onboard BLUETOOTH transceiver and into the vehicle's internal processor 3 . In the case of certain temporary data, for example, the data can be stored on the HDD or other storage media 7 until such time as the data is no longer needed.
Additional sources that may interface with the vehicle include a personal navigation device 54 , having, for example, a USB connection 56 and/or an antenna 58 , a vehicle navigation device 60 having a USB 62 or other connection, an onboard GPS device 24 , or remote navigation system (not shown) having connectivity to network 61 . USB is one of a class of serial networking protocols. IEEE 1394 (firewire), EIA (Electronics Industry Association) serial protocols, IEEE 1284 (Centronics Port), S/PDIF (Sony/Philips Digital Interconnect Format) and USB-IF (USB Implementers Forum) form the backbone of the device-device serial standards. Most of the protocols can be implemented for either electrical or optical communication.
Further, the CPU could be in communication with a variety of other auxiliary devices 65 . These devices can be connected through a wireless 67 or wired 69 connection. Auxiliary device 65 may include, but are not limited to, personal media players, wireless health devices, portable computers, and the like.
Also, or alternatively, the CPU could be connected to a vehicle based wireless router 73 , using for example a WiFi 71 transceiver. This could allow the CPU to connect to remote networks in range of the local router 73 .
In addition to having exemplary processes executed by a vehicle computing system located in a vehicle, in certain embodiments, the exemplary processes may be executed by a computing system in communication with a vehicle computing system. Such a system may include, but is not limited to, a wireless device (e.g., and without limitation, a mobile phone) or a remote computing system (e.g., and without limitation, a server) connected through the wireless device. Collectively, such systems may be referred to as vehicle associated computing systems (VACS). In certain embodiments particular components of the VACS may perform particular portions of a process depending on the particular implementation of the system. By way of example and not limitation, if a process has a step of sending or receiving information with a paired wireless device, then it is likely that the wireless device is not performing the process, since the wireless device would not “send and receive” information with itself. One of ordinary skill in the art will understand when it is inappropriate to apply a particular VACS to a given solution. In all solutions, it is contemplated that at least the vehicle computing system (VCS) located within the vehicle itself is capable of performing the exemplary processes.
In the illustrative embodiments, a vehicle component, such as, but not limited to, a vehicle computing system and/or vehicle infotainment system contains at least one module installed thereon that is capable of securing the module. Since vehicles have unique identification numbers, known as VINs, the module can be keyed to allow the system to operate only when installed in a vehicle whose VIN the module recognizes.
Thus, if the module is stolen and placed in a new vehicle, the module will not recognize the VIN, and will lock out the infotainment system. This should deter the theft of the systems, as they will only work in vehicles for which they were intended.
Of course, it is possible that the system will be permissibly removed, or recovered from an otherwise totaled vehicle and placed in a new vehicle with the permission of the system owner. In such an instance, the module may place the system in lockout mode. When the system is in lockout mode, however, an authorized service provider can be equipped with the capability to cause the system to begin normal operation, and re-pair itself with a new vehicle. In this manner, a system may not be rendered permanently inoperable if properly moved between vehicles.
FIG. 2 shows an illustrative example of a verification process. In this illustrative embodiment, at some point after the vehicle has been activated, such as in the case of a key-on event, the infotainment system will power up. This may cause the protection module (or similar software routine) to activated 201 .
Once the module has been activated, it may first check to see if the system has already entered a lock-down state 203 . An indicator that cannot be tampered with may have been set if a previous lock-down was engaged, and the module may be capable of detecting that the system is already in a state of lock-down 203 . If this is the case, a screen may be displayed (or an audio output may be engaged) 205 to notify the vehicle owner that the system is currently locked and in very limited functionality mode. This display can include, but is not limited to, lock-out of non-critical functions, play-back on ignition cycle of a message that the module is not genuine, etc.
In at least one instance, the functionality is limited to the output of the lockdown message and the ability to communicate with a dealer system to disengage the locking mechanism. In at least one alternative embodiment, the original owner of the system, or a new authorized owner, may be given the ability to unlock the system through the input of a password, or through the uploading of software provided in conjunction with a request from the manufacturer. The user seeking to unlock the system may be required to provide some form of verification before an unlock capability is provided.
If the system is not currently in a lock-down mode, the module may access a vehicle network, such as, but not limited to, a CAN bus 207 . Information about the vehicle, including, but not limited to, electronic VIN identification numbers, can be obtained over the CAN bus. Accessing the vehicle bus can give the module the ability to obtain a vehicle VIN 209 .
If a VIN is not present 211 , the module may persist in the attempts to discover the VIN. Due to a system error, the VIN may not be available (temporarily or permanently) and the vehicle manufacturer may have to determine whether a no-VIN state should result in system lockout or system accessibility. An alternative message, such as a VIN-error message, may be output to inform the user that a visit to a dealer may be required to repair the VIN-error. In at least one case, the module may allow access to the system for a limited number of times if an error occurs, before entering lockout mode. This will give an authorized user an opportunity to use the system while traveling to a dealer to have the issue repaired.
In another instance, the user may be able to input a temporary authorization code for the particular system. This can be obtained, for example, from a manufacturer or dealer. The temporary code can provide limited use of the system before lockout is entered, again giving the user time to get the vehicle to a scheduled dealer appointment. Also, with the case of a temporary authorization code obtained through provision of user credentials, the user can be assured that a thief is not simply using a stolen code to authorize the use of the system. To prevent exploitation of such a system, input of temporary codes may be limited to one or a few instances before lockout mode is entered.
If the VIN is detectable over the vehicle network 211 , the module may then determine if the detected VIN is the correct VIN 213 . In at least one instance, the module/system is paired to a vehicle's VIN upon completion of manufacture of the vehicle or at some point during the manufacturing process. It may be desirable to perform the pairing near the end of the process so that it is ensured that the vehicle has passed any quality control checks, but pairing can be done earlier if desired.
Once the module/system has been paired to a VIN, it is designed to only operate in conjunction with a vehicle having the same VIN number to which it is paired. This prevents stolen modules from operating in alternative vehicles. Modules/systems may also have an alternative option where they operate in conjunction with secondary VINs, such as testing VINs or alternative VINs, but in the example discussed here the module is designed to operate with a single VIN.
If the VIN is the correct VIN, the module allows the driver to access the system as usual 217 . Otherwise, the module may place the system in a lock-down mode 215 . As previously noted, the lockdown mode, in at least one embodiment, may only be removed through the aid of an authorized service provider. Even if a customer inadvertently purchased a stolen module, they would be prohibited from using it, and a trip to the dealer to rectify the problem would then result in recovery of the stolen module.
FIG. 3 shows an illustrative example of an unlock process. In this illustrative embodiment, the module has detected that it is in a locked state 301 , and is in the process of prohibiting system access while outputting a lockout message 303 . The limited system functionality may also include a list of authorized repair technicians in the area of the vehicle, and an ability to contact or direct the driver to one of the local repair technicians. This may aid in the case of inadvertent lock-out, in that the driver can still easily reach a repair technician to have the module/system unlocked.
Once the driver has reached an authorized repair location, such as a dealer or an authorized mechanic, a service tool may be connected to the vehicle through, for example, an ODB port or USB port. In at least one instance, the module is signed with an electronic serial number (ESN), providing a module specific identification serial number.
The technician, through a connected diagnostic tool or other backend system, may request the generation of a signed unlock application signed specifically to be recognized by the particular module installed in the vehicle being serviced. In other words, the application can only be used by a particular vehicle (in this instance) and cannot be used to unlock a plurality of vehicles if stolen from the dealer.
The backend system will generate a signed unlock application and provide it to the technician for installation on the vehicle. The module receives the unlock request from the service tool 307 , and verifies the signature of the unlock application to be installed 309 . This can be done, for example, by comparing the ESN associated with the module to the ESN associated with the unlock application.
If the unlock application has been verified as being suitable for that particular vehicle, this is presumably sufficient, in this case, to identify the provider of the application as being authorized to unlock the module/system. Other security protocol can be implemented as needed.
The unlock application is then installed/executed by the module 311 , and the module is placed in an unlocked state. As part of unlocking the module, the module is unpaired from the VIN 313 , so that the module does not immediately re-lock the system upon wake-up. The module then, having no paired VIN currently associated therewith, is free to re-pair itself with the VIN of the vehicle on which it is installed 315 .
FIG. 4 shows an illustrative example of VIN pairing process. This is a process that may occur several times during the life of a system, including, but not limited to, upon manufacturing completion, upon authorized sale of the system, upon recovery of the system from a damaged vehicle, etc.
Once the vehicle has been powered, the module may be enabled 401 and determine if a VIN is present and paired with the module currently 403 . If a VIN is present, the module may then proceed with a next authorization step 203 .
If a VIN pairing is not present, however, the module may determine if the system is in a suitable state to pair with a new VIN. Since the module may be started several times during manufacturing, while the VCS is still being provisioned, it may be desirable to determine if the system is in a provisioning mode before VIN-pairing is attempted 405 . This should help prevent inadvertent pairing of a module/system that may be moved to a new vehicle before leaving the factory, and should help prevent an attempt to pair the system in a state when a VIN may not be accessible on a system bus.
If the system is not in provisioning mode 405 , the module may further ensure that the system has entered an infotainment mode 407 . This indicates that the system is operating in a standard end-user mode, and is not in some form of diagnostic or other mode during which pairing may not be desired.
If all desired criteria (which may include criteria other than those listed here) are met, the module will access a vehicle bus or other information source from which it can obtain the vehicle's VIN 409 . The module may then seek out the VIN as electronic information 411 .
If the VIN is not found 413 , the module may persist in seeking the VIN until such time as a VIN is available. Once the VIN has been found, the module may pair with the VIN and enter an operational mode, for use with that VIN only. At this point, any attempt to place the system in a new vehicle would result in lockout of the system, until such time as the module was instructed to seek out a new VIN and was unlocked by an authorized party.
FIG. 5 shows an illustrative example of a VIN recording process. In at least one illustrative example, VINs with which the module is paired are recorded with respect to a history source, so that reporting of paired VINs can be obtained at a future time. This can help provide a history of what vehicles the module has been paired with, and may further provide information about any unauthorized unlocking of the system. Historical information can also be used to determine which vehicle a module is supposed to be paired with, in the event that a stolen system is recovered.
In at least one embodiment, ten VINs are stored as a maximum, although this can be adjusted as per a manufacturer's desire. Once a new VIN has been detected for pairing 413 , the module may check an existing history to determine what VINs have previously been paired with this system 501 . The history may be part of a special record that exists on the module and survives module reflashes, preventing attempts to clear a history.
If the history is full 503 , the process may proceed to pairing with the current VIN 415 . Although the new VIN may not be recorded in the history file, it can still be accessible through reporting from a memory location storing the identity of the currently paired VIN. Additionally, the process may check to see if the VIN of the current vehicle is already stored in the history list 505 .
If, for example, a module malfunction caused the system to lock, then there may be no reason to re-save the VIN number upon unlock and re-pairing. In this embodiment, only new, unstored VIN numbers will be saved during the pairing process.
If room remains in the history file, and the VIN is not already present in the file, the module may save the VIN number in the file 507 and then proceed with pairing 415 .
In at least one instance, certain aspects of the module may be saved in a device parameter store (DPS). DPS is a special flash area that survives image reflashes of the module, and maintains its values. This may be helpful in preventing a savvy thief from thwarting the module control by attempting to reflash the module. Since the VIN and any lock-state will be saved in the DPS, a reflashed module will still use these variables to determine functionality of the system, and improper usage of the system will still be prevented.
In certain instances, such a system can be included but disabled during production. Only if the system is enabled post-production will it go into effect, otherwise the relevant modules may lay dormant. In at least one embodiment, additional vehicle firmware/software modules may be disabled by this system as well.
While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention. | A computer-implemented method includes determining that an infotainment system has been activated. The method further includes accessing a vehicle network containing at least a unique vehicle identifier. The method additionally includes comparing the unique vehicle identifier to a stored vehicle identifier. The method further includes permitting access to the infotainment system only if the unique vehicle identifier matches the stored vehicle identifier. | 1 |
This application is a continuation of application Ser. No. 07/071,378, filed on July 9, 1987, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a separable fastener which is provided with a multitude of hooking elements on a substrate cloth.
2. Description of the Prior Art
There have thus far been known face-contacting separable fasteners which consist of a male fastener component having a multitude of upright hooking elements on one side of a substrate cloth and a female fastener component having a multitude of loop elements distributed on a contacting side of its substrate cloth for disengageably engaging with the hooking elements on the male fastener component. In most cases, for forming the male or hooking fastener component, firstly loops are formed by using monofilaments as warps in the weaving process of the substrate cloth to obtain an elongated or broad male fastener strip. Then, in order to enhance the interlocking action of the male fastener component with the female fastener component, the loops are cut open by the so-called clipping method employing a cutter blade assembly which is provided with a fixed cutter blade between a couple of movable cutter blades, to form hooks which are each opened by a clipped space of a width corresponding to the thickness of the intermediate fixed cutter blade. Although many of known male fastener components are made by this method, it is the general practice to narrow the intervals of the individual hooks to increase the number of the hooks in the transverse or longitudinal direction of the fastener for the reason that a greater hook density will increase the chances of engagement between the hook and loop elements. As a matter of fact, a study on the currently available male fastener components could not find any article which had hook elements at intervals greater than about 1.6 mm.
However, the conventional male fastener strips have drawbacks that they are hard in texture and that the small pitch hook-forming cutter blades which are used in the manufacturing process are apt to be blocked with the loop fragments which are clipped off to form the void spaces in the hooks, resulting in failure in clipping the loops appropriately or in undesirably impaired appearance. In addition, the positions of the void spaces in the individual hooks are extremely deviated to one side in the longitudinal direction of the fastener.
Therefore, a male fastener component with such a construction has a problem that the coupling rate is varied depending upon the direction of engagement when the fastener is brought into face-to-face engagement with a female or loop fastener component, showing a different coupling strength depending upon the direction of engagement. It follows that, when such a separable fastener is attached as a joining or connecting member to articles of apparel, shoes, seat covers, or the like, it is necessary to pay attention to the fastener mounting direction--although discrimination of the fastener mounting directions is difficult in some cases. Particularly, it is unsuitable for application to shoes, gloves, diapers, belts or other articles which require a coupling force in one lateral direction. The fastener has another drawback that its stiffness is incongruous with an apparel or cloth of fine texture if used as a fastener therefor.
OBJECT OF THE INVENTION
It is an object of the present invention to provide a male fastener component which is smaller in directional variations of the coupling force when engaged face-to-face with a female fastener component than previously known male fastener components, and which is soft in texture.
SUMMARY OF THE INVENTION
In accordance with the present invention, the above-mentioned object is achieved by the provision of a male fastener component having a multitude of hooking elements on one side of a substrate cloth, in which the individual hooking elements are formed at intervals of X(mm) in the transverse direction and at intervals of Y(mm) in the longitudinal direction, the value of X being between 2.0 to 4.0 mm, inclusive, and the ratio X/Y being in the range of 0.5 to 3.5, inclusive.
The hooking elements which constitute the male fastener component of the present invention can be formed by weaving monofilaments of nylon, polyester or other arbitrary synthetic resin fibre as auxiliary warps into the substrate cloth in the weaving process of the latter to form outwardly projecting loops on a surface of the cloth and clipping the loops into a hook shape. In order to fix the leg portions of the hooking elements which are formed on one side of the substrate cloth, normally a synthetic resin such as polyurethane or the like is coated on the other side of the substrate cloth.
The hooking fastener component according to the present permits the broadening of the pitches in the transverse direction of the teeth of the fixed blades and upper and lower movable blades to be used for clipping the loops into a hook shape, as well as the pitch of the grooves between the respective clipping blade teeth, precluding blocking of the grooves by the fragments of the clipped loop portions. Therefore, it is possible to form hooks which have in one leg portion thereof a clipped portion of a width corresponding to the thickness of the fixed blade. Accordingly, the male fastener component according to the invention has an advantage that the directional variations of the coupling force are extremely small. Besides, since the intervals between adjacent hooking elements in the transverse direction of the substrate cloth of the fastener are broadened, a given number of hooking elements per unit area can be formed by the use of a reduced number of monofilaments as compared with the conventional counterparts, softening the texture of the fastener and permitting reduction of its production cost.
Shown at (1) of FIG. 1 is the manner of forming hooks on a substrate cloth by means of the clipping method, and at (2) is the conventional method of forming hooks on substrate cloth by a similar clipping method. In these drawings, the reference numeral 1 indicates hooking elements, the reference numeral 2 indicates fixed cutter blades, and the reference numeral 3 indicates movable cutter blades.
The expression "intervals (X) between adjacent hooking elements in the transverse direction" as used in this specification means the distance between a point of the substrate cloth which constitutes a longer leg of a hook and a point of the substrate cloth which constitutes a longer leg of a hook which is located adjacently in the widthwise direction (i.e. in the direction of the array of hooks extending across the width of the substrate cloth or parallel with the weft yarns). The expression "intervals (Y) between longitudinally adjacent hooking elements" means the distance between a point of the substrate cloth which constitutes a longer leg of a hook and a point of the substrate cloth which constitutes a longer leg of a hook which is located adjacently in the longitudinal direction (i.e. in the direction of the row of hooks extending in the longitudinal direction of the cloth or parallel with the warp yarns).
In accordance with the present invention, it is necessary to fulfill simultaneously the conditions of X=2.0 to 4.0 mm and X/Y=0.5 to 3.5. Accordingly, even if the ratio of X/Y is in the range of 0.5-3.5, the pitch of the hook-clipping cutter blades is minimized unless the value of X is greater than 2.0 mm, increasing the possibilities of blockage of the cutting blades with the fragments of the clipped loop portions or failing to clip the loops to a material degree to cause directional irregularities in coupling strength when engaged face-to-face with a female fastener component. On the other hand, when the value of X is greater than 4.0 mm, the number of the hooking elements per unit area of the substrate cloth becomes too small, resulting in a lower coupling strength with the female fastener and instable hook conditions. More preferably, the value of X is in the range of 2.7-2.9 mm, and the ratio X/Y is in the range of 0.9-1.6. Where the values of X and X/Y are set in these ranges, it is possible to obtain a fastener which has less directional irregularities in coupling strength and which is soft in texture--that is to say, a fastener which is well-balanced in terms of coupling strength and disposition of the hooking elements. With regard to the value of Y, normally it is selected arbitrarily from a range of 0.6-4.0 mm.
The hooking elements on the fastener according to the present invention may be arranged in any pattern as long as they are arrayed regularly at certain intervals in the transverse and longitudinal directions of the substrate cloth. However, in case of a fastener which has two variations in the transverse intervals (X) of the hooking elements or two variations in the longitudinal intervals (Y), it is a mandatory requisite that the values of X and X/Y are in the above-defined ranges. Examples of arrangements of the hooking elements are shown in FIGS. 2(1) to 2(6), in which X'-X" and Y'-Y" indicate the transverse and longitudinal directions of the fastener component, respectively, and X1 to X9 and Y1 to Y9 indicate the transverse and longitudinal intervals of the hooking elements, respectively.
In accordance with the invention, the height of the hooking elements is preferred to be in the range of 1-5 mm, and the inside diameter of the loops is preferred to be in the range of 0.1-1 mm. Further, the hooking elements are preferred to be arranged on the substrate cloth in a density of 20-70 hooks/cm 2 .
The female fastener component to be used in face-to face engagement with the male fastener component according to the invention may carry the loop elements in any arrangement or pattern as long as it will not impair the functional characteristics of the fastener.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a schematic illustration explanatory of the manner of forming hooks on substrate cloth by a clipping method, showing at (1) a male fastener component according to the invention and at (2) a conventional counterpart; and
FIG. 2 is a schematic illustration giving examples of the arrangement of the hooking elements of the male fastener component according to the invention, in which X'-X" and Y'-Y" indicate transverse and longitudinal directions of the fastener component, respectively, and X1-X9 and Y-Y9 indicate transverse and longitudinal intervals of the hooking elements.
DESCRIPTION OF PREFERRED EMBODIMENTS
Hereinafter, the invention is illustrated more particularly by way of examples, but it is to be understood that the invention is not restricted to the specific examples given.
EXAMPLE AND COMPARATIVE EXAMPLE 1
Substrate cloth specimens having loops arranged as shown at (1) of FIG. 1 with intervals of 2.7-2.9 mm in a direction parallel with the wefts (in the transverse direction of the fastener) and intervals of 1.9-2.1 mm in a direction parallel with the warps (in the longitudinal direction of the fastener) and a loop height of 1.8-2.0 mm were woven, using nylon 110 denier/24 filaments as ground warp yarns, nylon 110 denier/24 filaments as ground weft yarns, and 330 denier nylon monofilament as looping wefts (all products of Toray Industries, Inc.). Then, the substrate cloth specimens were thermally set for 13 seconds at 230° C. for shape retention, and a solvent type urethane resin ("Urethane 300", a product of Nippon Oil & Fats Co., Ltd.) was coated on the back side of each specimen (i.e., on the loop-free side) at a rate of 40 g/m 2 dry. After drying, one end of each loop of the substrate cloth was clipped off by the use of a 1.4 mm pitch fixed blade and 2.8 mm pitch upper and lower movable blades to obtain male fastener components having X=2.7-2.9 mm, X/Y=1.28-1.53, and a hook density per unit area of 33-36 loops/cm 2 .
The male fastener components thus obtained were tested for coupling strength with a female fastener (B1000 Magic Tape (trademark) of Kuraray Co., Ltd.) at a tensile speed of 300 mm/min by the use of Shimazu Autograph (a product of Shimadzu Corporation). The results are shown in Table 1, in which the coupling strength (shearing strength) indicates a strength for an area of engagement of 25 mm (width×50 mm (length), and the strengths (1) and (2) indicate a strength when the fastener is pulled in the longitudinal direction and a strength when the fastener is pulled in the opposite direction, respectively.
During and after a loop clipping operation which was continued for 8 hours, the grooves between the fixed clipping blades were completely free of blockage by clipped loop fragments. Clipping or cutting failures as well as the blockage of the fixed blade grooves did not occur even in high speed clipping operations.
For the purpose of comparison, substrate cloth specimens with loops at intervals of 1.39-1.41 mm in a direction parallel with the weft yarns and at intervals of 3.9-4.1 mm in a direction parallel with the warp yarns were woven from the same nylon materials and by the same method and procedures as described above. The loops on the substrate cloth were clipped by means of 0.7 mm pitch fixed blades and 1.4 mm pitch upper and lower blades to obtain male fastener components with X=1.39-1.41 mm, X/Y=0.33-0.37, and a hook density per unit area of 33-36 hooks/cm 2 . The coupling strength was measured in the same manner as described above. The results are also shown in Table 1.
In this case, the grooves between the fixed blades were blocked with clipped loop fragments up to about 1/2 of the depth of the respective grooves already in about 10 minutes after starting the loop clipping operation. In addition, there were observed trends of loop clipping failures and irregularities in hook shape, and especially these trends became conspicuous in high speed clipping operations.
Comparison of the male fastener components of Example 1 with those of Comparative Example 1 revealed that the former showed less directional variations of the coupling strength, permitted a saving of the loop monofilament by about 25%, and were softer in texture by about 20%.
EXAMPLES 2-4 AND COMPARATIVE EXAMPLES 2-4
Male fastener components were prepared in the same manner as in Example 1 except for various variations of the distances of the loop intervals in the directions parallel with the warps and wefts and of the material for the substrate cloth. Their coupling strengths were measured in the same manner as in Example 1. The results are also shown in Table 1.
TABLE 1__________________________________________________________________________ Compara- Compara- Compara- Compara- tive tive tive tive Example Example Example Example Example Example Example Example 1 2 3 4 1 2 3 4__________________________________________________________________________Fabric MaterialGround Nylon 66 Nylon 6 Polyester Polyester Nylon 66 Nylon 6 Polyester PolyesterWarps 110d/24f 110d/30f 100d/20f 100d/20f 110d/24f 110d/30f 100d/20f 100d/20fGround Nylon 66 Nylon 6 Polyester Polyester Nylon 66 Nylon 6 Polyester PolyesterWefts 110d/24f 110d/30f 100d/20f 100d/20f 110d/24f 110d/30f 100d/20f 100d/20fLooping Nylon 66 Nylon 6 Polyester Polyester Nylon 66 Nylon 6 Polyester PolyesterWarp 330d 350d 470d 600d 330d 350d 470d 600dYarnsX (mm) 2.7-2.9 2.7-2.9 2.8-3.1 2.8-3.1 1.39-1.41 1.39-1.42 1.39-1.42 1.39-1.43Y (mm) 1.9-2.1 1.9-2.1 2.8-3.1 2.8-3.1 3.9-4.1 4.0-4.1 4.2-4.5 4.2-4.5X/Y 1.28-1.53 1.28-1.53 0.90-1.11 0.90-1.11 0.33-0.37 0.34-0.36 0.31-0.34 0.30-0.34Number of Hooksper Unit Area 33-36 33-36 30-33 30-33 33-36 33-36 30-33 30-33(hooks/cm.sup.2)CouplingStrength 1 11.0 10.5 14.0 20.0 12.0 11.0 16.0 22.0(kg) 2 11.0 10.5 14.0 20.0 9.0 8.0 12.0 18.0Stiffness* 44 46 41 41 37 38 33 33(mm)Consumption ofLooping Yarns 80 88 128 164 108 116 172 220(g/m.sup.2)__________________________________________________________________________ * Measured by the heartloop method according to Japanese Industrial Standards (JISL-1096-79') | Described herein is a male fastener strip having a multitude of hooking elements on one side of substrate cloth, which is characterized in that the individual hooking elements are spaced from adjacent hooking elements by X(mm) and Y(mm) in the transverse and longitudinal directions of the fastener strip, respectively, such that X is between 2.0 and 4.0 mm, inclusive and X/Y is in the range of 0.5 to 3.5. | 8 |
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,027,277, issued May 31, 1977, is a prior art form of relay apparatus for accomplishing the general purpose of the present invention, the present device having advantages thereover as will be hereinafter noted.
FIELD OF THE INVENTION
The present invention relates to hermetically sealed relays, and is adapted to vacuum or gas-filled relay technology with or without a latching capability.
DESCRIPTION OF THE PRIOR ART
Vacuum type and other sealed relays of the general class and performing the general functions provided by the combination of the present invention are known. U.S. Pat. No. 3,576,066 illustrates and describes such a relay as known in the prior art, with particular emphasis on processes useful in its manufacture.
Although devices of the general type are usually thought of as vacuum relays, they can be constructed as gas-filled switching devices, if desired.
Prior art devices of the type to which the present invention applies generally comprise two separately manufactured subassemblies prior to final assembly. One of these subassemblies is the hermetically sealed switch assembly itself, and the other is the actuator assembly. In the aforementioned U.S. Pat. No. 3,576,066, the first of these subassemblies is typically illustrated in FIG. 2, and the second in FIG. 5.
Although the present invention is not confined to the use of stacked ceramic cylinders forming the evacuated switch enclosure, that type of construction is well known in the prior art and affords significant manufacturing advantages, vis-a-vis, blown-glass bulb enclosures or the like.
Prior art actuators of the required type have taken several basic functional forms, including those which provide latching in first and second controlled positions by mechanical means and those providing magnetic hold in first or second positions to achieve a similar latching effect. These prior art actuator arrangements have also operated against discrete internal limits, i.e., against their own internal stops, and it therefore has been necessary to very carefully control the switch gap in the mating vacuum switch part so that the switch contacts in one or both directions will be effected with some residual force. Once the vacuum switch enclosure is fully assembled and sealed, it is not possible from a practical point of view to adjust the switch gap (i.e., the spacing between the two switch positions), and if the actuator does not provide an appropriate "overtravel" to absorb at least a portion of the switch contacts at the alternate positions, the manufacturing reject rate is likely to be high and the life of the assembly and vacuum brazing tools and fixtures quite limited.
In the prior art actuators of the type, the overall performance characteristics cannot be appropriately evaluated or production tested until after final assembly to the vacuum switch housing. Therefore, previously undetected dirt or foreign matter in the actuator may cause its rejection along with that of the switch enclosure, since the prior art actuators are not readily opened for cleaning or inspection.
Where the actuator operates against a definite stop within itself in each of two positions, any effort to relieve its own tolerance problems can result in loose parts. The same may be said of the switch assembly, per se.
Thus, the prior art arrangements in which both the switch assembly and the driving actuator operate against their own definite internal stops gives rise to manufacturing problems, particularly in respect to tolerances.
The manner in which the present invention deals with the problems of the prior art to produce a novel and improved overall device will be evident as this description proceeds.
SUMMARY OF THE INVENTION
In accordance with the disadvantages and problems of the prior art, it may be said to have been the general objective of the present invention to produce a hermetically sealed relay of the type described, which may be constructed as a simple electromagnetically controlled switch of simple form, or as a latching relay, in an arrangement which is relatively insensitive to manufacturing tolerances, including those induced by tooling wear, and the normal tolerances of the component parts themselves.
The invention applies typically to the type of hermetically sealed relay constructed from a plurality of stacked hollow cylindrical sleeve sections of insulating material (most commonly of ceramic material). This assembly of insulating sleeve sections forms an elongated enclosure or housing. The sleeve sections are furnace-brazed (preferably in a vacuum), the end surface annulus of each such sleeve section having been prepared for sealing according to a well-known procedure in this art. The electrical terminal structure is integrally sealed between the sleeve sections, that terminal structure also providing the support means for the internal contacts. One end of the enclosure is capped in the process and the other is sealed by means of a flexible conductive diaphragm member, through the center of which a switching control rod or rod member generally axially extends within the sealed housing and for a small distance outside the diaphragm. That portion of the overall structure generally comprises the sealed switch assembly, and is manufactured independently of the actuator.
The bars which comprise the fixed contacts also provide fixed stops against which the switching rod member rests in each of the two discrete angular positions thereof.
The separately manufactured actuator is capable of angularly controlling the external end of the said switch rod member when mated to the sealed switch assembly. Within the actuator, a clapper is drawn to a pole piece in response to energization of a cooperating electromagnet, the clapper is formed of magnetic flux-transmissive material as is the pole piece and the housing surrounding the coils and pole piece. The pole piece is generally axially disposed along the centerline of the actuator device, which is substantially also the centerline of the switch enclosure, when these are mated together in final assembly. When the electromagnet is deenergized, a spring pushes against a relatively rigid portion of a mechanical linkage extending generally axially and normally from the surface of the clapper, to urge the clapper away from the pole piece, i.e., rotate it about pivot point along one edge of the said clapper.
The aforementioned member, which is a portion of the mechanical linkage between the actuator proper and the switch rod member, extends and engages laterally against the said rod member and includes additional resilience serving to provide an "overtravel" or residual pressure tending to keep the switch rod member firmly in the corresponding angular limit position against the corresponding stop within the switch structure. The actual switch rod engagement part comprises a relatively resilient leaf spring member and provides the additional resilience. When the clapper position is against the aforementioned pole piece, corresponding to energization of the electromagnet, this leaf spring will be slightly deflected, thereby providing the same type of residual pressure against the switch control rod member as provided in the other clapper position by the first-mentioned spring. In this way, the so-called "switch gap" tolerance may be absorbed in each of the two switch positions.
The magnetic actuator itself may include, in addition to the electromagnet, a second electromagnet and one or more permanent magnets contributing flux to the same magnetic circuit, i.e., through the center pole piece, through the clapper, and returning to the other side of the pole piece through the magnetic flux transmissive housing containing the actuator magnetic components as aforementioned.
The device may thereby be constructed as a "latching" relay, the permanent magnet flux being sufficient to hold the clapper seated against the pole piece against the first spring means force in the absence of energizing of either of the electromagnets. The permanent magnet field intensity is not sufficient, however, to draw the clapper into position against the first spring means from the "clapper open position" corresponding to the other switch control rod member angular position. One of the two electromagnets is designed to provide sufficient augmentation of the permanent magnet field to draw the clapper against the pole piece. That electromagnet need only be momentarily energized, since the permanent magnet field thereafter holds the clapper in that "closed" position, as aforesaid. The other electromagnet provides a bucking field upon momentary excitation so as to cancel at least a sufficient portion of the permanent magnet field to permit the clapper to be restored to the "open" position by the first spring means. Thus, that particular variation of the basic combination of the present invention provides a latching relay.
It will be realized as this description proceeds that the relay in accordance with the present invention is basically most adapted for single pole, single throw (SPST), or single pole, double throw (SPDT) configurations.
Other improvements over the prior art will be noted as this description proceeds.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view of a prior art sealed switch subassembly of a relay for use in the combination of the present invention.
FIG. 2 is a sectional view taken orthogonally through FIG. 1 as indicated.
FIG. 3 is a sectional view of the actuator and mechanical linkage subassembly according to a prior art arrangement.
FIG. 4 is an end view of the actuator and mechanical linkage of FIG. 3.
FIG. 5 is a block diagram showing a typical relay in the latching variation with sources of latching and bucking current.
FIG. 6 is a sectional view of an actuator and mechanical linkage according to a the invention.
FIG. 7 is an end view, as indicated, taken from FIG. 6.
FIG. 8 is a further partial view of FIG. 6, as indicated.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1, the switch subassembly of a relay for use in the combination of the present invention will be described. A vacuum relay form of this element will be described.
The switch subassembly of FIG. 1 is identified generally at 10 and comprises three of the hollow cylindrical shell ceramic body or housing members 11, 12 and 13 which form the insulating portions of the sealed enclosure. These ceramic hollow cylinder members may be joined either by hydrogen furnace brazing with subsequent defusion exhaustion of the hydrogen or in a vacuum furnace, the latter being preferred. To carry out the brazing process, the parts illustrated in FIG. 1 are assembled in a V-grooved jig composed of graphite or other material of similar characteristics. The V-groove may be tilted slightly so that the parts tend to be held together axially by gravity during the brazing process. End sealing is effected by the metallic cap 14 on one end and by the diaphragm 35 on the other end. Cupped flange parts 15, 18 and 23, having outside diameter substantially the same as that of the hollow cylindrical ceramic body parts, are brazed to the prepared ends of these ceramic parts, and in the case of the cap end, the cup flange 15 and end cap 14 are brazed together. As the parts illustrated on FIG. 1 are assembled into the brazing jig, annular discs ("washer-like" parts) of brazing material are inserted, particularly at 28, 29, 30, 31, 32, 33, 34 and 25. The flange part 24 is brazed to the ceramic part 13, thereby providing convenient means for connecting the actuator to the finished switch device.
A switching rod member 27 of a conductive material, which is relatively hard and possessed of known desirable electrical contact characteristics, such as one of the refractory metals (i.e., titanium tungsten molybdenum or one of the alloys known for the purpose). At 36, this conductive rod 27 is affixed to an insulating sleeve 26 (preferably of a ceramic material similar to that of parts 11, 12 and 13), to provide an insulating mechanically controllable free end for switching control. At 36, the rod passes through a central aperture formed in the flexible diaphragm 35 and is hermetically brazed thereto. The flexibility of diaphragm 35 permits the angular displacement of rod 27 between the extremes or stops provided by contacts 16 and 19.
Referring also to FIG. 2 for clarity, it will be seen that these contact rods 16 and 19, which are ordinarily of the same material as rod 27, are brazed or welded in place in corresponding convolutions 17 and 20 in the respective cup flange parts 15 and 18, respectively. Each of the cup flange parts aforementioned has a central opening typically 21, through which rod member 27 passes.
The technical literature of the prior art, including U.S. Pat. No. 3,576,066 aforementioned, contains additional information regarding materials for the various parts of the switch subassembly 10. The end cap 14 would normally be of metallic material (such as nickel) permeable to hydrogen at high temperatures if the hydrogen atmosphere furnace brazing operation with subsequent diffusion processing to remove the hydrogen is employed. In the preferred vacuum brazing operation, however, there is no such requirement for the material of the end cap 14, and it may therefore be selected in accordance with environmental performance requirements and suitability for withstanding the temperatures of the vacuum brazing operation, as a matter of design choice. Much the same design choice applies to the selection of the cup flange parts, typically 15 with its integral connection lug 15a.
In accordance with the foregoing, it will be noted that a single brazing operation effects the sealing and mechanical assembly, and it emerges therefrom ready for assembly to the actuator device. The emplacement of the fixed contact rods 16 and 19 to the respective parts 15 and 18, as well as the hermetic sealing of the rod 27 to the diaphragm 35 and 36, are best accomplished prior to the vacuum furnace brazing operation by individual welding or brazing operations. The mechanical joint between 27 and 26 at the joint 36 is outside the evacuated interior of the switch assembly, and there is no requirement for hermetic sealing at that point, the diaphragm 35 having already been sealed to 27. Brazing onto a prepared surface of 26 can be employed, however, a properly chosen industrial adhesive is capable of providing this function. In any event, the exposed end of 26 to the right of the diaphragm 35, as viewed on FIG. 1, provides the opportunity of installing the insulating sleeve part 26 after completion of the vacuum brazing step, the part 26 then mechanically becoming a part of the switch control rod.
Referring now to FIG. 3, a prior art actuator with integral mechanical linkage for connecting it to the switch rod assembly 26 is seen generally at 11'. The discussion and explanation of FIG. 3 will be undertaken in connection with the end view, FIG. 4, for maximum clarity.
The actuator embodiment depicted in FIG. 3 is that involving two electromagnet coils 45 and 46 and a pair of permanent magnets 51 and 52, all of these being capable of contributing magnetic flux to essentially the same magnetic circuit, comprising the centerpole piece 44, clapper 43, the magnet housing 38 (including the inwardly turned lip 38a), and back through the permanent magnets 51 and 52 to the centerpole piece 44 to form a complete loop.
It should be understood that, although the actuator structure being described is the "latching" version, the invention is also applicable to the simplest format in a relay, namely, the single electromagnet nonlatching version. In such a device, only a single electromagnet coil, for example 45, need be used, and this might occupy the space devoted to 45 or 46 on FIG. 3. Also, the permanent magnets on the right beyond the magnet coil spool edge 47 would be replaced by a return magnetic circuit plate (not shown), bridging the pole piece right end to the open right end of housing 36, 37 would be omitted in such a version.
The clapper 43 is illustrated in its "closed" position, i.e., drawn against the end of the pole piece 44, and the permanent magnets 51 and 52 are sufficiently strong to retain it in that position. The parts of the magnetic circuit, including the clapper 43, the magnet assembly housing 38 and the pole piece 44 are to be understood to be materials of relatively high magnetic flux transmission capability but of low retentivity. The permanent magnets 51 and 52 are the exception to this, however, in that they must also exhibit high retentivity, a characteristic well understood in connection with permanent magnets.
Let it be assumed that neither electromagnet coil 45 nor 46 is energized, and the clapper 43 being in the (closed) position illustrated, the actuator is controlling the switch subassembly into one of its two switch positions. A relatively rigid, or inflexible, mechanical linkage member 40 having side stiffening gussets 40a extends leftward (as seen on FIG. 3) essentially with its top surface parallel to the axial centerline of the actuator. The opening at the end, identified as 60, will be seen to be shifted upward with respect to the said axial centerline. Since the completed device involves the attachment of the flange 53 of the actuator shell 36 to the surface 54 of flange 24 (see FIG. 1), thus in the closed clapper position, the right end of the switch rod sleeve 26 would be mechanically urged upwardly as seen on FIG. 1, and the rod 27 left of the diaphragm fulcrum point 36 would be correspondingly urged downward into contact with 19.
From FIGS. 3 and 4, it will be seen that leaf spring part 42 would be resiliently "down-sprung" in order to accommodate the circular cross-section of part 26. Depending upon the tolerance conditions all around, the part 26 might ride (in that situation) less than completely seated in the arcuate opening 40b at the top of the opening 60. Thus, there is residual mechanical force tending to keep the rod 27 in firm contact against contact 19, irrespective of nominal tolerance variations in the switch and actuator. The end lip 42a of the leaf spring 42 may also be made slightly concave as a design variation.
It will be understood that the compression spring 41 exerts a force against 40, tending to cause the clapper 43 to rotate "open" about the pivotal points 43a, however, it is not a sufficiently great force to counteract the latching force exerted by the permanent magnets. If the smaller electromagnet coil 46 is momentarily energized in the bucking current direction (i.e., so as to create a flux opposing that of the permanent magnets) then the net magnetic retention force action on the clapper 43 is reduced to the point where the spring 41 can operate to rotate the clapper about the said points 43a. In that event, the opening 60, which accommodates the rod sleeve 26 of the switch subassembly, is shifted downward as viewed on FIG. 3. The result is that the rod 27 changes to a position in contact with 16. In that case, the spring 41 exerts a residual force tending to hold it there and overcoming any tolerance buildup which might otherwise prevent positive switch contact pressure. This capability for "overtravel" of the mechanical linkage comprising the parts 40 and 42 basically, thus employs both the spring 41 and the resilient (leaf spring) member 42 to effect the aforementioned contact retention force in both switch positions.
Once the switching operation corresponding to clapper "open", clapper 43 has rotated about 43a away from the pole piece, and here the permanent magnet flux is not sufficient to pull the clapper 43 back against the pole piece 44 against the force of spring 41. It is, of course, well known, that as the gap in a magnetic circuit increases, a larger magnetomotive force is required to produce an equivalent flux, vis-a-vis, that required to produce the same flux in a minimum or zero gap situation.
If the larger electromagnet coil 45 is next momentarily energized so as to produce a sufficient magnetic force aiding that of the permanent magnet, the clapper 43 will be again drawn against the pole piece 44 and will remain there because of the retention force exhibited by the said permanent magnets around the aforesaid magnetic circuit, even though the electromagnetic coil 45 is only momentarily energized.
As illustrated on FIG. 3, the space 48 comprises a keeper of nonmagnetic insulating material for preserving the magnet coil alignment illustrated. Electrical leads 49 and 50 are shown for the sake of completeness, these being only two of four required for the two electromagnet latching versions illustrated, as will later be seen more clearly in connection with FIG. 5.
A washer 39, of nonmagnetic material, such as monel, may be brazed through its center hole over the end of the pole piece 44 to serve as a mechanical closure over the clapper end of the electromagnet assembly. It is necessary that this part be non-magnetic in order to avoid "short circuiting" the magnetic flux which it is desired to have pass through the clapper 43.
The more or less rectangular nominal shape of the clapper 43 may be observed from FIG. 4, however it will be realized that this shape is arbitrary and a matter of design choice only.
A keeper 61 of partial circular shape as illustrated in FIG. 4, has a raised portion 62 acting as a retainer for the clapper 43 by forming a pocket as seen from FIGS. 3 and 4. This expedient is more important as an assembly convenience than a functional necessity once the switch and actuator subassemblies are fully mated. This pocket formed by the raised portion of 61 at 62 is sufficiently loose to avoid binding of the clapper in the vicinity of the pivot points 43a. The keeper portion 61 may be readily attached, as by spot welding to the magnet assembly housing lip 38a.
The completed switch and actuator sub-assemblies 10 and 11' respectively, are very conveniently mated by first applying several spot welds through the actuator housing flange 53 and the switch sub-assembly flange 54. Thereafter, if required, heliarc welding, external brazing or the like, can be applied to environmentally seal the assembly, although only the interior of the switch sub-assembly between the end cap 14 and the diaphragm 35 (comprising the space 59) is normally hermetically sealed. An end-bell 37 joined by an adhesive seal 80, serves as a protective cover at the other actuator end and would normally be of non-magnetic metal material in the arrangement as illustrated in FIG. 3, although that is not a functional requirement.
Referring now to FIG. 5, a pictorial view of the typical assembly of switch sub-assembly 10 and actuator sub-assembly 11, is shown. In the embodiment depicted in FIG. 3, four leads, i.e., two for each of the magnet coils 45 and 46, are usually required, unless one leg of each coil is considered "common", in which case only three external leads need be used.
It may be assumed that leads 49 and 50 from the source of latching current 55 lead to the larger coil 45, i.e., the electromagnet capable of drawing in the clapper 43 from its "open" position. Leads 57 and 58 are shown in FIG. 5 conducting current from a bucking current source 56 to the smaller coil 46, i.e., for producing the relatively small cancellation or bucking flux necessary to overcome the retentive effect of the permanent magnets in order to release clapper 43 from the "closed" position illustrated and allow spring 41 to rotate it and the parts of the aforementioned mechanical linkage about the pivot point 43a, as already described.
Referring now to FIGS. 6, 7 and 8, the actuator and mechanical linkage (generally at 11") will be described as they are for the improved combination of the invention. This arrangement affords certain advantages, vis-a-vis, the actuator and mechanical configuration described in FIG. 3. Insofar as its application to the switch "bottle" of FIG. 1 is concerned, the actuator and mechanical linkage assemblies of FIGS. 3 and 6 are interchangeable. Like parts carry the same identifying numerals among the illustrations.
The actuator mechanical linkage device of FIG. 3 provides for the gripping of the switch subassembly control rod 26 on either side thereof in a type of zero force play arrangement, as already described. In instances where the operating voltages are relatively high, the projected edges of parts 42a and 40b (as seen in FIG. 4) can produce a localized high voltage stress, with resultant localized corona. The invention embodiment of FIGS. 6, 7 and 8 employs a different design more suitable for higher voltage applications in that the overtravel spring 65 has an orthogonally oriented end 65a with a clearance hole 66 therethrough. The switch subassembly control rod 26 fits sufficiently loosely through the hole 66 so that no binding occurs at either angular extreme of the rod 26, corresponding to either the closed or opened position of the clapper 63. The additional play introduced, as compared to that extant in the FIG. 3 configuration at that point, is readily compensated for by the overall tolerance-absorbing characteristic of the design, this being a significant overall feature of the invention.
The embodiment of FIG. 6 will be seen to permit the use of a longer, larger diameter spring 67 having a lower spring rate selectable from a broader group of commercially available springs. This longer, larger diameter spring 67 is also less sensitive to the relative locations of its mounting surfaces and makes possible a somewhat more relaxed spring rate and mounting surface tolerance situation.
Still further, the novel arrangement depicted in FIGS. 6, 7 and 8 provides inherent freedom from spot-weld-induced distortion of the clapper magnetic interface surface (i.e., against the pole piece 44a and the other magnetically active parts of the magnet structure). This is accomplished by confining the spot-welds to the orthogonally oriented projection 64 of the clapper 63. Such welds are in the vicinity of 78 as seen on FIG. 6 and are more specifically shown as spot-welds 71, 72, 73 and 74 on FIG. 8.
Spot-welding directly to any part of the coil housing face has also been eliminated from FIG. 6 in order to obviate the possibility of any weld-induced distortion from that source. To produce the same clapper and spring-retaining functions as provided in FIG. 3, an inner sleeve 69 is press-fitted or otherwise secured within an outer actuator housing member 36a. This inner sleeve 69 has a side wall hole at 68 within which the spring 67 nests against the inside surface of 36a.
It will be noted that an annular cavity 79 is formed because the inner sleeve 69 is not inserted into complete contact with the radius portion of the magnet housing 38a. This provides a capture groove for the clapper lower portion 63a, with a small gap 76 remaining.
A cup 70 receives the bottom end of the spring 67, as shown on FIG. 6. This cup 70 may be spot-welded, typically at 75, to the top of the clapper axially extending portion 64, as also seen in FIG. 6. This spot-weld 75 may, for example, be in the location illustrated at 75 in FIG. 8.
It will be noted, particularly from FIG. 7, that the right angle portion 65a of the overtravel spring 65 has a rounded edge configuration, for minimum corona generation. It will also be noted, especially from FIG. 8, that the overtravel spring 65 is actually bifurcated in order to provide an appropriate leaf spring characteristic without making the spring metal thickness thereof unduly thin and fragile.
In operation, the device of FIG. 6 is illustrated with the clapper 63 drawn against pole piece 44a. The spring 67 would then be under maximum compression and on FIG. 6, the overtravel leaf spring 65 would actually be deflected downward away from 64, producing a gap at 77 and thereby resiliently maintaining the switch subassembly control rod 26 in one extreme position, the said 26 extending through the hole 66, of course.
The functions of 44a, 45a, 49a and 50a are the same as 44, 45, 49 and 50 in FIG. 3. FIG. 6 is actually illustrated with only a single actuating coil 45a, rather than with 45 and 46 as shown in FIG. 3, it being understood that this is indicative of an alternate electromagnetic actuating option as hereinbefore referred to.
The functions of 38a and 39a are to be understood to be equivalent to those of 38 and 39, as described in connection with FIG. 3.
In the other extreme of operation of the device in FIG. 6, the clapper 63 would be away from the pole piece 44a, pivoting about its lower corner adjacent to the gap 76. The overtravel leaf spring 65a would, in this case, be snug against 64 (no gap in the vicinity of 77), and the spring 67 would provide the residual force against the switch subassembly control rod 26 in that situation.
A number of variations will suggest themselves to those skilled in this art, once the concepts of the present invention are fully appreciated. Accordingly, it is not intended that the drawings or this description should be considered as limiting the scope of the invention, the said drawings and specification being typical and illustrative only.
Certain additional features of interest and practical importance which are prior art per se, are pointed out to the skilled reader. For example, the cupped flange contact supports, such as 15, provide an inside baffling effect tending to reduce the tendency for corona to develop within the evacuated space. While it is known, for example, from the aforementioned U.S. Pat. No. 3,576,066, and also U.S. Pat. No. 4,027,277 to cup the contact supports, an improvement in the structure of the present device has been effected by also cupping the part 23. Thus, the surface at point 22 tends to retain the shape of the brazing material washer 32 during the furnace braze operation, to avoid the development of sharp points and irregularities which tend to give rise to internal corona.
Further, prior art devices have frequently used a reentrant type seal whereby the flange part 24 is joined to the outside circumference of ceramic part 13. In the present device, a so-called "cookie-cutter" seal (also known per se) is made between 13 and 24 and the need for a specially prepared ceramic part 13 is thereby eliminated. Accordingly, the ceramic parts 11, 12 and 13 may be identical. | A hermetically sealed relay of the reed-type in which an elongated switching control rod is angularly displaced in operation. The extreme positions include internal stops, which may be contacts, in which case the switch is a single-pole-double-throw device. An attached actuator for the switch device provides tolerance-absorbing overtravel by means of uniquely arranged resilient means, such that switch-gap tolerances are effectively absorbed. The device may be of the magnetically latching type or may, in simplest form, include a single controlling electromagnet and only one fixed contact. Two embodiments are described. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to an airing and drying frame having a vertical mast on which a multiple-arm frame is mounted, which are generally known as clothes umbrellas.
These so-called clothes umbrellas, are known, for example, from U.S. Pat. No. 4,574,961 and Swiss Patent No. 390,863 and are very popular as airing and drying devices for clothing and laundry. They allow hanging of a large number of pieces of clothing and laundry in a small area. Even large articles, such as bed linens and tablecloths present no problems. These known clothes umbrellas have the advantage that they can be collapsed or folded and can be stored in a very small space when not in use, and that the clothesline is fully retracted into the arms of the device, protecting the clothesline from getting dirty. The disadvantages of the known designs are that the mechanism for retracting the clothesline is very complex, and that considerable force is necessary to open and close the arms.
The object of the present invention is to create an airing and drying frame with a device for retracting the clothesline, wherein the device for retracting the clothesline only requires insignificant additional technical expenditure compared with, for example, a clothes umbrella according to Swiss Patent No. 390,863, and wherein it can be opened and closed with very little force.
SUMMARY OF THE INVENTION
According to the present invention, a frame for airing and drying articles comprises support means; a plurality of arms extending from said support means and being pivotable relative to said support means between a folded position where said arms are adjacent said support means and an open position where said arms extend from said support means; a clothesline extending between adjacent arms and on which articles are to be hung; and wherein said arms each including retracting means for retracting the clothesline into the arms when the frame is folded to said folded position where said arms are adjacent said support means. The retracting means comprises a plurality of slider members slidable on said arms and which are movable relative to each other, end portions of said clothesline being attached to respective slider members; and an operating weight member at the outermost slider member on each of said arms, said operating weight member being slidable along the respective arm solely by the force of gravity, responsive to a raising movement of said arm from said open position to said folded position, and for acting on the outermost slider member to cause said outermost slider member to slide downwardly of said arm when said arm is raised toward said folded position, to thereby draw the clothesline into the respective arms.
According to the present invention, a very simple construction, combining an arm and a slideable weight, is achieved. The use of lead as a weight material for the operating element is particularly advantageous since it offers excellent sliding and, therefore, moving properties in its interaction with a sliding channel of the arm, and can additionally be coated with friction reducing material. Very easy handling and operation is the result.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a partly sectional view of an airing and drying frame according to the present invention, with the left half shown in an extended or unfolded position and the right half shown in a closed position, with the arms shown in cross section;
FIG. 2 is a partial view taken in direction II of FIG. 1;
FIG. 3 is a cross sectional view taken along the line III--III in FIG. 2; and
FIG. 4 is a cross sectional view taken along the line IV--IV in FIG. 2.
DETAILED DESCRIPTION
A mounting member (star) 2 is slideably mounted to a mast 1 in a manner as to be slidable along mast 1 in relation to a fixed member 3. The member 2 is lockable relative to the mast (locking means not shown) when in its upper position adjacent the fixed member 3. Swing-out arms 4 are pivotally mounted to the mounting member 2 with rope members (segments) 5 suspended between them. Swing-out arms 4 are supported relative to the fixed upper member 3 by means of pivotable expansion arms 6. The individual ends of the rope members 5, in the vicinity of the respective rope corners or bends 51, are each connected to a respective slider 7 which is mounted inside a sliding channel 20 of the arm 4. A weight 9 is situated in front of each outermost slider 8 in each arm 4, or the outermost slider 8 is designed as a weight. Preferably, the weight 9 or outermost slide 8 (weight) is made of lead and is slideably guided in the sliding channel 20 formed in each arm 4.
To open the expansion frame 10, which comprises the swing-out arms 4 and the expansion arms 6, a pull rope 11 is attached to the fixed member 3 near the top of the mast 1. As seen in FIG. 1, the pull rope 11 runs from the fixed member 3, is mounted around a pulley-type device 12 on the mounting member 2, is then run around another pulley-type member 13 on fixed member 3 and is again returned to another pulley-type device on the mounting member 2, and rope part 14 extends to the user for operating the device.
Each of the swing-out arms 4 comprises an elongated member having a generally box-type profile, open on one side, as seen in FIG. 4. Longitudinal fins or projections 19 (FIG. 4) extend from the inner side walls and divide the inner space of the arms 4 into a sliding channel 20, serving as guide for sliders 7 and 8 and slideable weight 9, a clothesline compartment 21 for receiving the clothesline 22, and a compartment 23 for the segment covers 24. The segment covers 24 are preferably of the same length as the rope corner distance 25 (see FIG. 2) between two neighboring rope corners 51 and are provided with respective openings 26 (FIG. 4) for the clothesline 22 to pass therethrough.
The clothesline 22 is designed in the shape of individual rope segments 5. The rope segments 5, when projected to the ground, form a substantially square shape and are provided with clips or clamps 27 (see FIGS. 3 and 4) at their end portions 28. With these clips 27, the end portions 28 of the individual rope segments 5 are clipped or fixed in the individual receiver areas 29 of the sliders 7 and 8. As seen clearly in FIG. 4, the clips or clamps 27 cannot pass through the openings 34 in the sliders 7 and 8, thereby fixing the end portions 28 of the rope segments 5 to the sliders 7, 8.
The sliders 7 and 8 are preferably provided with two glide risers 33, as can be seen clearly in FIG. 4 to enhance slideablility in sliding channel 20. An oblong hole 34 (see FIG. 2) with a broadened inlet opening 35 facilitates the mounting of the clips 27.
Referring to FIG. 1, the sequence of movements in operating the airing frame is explained. Beginning with the closed position, when pulling on the operating part 14 of the pull rope 11, the mounting member 2 will move upwardly in the direction of the arrow 15, and the swing-out arms 4 will undergo an expansion or swinging out movement as shown by the arrow 16 in FIG. 1. Sliders 7 and 8 are pulled into their respective final positions 17 (see FIG. 1 and FIGS. 2 and 3), and the rope segments 5 are pulled taut due to the rope 5 passing through the openings 26 of the segment covers 24.
When closing the airing frame, the mounting member or star 2, being secured or locked in the upper position to the mast 1 with a latch, not shown, is unlatched. The closing sequence is initiated by tilting the pivotable arms 4 upwardly in the direction of the arrow 40 (FIG. 1). In the initial phase of the closing process, the path of the mounting member or star 2 on the mast 1 is longer than the retraction of the clothesline. Beginning at a certain expansion angle 38 (FIG. 1), the inertia of the outermost slider 8, or the weight 9 respectively, is overcome. It begins sliding inwardly toward the mast 1 in the direction of arrow 18. Through the sliding action of the weight 9 (or 8), the retraction of the rope segments 5, beginning with the outermost rope segment S 1 , starts. The outermost slider 8 begins to move toward the inside (i.e., toward the mast 1) and takes the next slider 7 along with it. Retraction of the next rope segment S 2 starts and cause retraction of the next rope segment S 3 , after slider 7 strikes the next slider. Tilting of the arms 4 is aided by the pull of the weights 9 through the clothesline. In the closed position of the expansion frame 10, (as shown at the right side of FIG. 1), the sliders 7, 8 are close to each other; the clothesline 22 and the rope parts 41 of the rope segments 5 close to the mast 1, respectively, are taut.
To achieve substantially equal tension of the rope parts 41 close to the mast 1, the sliders 7 and 8 each must have a length 39 (see FIG. 3) equal to half the difference in length between two neighboring rope segment sections, for example 1/2(S 2 -S 3 ).
The distance between the innermost connection point 42 (see FIG. 2) of the innermost rope segment S 3 from the mast 1 is equal to half the length of the rope segment S 3 plus the length 39 of slider 7. The sliders 7, 8 are all of the same length when the distances 25 (FIG. 2) between the end portions of the individual adjacent rope segments 5 are equal.
In order to improve sliding of the sliders 7, 8 within the sliding channel 20, the sliders 7, 8 can be coated with a friction reducing material such as polytetrafluoroethylene (Teflon) or other appropriate friction reducing coatings. Alternatively, or in addition to coating sliders 7, 8, the inner sliding surfaces 31 of the sliding channel 20, along which the sliders 7, 8 slide, may be coated with a friction reducing material such as polytetrafluoroethylene (Teflon) or other suitable material.
While two glide risers 33 are shown in FIG. 4, other surface configurations having reduced surface-to-surface contact areas, could be used to enhance slideability.
If desired, all or some of the sliders 7, 8 can be made of a heavy material, such as lead, to serve as weights. At least the outermost slider or sliders should preferably serve as weights.
While having described above the principles of the invention in connection with specific apparatus, it is to be clearly understood that this description is made only by way of example and not as a limitation to the scope of the invention as set forth in the accompanying claims. | An airing and drying frame comprises a vertical mast (1), a plurality of arms (4) for holding a clothesline (22), the arms (4) being pivotally mounted to the mast (1), and a retraction device for retracting the clothesline (22) into the arms (4) when the frame is being closed. During a closing action the clothesline (22) is pulled inward within the arms (4) by means of weights (9) sliding in a sliding channel (20) into a storing compartment (21) within the arms (4). | 3 |
The present invention relates to expansible receiver modules. In particular, the present invention relates to expansible receiver modules for hearing aids. Such expansible receiver modules are suitable for being mounted within the bony area of the ear canal.
BACKGROUND OF THE INVENTION
Hearing aids today are typically manufactured in one piece—i.e. one component comprising all necessary sub-devices such as microphone, amplifier and receiver—the latter being used to generate a sound pressure so as to excite the eardrum in response to sound pressure captured by the microphone. The components—microphone, amplifier and receiver—are encapsulated in a common plastic shell as illustrated in FIG. 1 .
As seen in FIG. 1 , the hearing aid is positioned at a relatively large distance from the eardrum—in front of the bony area of the ear canal. The reason for this being that the plastic material forming the shell encapsulating the above-mentioned components is hard, which makes it impossible to position a conventional hearing aid with a plastic shell in the bony area of the ear canal without introducing pain to the user of the hearing aid.
Another disadvantage of one-piece hearing aids is the large distance between the receiver output and the eardrum to be excited.
Other disadvantages relating to one-piece hearing aid are acoustic feedback from the receiver to the microphone, vibrations of the receiver, which is transmitted to the ear canal, unpleasant for the user and finally the rather complicated and painful mounting of the hearing aid.
U.S. Pat. No. 6,094,494 discloses a device and a method for fitting a sound transmission device to provide an easy and effective fit, reduce feedback, and improve user comfort comprises an ear-piece component having a face at one end with operative components and a stem adjacent the other end. The stem houses a speaker tube which protrudes from the component, and it has a retaining means for securing an inflatable, resilient fitting balloon thereon. The balloon has a sound transmission duct within it which can be coupled to the speaker tube so that when the balloon is secured to the stem, a continuous path is provided for the transmission of sound from the component to the user's ear canal external the balloon. This assembly (e.g., the component and attached balloon) is inserted into the ear canal when the balloon is in a deflated configuration. Air is then pumped into the balloon, e.g., through an air channel in the ear-piece component, to inflate the fitting balloon. The inflated fitting balloon engages the ear-piece component against the walls of the user's ear canal and prevents sound from travelling to the external ear and face of the component.
U.S. Pat. No. 4,133,984 discloses a plug-type hearing device comprising a sound-leading portion being inserted into the auditory miatus, a first envelope attached around the sound-leading portion, a second envelope being positioned at the outside of the auditory miatus and being communicated with the first envelope through a pipe, and a holding means for holding an expanded state of the first envelope when the volume of the latter is increased, wherein the volume of the second envelope is decreased to increase the volume of the first envelope by the pressure of a fluid contained inside, and the expanded first envelope is closely contacted with the wall surface of the auditory miatus.
However, the balloon introduced in U.S. Pat. Nos. 6,094,494 and 4,133,984 does not solve the above-mentioned problems in that the hearing aid is still a one-piece device—the only difference compared to the hearing aid of FIG. 1 is that a flexible sound-leading portion has been attached to the hearing aid in order to guide sound from the receiver, which is still positioned at a large distance from the eardrum, to an opening near the inner end of the flexible sound-leading portion.
Thus, problems related to the large distance between the receiver output and the eardrum is not solved by the set-ups suggested in U.S. Pat. No. 6,094,494 and 4,133,984. Even further, since the systems of U.S. Pat. No. 6,094,494 and 4,133,984 are still one-piece hearing aids problems such as acoustic feedback from the receiver to the microphone, vibrations of the receiver, which is transmitted to the ear canal, are still present and may easily influence the performance of the hearing aid in a negative direction.
It is an object of the present invention to provide an external receiver module, which solves the above-mentioned problems. The external receiver module according to the present invention has the following advantages:
The receiver may be brought close to the eardrum (in the bony area). Using an expansible, preferably inflatable, medium to keep the receiver in its place instead of a plastic shell. Dividing the conventional one-piece hearing aid into two parts connected by a tube. That part of the hearing aid comprising the microphone may be removed—e.g. for repair—without removing the receiver module from the ear canal. No problem with cerumen. No acoustic feedback to the microphone. No occlusion effect. The expansible medium may be expanded to the user's wishes (comfort). Easy to fit in the ear. The expansible medium is soft which is of importance in the bony area. No vibration transfers from the receiver to the ear canal. The receiver module including the expansible medium may be removed and cleaned without surgery by the audiologist.
SUMMARY OF THE INVENTION
The above-mentioned object is complied with, and the above-mentioned advantages are achieved, by providing, in a first aspect of the present invention a receiver module being adapted to be positioned in an ear canal, the receiver module comprising
a receiver having a receiver housing, said receiver being adapted to receive a time dependent electrical signal, said receiver further being adapted to generate outgoing acoustic waves via an output port in the receiver housing in response to the received time dependent electrical signal, and expansible means surrounding at least part of the receiver housing, said expansible means having an opening aligned with the output port of the receiver housing so as to allow the generated outgoing acoustic waves to penetrate away from the receiver module and into the ear canal.
The expansible means is preferably inflatable means, which may be a balloon-like device, which may be inflated with air, liquids, gel or foam or the like. In order to inflate the balloon-like device, air or liquid may be pumped into the balloon-like device. The balloon-like device may be fabricated in a flexible material such as latex, silicone or any other elastomer. The material may be chosen so as to provide a permeable inflatable means so that a medium being held inside the inflatable means may penetrate the material forming the inflatable means so as to enter the bony area of the ear canal.
Alternatively, the expansible means may be mechanically expansible means, which may be expanded in the ear canal. Such a mechanical arrangement may be an umbrella-like system such as shown in FIG. 17 .
The inflatable means may also be a balloon-like device filled with some sort of elastic foam. The dimensions/volume of such balloon-like device may be controlled by controlling the amount of air in the foam. For example, the volume of the balloon-like device may be reduced by pumping air out of the foam whereby the balloon-like device may be brought into its final position—e.g. its final position in an ear canal. The pump may then be disconnected, and the foam will now be filled/or at least partly filled with air whereby its dimensions will increase so as to fit the dimensions of the ear canal. The expansible means may be made of a sponge-like material, so that it is self-expansible (e.g. similar to the known self-expansible ear plugs).
The receiver module may further comprise a tube section having first and second end parts, the first end part being connected to the expansible means and/or the receiver. The tube section may be adapted to provide to the inflatable means a medium to inflate the inflatable means. This medium may be water, saltwater, glycerine, or silicone oil. Preferably, the tube section comprises a hollow inner section, said hollow inner section being adapted support electrical means for providing the electrical signal to the receiver. These electrical means may be electrical wires or the like. The tube section is preferably formed as a one-piece component with the inflatable means. In this situation, the tube/inflatable means may be fabricated as a single flexible tube having at least two sections with different diameters—one diameter being larger than the other. The integrated tube/inflatable means may then be provided by pulling the section having the smallest diameter into the section having the larger diameter, whereby a hollow tube with “integrated” inflatable means may be established.
The second end part of the tube section may be connected to a connection terminal, said connection terminal having electrical contacts connected to the electrical means supported by the inner section of the tube section. The connection terminal may comprise means for handling the medium for inflating the inflatable means.
Preferably, the connection terminal is a socket having electrical terminals for connecting the receiver to external electronic devices in terms of power, electrical signals representing amplified sound pressure etc. Such external electronic devices may be that part of a hearing aid comprising the microphone and the amplifier. The handling means for handling the medium for inflating the inflatable means may be some sort of canal in which the medium may flow. The canal will typically be combined with some kind of closing or switch.
The receiver module may further comprise a filter positioned in the opening of the expansible mean so as to cover the output port of the receiver housing. Alternatively, the receiver module may comprise a membrane positioned in the opening of the expansible mean so as to cover the output port of the receiver housing in order to protect the receiver against cerumen.
The receiver module may further comprise pump means for providing the medium to inflate the inflatable means to the inflatable means. As already mentioned this medium may be air, liquids, gel or the like. This pump means may be driven electrically or mechanically. In one embodiment, the receiver of the receiver module may act as the pump for inflating the inflatable means. The pump means may be controlled by activating an external string. By external is meant that the string is accessible for e.g. the user of the receiver module—e.g. accessible from the outside of the ear. Activation may be achieved by rotating, bending, pulling and/or pushing the string relative to the receiver module, whereby the pump means may be switched on and/or off. Even further, by activating the string the pressure in the inflatable means may be adjusted. Finally, the string may be used to remove the receiver module from the ear canal—simply by pulling the string.
The receiver may be connected to the inflatable means, so that the back volume of the receiver is used for inflating the inflatable means. This back volume may act as a reservoir for housing the medium to be pumped into the inflatable means when the receiver module is to be positioned in the ear canal. When the receiver module is to be removed from the ear canal, the medium is pumped back into the back volume. Further, the tube section may be used as an extra back volume, and in that case the second end of it will be closed, as shown in FIG. 13 .
The receiver module may further comprise a vent canal, said vent canal forming part of the inflatable means and the tube section so as to establish an unbroken vent canal from the second end part of the tube section to a point adjacent to the opening of the inflatable means. This vent canal is used to avoid occlusion and to equalise pressure between the area between the receiver module and the eardrum, and the outside. The vent canal may be provided/established by folding the inflatable means in a predetermined way so that parts of the folded areas define the vent canal.
In a second aspect, the present invention relates to a receiver module being adapted to be positioned in an ear canal, the receiver module comprising
a flexible membrane having predetermined magnetic properties within a predetermined region of the membrane, expansible means having an opening holding the membrane, a tube section having first and second end parts, the first end part being connected to the expansible means, and means for generating a magnetic field in response to a provided time dependent electrical signal, the generated magnetic field displacing the flexible membrane in accordance with the provided time dependent electrical signal so as to generate outgoing acoustic waves which penetrate away from the flexible membrane and into the ear canal.
Again, the expansible means is preferably inflatable means, which may be a balloon-like device, which may be inflated with air, liquids, gel or the like. In order to inflate the balloon-like device, air or liquid may be pumped into the balloon-like device. Alternatively, the expansible means may be mechanically expansible means, which may be expanded in the ear canal, like the system shown in FIG. 16 . The tube section may be adapted to provide to the inflatable means a medium to inflate the inflatable means.
The receiver module may further comprise a vent canal, said vent canal forming part of the inflatable means and the tube section so as to establish an unbroken vent canal from the second end part of the tube section to a point adjacent to the opening of the inflatable means. This vent canal is used to avoid occlusion and to equalise pressure between the area between the receiver module and the eardrum, and the outside.
The expansible means may be as describes in relation to the first aspect of the present invention. The same holds for the suggested media for inflating the inflatable means.
The predetermined magnetic properties may be determined by a magnet attached to the membrane. Alternatively, the predetermined magnetic properties may be determined by the membrane itself in case the membrane is magnetised by a magnetic material. The magnetisation may be provided by doping the membrane with a magnetic material such as iron. The magnetic field may be generated by means of a coil of wounded wire.
In a third aspect, the present invention relates to a receiver module being adapted to be positioned in an ear canal, the receiver module comprising
a flexible membrane having predetermined magnetic properties within a predetermined region of the membrane, expansible means having an opening holding the membrane, a tube section having first and second end parts, the first end part being connected to the expansible means, and driving means for driving the flexible membrane in response to a time dependent electrical signal provided to the driving means so as to generate outgoing acoustic waves in accordance with the time dependent electrical signal.
Similar to the first and second aspects, the expansible means is preferably inflatable means, which may be a balloon-like device, which may be inflated with air, liquids, gel or the like. In order to inflate the balloon-like device, air or liquid may be pumped into the balloon-like device using pump means. Alternatively, the expansible means may be mechanically expansible means (e.g. an umbrella-like opening system or a sponge-like material), which may be expanded in the ear canal, like the system shown in FIG. 16 . The tube section may be adapted to provide to the inflatable means a medium to inflate the inflatable means.
The expansible means may be as previously described in relation to the first and second aspect of the present invention. The same holds for the suggested media for inflating the inflatable means (air, a gel, a foam, or a liquid) and the preferred implementation of the vent canal—i.e. an unbroken vent canal from the second end part of the tube section to a point adjacent to the opening of the inflatable means. The driving means may comprise piezo-electrical materials. Alternatively, the driving means may comprise a flexible polymeric charged film or magnetostrictive materials.
The second end part of the tube section may be connected to a connection terminal, said connection terminal having electrical contacts connected to electrical means for providing the time dependent electrical signal to the receiver. The connection terminal may comprise means for handling the medium for inflating the inflatable means.
The receiver may be connected to the inflatable means so that a back volume of the receiver inflates the inflatable means upon providing a pressure the back volume of the receiver. The receiver may further comprise a layer of soft and flexible material surrounding the expansible means. This soft and flexible material will, when the receiver module is positioned in the ear canal, be positioned between the bony area of the ear canal and the expansible means.
It may be advantageous to shape the expansible means in a way so that, in a cross-sectional profile, the expansible means takes an elliptically shaped profile.
In a fourth aspect, the present invention relates to a hearing aid comprising a receiver module according to any of the preceding aspects. The hearing aid may in principle be any type of hearing aid, but it is preferably selected from the group consisting of BTE, ITE, ITC or CIC.
In relation to the first, second, third, and fourth aspects, the electrical signal may e.g. represent incoming acoustic waves and/or electromagnetic waves. The source providing the waves may e.g. be synthetic speech or music e.g. generated by a computer or it could be normal regular speech. Thus, beside hearing aids, the receiver module may be used in head-sets, headphones, ALDs and of course hearing instruments.
It should be understood that, though the present invention relates to a number of independent aspects, any combination of these aspects is possible within the scope of the present document.
BRIEF DESCRIPTION OF THE INVENTION
The present invention will now be described in further details with reference to the accompanying figures, where
FIG. 1 shows a conventional hearing aid arrangement,
FIG. 2 shows the general principle behind the present invention where a normal receiver B is partly surrounded by flexible member A which is connected by tube section C to hearing aid D. The flexible member—e.g. a balloon—is connected to the outside and can there be inflated with some kind of small pump,
FIG. 3 shows a membrane attached to the balloon as a cerumen filter,
FIG. 4 shows that the membrane may be driven by a magnet attached to the membrane, the coil generates the required magnetic field,
FIG. 5 shows an alternative to the embodiment of FIG. 4 , the membrane is now driven by another type of driver (piezo, a flexible polymeric charged film, magnetostrictive, etc),
FIG. 6 shows an embodiment including a pump for pumping air, liquid or gel in or out of the flexible member,
FIG. 7 shows an arrangement where the receiver and flexible member is attaching to the hearing via a socket whereby the two parts (receiver with flexible member and hearing) may be easily disconnected and reconnected again,
FIG. 8 shows an arrangement including a vent canal so as to avoid occlusion,
FIG. 9 shows an arrangement where the tube and balloon are of a different material,
FIG. 10 shows an arrangement where an extra snout is added so that the back volume of the receiver works as a pump for blowing up the balloon,
FIG. 11 shows an arrangement where the balloon is filled with a liquid,
FIG. 12 shows an arrangement where a hole is provided in the receiver in order to connect the receiver back volume with the volume of the tube,
FIG. 13 shows an arrangement where the balloon is filled with foam,
FIG. 14 shows an arrangement where a moving coil is used as receiver,
FIG. 15 shows an arrangement where a ring of soft material is put around the balloon,
FIG. 16 shows an arrangement where the expansible means comprises a mechanically “umbrella-like” system shows as to expand the expansible means mechanically,
FIG. 17 shows the present invention applied in connection with a BTE hearing aid, and
FIG. 18 shows the present invention applied in connection with a ITE hearing aid.
DETAILED DESCRIPTION OF THE INVENTION
The main aspect of the present invention is illustrated in FIG. 2 where receiver B is at least partly surrounded by inflatable means A (e.g. balloon) which is connected to hearing aid D via tube section C. Inflatable medium A is connected to the outside and can be inflated using some kind of pump.
Inflatable means A could be a balloon which, after being inserted in the ear canal, is inflated with air, liquids, gel or the like. An external pump is used to inflate the balloon. Preferably, the pump may be controlled by the user so that the user may adjust the pressure in the balloon so as obtain maximum comfort.
In an alternative embodiment, the inflatable means can also be a flexible member filled with some sort of elastic foam. The dimensions/volume of this flexible member can be controlled by controlling the amount of air in the foam. For example, the volume of the flexible member can be reduced by pumping air out of the foam whereby the flexible member can be brought into its final position in the ear canal. At its final position air will be provided to the foam causing the foam to expand so as to fill up the area between receiver B and the ear canal as shown in FIG. 2 .
The receiver module is connected to hearing aid D via tube section C. Hearing aid D typically comprises a microphone and an amplifier to amplify electrical signals generated by the microphone. The amplified signals are provided via tube section C to receiver B.
In a preferred embodiment, tube section C has first and second end parts, the first end part being connected to inflatable means A. Tube section C is also adapted to provide to inflatable means A the medium to inflate the inflatable means (air, liquid, gel or the like). Preferable, tube section C comprises a hollow inner section for carrying electrical wires from hearing aid D to receiver B.
FIG. 3 shows a similar system as shown in FIG. 2 now with a membrane positioned in front of the receiver. This membrane acts as a filter against cerumen and thereby protects the receiver.
FIGS. 4 and 5 show alternative embodiments of the present invention. In FIG. 4 the membrane has predetermined magnetic properties determined by a magnet attached directly to the membrane. Alternatively, the predetermined magnetic properties can be achieved by doping the membrane—e.g. during manufacturing—with a magnetic material. In FIG. 4 , the membrane is driven by a coil electrically connected to the hearing aid. In FIG. 5 , the membrane is driven by some sort of driver—e.g. a driver comprising piezo-electric, a flexible polymeric charged film or magnetostrictive materials.
In FIG. 6 , a pump has been added to the embodiment shown in FIG. 3 . The pump is adapted to provide to the inflatable means the medium for inflating said means. As already mentioned, this medium could be air, liquid or gel or the like. The pump can also be used to empty the inflatable means and thereby reduce the volume of the in flatable means. Alternatively, the pump can be used to pump air out of a foam-filled flexible member so as to reduce the volume of the flexible member constituting the inflatable means. The pump can be operated either mechanically or electrically. In case of an electrical pump, the receiver of the receiver module can act as a small pump for inflating/emptying the inflatable means/foam-filled flexible member.
In FIG. 7 , the second end part of tube section C is connected to a socket having electrical terminals for connecting the receiver to the hearing aid via electrical terminals in the socket. Power signals and electrical signals representing amplified sound pressure or the like can be exchanged across the socket between the hearing aid and the receiver. Preferably, the socket also comprises handling means for handling the medium for inflating the inflatable means. This can be in form of a canal in which the medium is guided. The canal will typically be combined with some kind of closing or switch so that the medium remains within the tube section in case the socket is removed from the hearing aid.
The receiver module can also include a vent canal—see FIG. 8 . Preferably, the vent canal forms part of the inflatable means and the tube section so as to establish an unbroken vent canal from the second end part of the tube section to a point adjacent to the opening of the inflatable means. This vent canal is used to avoid occlusion and to equalise pressure between the area between the receiver module and the eardrum, and the outside.
FIG. 9 shows an arrangement almost similar to that of FIG. 3 , but wherein the tube and balloon is made of different materials.
In FIG. 10 , an extra snout is added to the receiver so that the back volume of the receiver may work as a pump for blowing up the balloon. Thus, this embodiment does not require a separate pump. The rear snout of the receiver is connected to the air canal.
FIG. 11 shows an arrangement where the balloon is filled with a liquid instead of air. The balloon may be filled with both air and liquid. Alternatively or additionally, the balloon may inflate itself from a vacuum (or lower pressure) position. Thus, in order to remove the hearing aid, the air should be pumped out, and in this “vacuum position” the balloon should be pre-tensioned so as to inflate itself upon releasing said vacuum. One way of providing a self-inflating balloon could be to manufacture it of a sponge-like material.
In FIG. 12 , the back volume of the tube is used as extra back volume for the receiver. A hole (not shown) is provided in the receiver so as to connect the receiver back volume to the volume of the tube. The tube is closed in the end opposite to the receiver by a membrane. In FIG. 13 , the balloon is filled with foam.
In FIG. 14 , the receiver comprises a moving coil (instead of a regular receiver) positioned in the inflatable balloon.
FIG. 15 shows an arrangement where a ring of soft material is put around the balloon. The soft ring may provide an even softer and painless mounting of the receiver module in the ear canal than the embodiments shown in the previous figures.
In FIG. 16 , the balloon is opened with an “umbrella-like” system so as to open the balloon mechanically. The umbrella is opened when pushing the rod E inwardly towards the receiver so as to push the soft material towards the ear wall. Pulling the rod E outwardly closes the umbrella.
FIG. 17 shows the present invention in combination with a BTE hearing aid. The receiver module is positioned within the bony area of the ear canal whereas the BTE hearing aid is outside the ear canal. The receiver module and the BTE hearing aid are connected via an extended tube section and a socket. Thus, the two parts can be easily separated in case that should be required.
FIG. 18 shows the present invention in combination with an ITE hearing aid. Again, the receiver module is positioned within the bony area of the ear canal whereas the ITE hearing aid is positioned in the soft area of the ear canal. The receiver module and the ITE hearing aid are connected via a tube section and a socket whereby the two parts can be easily separated. The concept of FIG. 18 also applies for ITC and CIC hearing aids.
It is a common feature of the combinations of FIGS. 17 and 18 that they both offer a huge adaptability. The user of the receiver module takes advantage of this adaptability in that the balloon/flexible member continuously adapts its shape to the ear canal—for example in the situation where the ear canal changes due to ageing.
In general it should be mentioned that the present invention may be applied in connection with all types of known hearing aid systems, such as BTE, ITE, ITC and CIC. Thus, variations and modifications of the disclosed embodiments may be implemented by a skilled person in the art without departing from the spirit and scope of the present invention. | The present invention relates to a receiver module being adapted to be positioned in an ear canal, the receiver module comprising a receiver having a receiver housing, said receiver being adapted to receive a time dependent electrical signal, said receiver further being adapted to generate outgoing acoustic waves via an output port in the receiver housing in response to the received time dependent electrical signal, and expansible means surrounding at least part of the receiver housing, said expansible means having an opening aligned with the output port of the receiver housing so as to allow the generated outgoing acoustic waves to penetrate away from the receiver module and into the ear canal. | 7 |
CROSS-REFERENCE
This application is a continuation application of U.S. patent application Ser. No. 13/236,220 filed Sep. 19, 2011, now U.S. Pat. No. 8,234,462 issued Jul. 31, 2012, which is a continuation of U.S. patent application Ser. No. 12/686,291 filed Jan. 12, 2010, now U.S. Pat. No. 8,024,530 issued Sep. 20, 2011, which claims priority from provisional application No. 61/144,670, filed Jan. 14, 2009, the disclosure of which is herewith incorporated by reference in their entirety.
BACKGROUND
There has long existed a basic need for rendering old, expired, or sensitive data unreadable by forensic methodologies. Businesses routinely reformat and/or carry out other actions, such that externally attached disk drives and other storage media such that sensitive data can not be read by persons who should not have access to that data. Over the years several schemes have been designed to thwart attempts to recover data from storage devices where the files have been deleted and in some cases where the storage device itself has been reformatted. However, it is believed that it is still possible to recover sensitive classified and business data from such a hard drive.
Typical methods of rendering data residing on storage devices unreadable involve writing different patterns over the old data. While this would seem to render the older data unrecoverable, it often is not the case. Different physical media types often do not completely switch the magnetic state of bits of the old data when written over. Sophisticated recovery techniques, therefore, can still obtain the data that has been “deleted” in this way.
Generally the types of utilities that attempt to render data unrecoverable require the user to explicitly execute the program and to name the file to be security wiped or erased. Other utilities are launched on a scheduled basis and are driven by script files. Still other methodologies are in place to allow IT departments and administrators to decide when and what behavior the security erase programs are to exhibit.
SUMMARY
The embodiments define ways to overcome these shortcomings for security erasing and rendering forensic attempts at recovering data unsuccessful.
Embodiments maintain a database with optimal overwrite patterns for each type of physical media that will be security erased. The embodiments have at least two basic modes of operation. A first mode security erases files when the file is deleted by the file system. A second mode covers those cases where allocation units in the form of single sectors or clusters of sectors have been pruned from a file and thus escape the security erase at file delete time; or are sectors that were returned to a sector/cluster allocation table without being security erased due to some software or hardware design, malfunction, or failure. This mode is triggered on a cyclic or scheduled basis. The embodiments scan the sector/cluster allocation table, reading unallocated sectors and comparing the data on the sector with the final pattern used to overwrite data on that specific physical media type. If the final pattern is not present on the sector, these embodiments will initiate a security erase.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the embodiments are illustrated by way of example, and not by way of limitation. The following figures and the descriptions both brief and the detailed descriptions of the embodiments refer to similar elements and in which:
FIG. 1 depicts a sector or cluster allocation table or map.
FIG. 2 depicts a sector of data and 5 overwrite patterns.
FIG. 3 depicts a database with entries specific to different physical media types and specific data overwrite patterns for each physical media type.
FIG. 4 depicts the logic flow chart for a software program that is launched by the file system or operating system either just before a file is deleted or just after a file is delete such that the software program depicted by FIG. 4 can perform a secure erase of the file.
FIG. 5 depicts the logic flow chart for a software program that is launched by the operating system on a cyclic basis such that the program can scan the allocation table or map of the storage device and perform a security erase of any unallocated sector or cluster that had not been security erased.
FIG. 6 depicts the logic flow chart for a software program that ensures that hard disk drives do not contain previously written data on the inner track areas of the disks.
FIG. 7 shows a block diagram of a computer system using this technique.
DETAILED DESCRIPTION
The present embodiments operate a computer system of the type shown as 700 in FIG. 7 . Boot is carried out using a processor 710 to execute the instructions in a system BIOS. There is at least one physical storage device, e.g. a hard drive 730 or solid state drive residing within said computer system or attached to said computer system through an external bus 735 . The external bus can be any of USB, IEEE-1394, E-SATA, SATA, Ethernet. The external bus can be any of a plurality of wireless links such as but not limited to 802.11. The computer runs an operating system encompassing a file system. The storage device stores information, as described herein. As conventional, the computer 700 can also have a user interface, RAM, display ports, and other conventional parts.
FIG. 1 shows a representation of a sector or cluster allocation map 10 of a hard drive such as 730 . This particular map is 1,024 bits wide which represents a storage device or partition that has 1,024 sectors or 1,024 clusters. If this map represented 1,024 sectors, the storage device would be 524,288 bytes in size. These maps generally represent clusters where a single cluster may contain from one sector to many sectors. Typically a cluster would contain 16, 32, or 64 sectors. A cluster size of 64 means that each cluster is made up of 64 sectors of 32,768 bytes. If the cluster map were 1,024 bits in size, that means that the storage device contains 33,554,432 bytes. There are many trade-offs in selecting cluster sizes which are not germane to the embodiments.
The representation of cluster maps in the following descriptions show allocated sectors/clusters as a binary “1” and a binary “0” if they are unallocated.
The sector/cluster map 10 depicted in FIG. 1 , 10 , contains 1,024 bits. Bit address map 11 shows the first 8 addresses and the last 8 addresses for purposes of clarity. The first sector/cluster 13 which is bit address 0000 14 shows that sector/cluster 13 is allocated by virtue of its value being equal to “1”. Thus sector/cluster map 12 has the first 3 sectors/clusters allocated (value=“1”). Sector/cluster map 12 also shows that last bit address 15 in sector/cluster map 12 is un-allocated by virtue of its value equal to “0”.
FIG. 3 is a representation of a database 40 where each entry 42 , 43 , and 44 contain sets of records specific to particular types of storage media. Entry 3 ; item 44 , contains specific overwrite data for media type 45 . Entry 3 also contains number of patterns 46 which specifies the number of unique overwrite patterns for this storage media type. For entry 3 ; 44 there are “n” overwrite patterns represented by pattern 1 ; 47 to pattern “n” 48 . When an overwrite operating is being executed, the software program 50 or 70 uses number of patterns 46 and pattern 1 47 through pattern “n” 48 to ensure that overwritten data is not recoverable.
FIG. 2 shows a representation 20 of a single sector of data. Sector byte address map 21 shows the byte addresses ranging from 000 23 to 511 24 . Note that this address map shows sector 22 which contains 512 addressable bytes of data. The first byte of data is sector address 0 23 and the last byte of data is sector address 511 26 . Also note that only the first 8 bytes of sector 22 and the last 8 bytes of sector 22 are shown for purposes of clarity. In FIG. 2 , sector data is represented as hexadecimal values. Sector 22 contains the data that was written to the storage device by some application. Also shown are 5 overwrite patterns as pattern 1 27 , pattern 2 28 , pattern 3 29 , pattern 4 30 , and pattern 5 31 . Overwrite patterns typically contain alternate bit patters. For example, pattern 1 27 contains the hexadecimal value “AA” which has a binary pattern of “1010 1010”. Pattern 2 28 contains the hexadecimal value “55” which has a binary pattern of 0101 0101″. Note that these 2 patterns are made up of alternating bits and the bits between each pattern are different. When pattern 1 27 is written, then pattern 2 28 is written over pattern 1 27 , each bit will have been written as a “1” and then written as a “0”.
Pattern 3 29 contains the hexadecimal value “CC” which has a binary pattern of “1100 1100”. Pattern 4 30 contains the hexadecimal value “33” which has a binary pattern of 0011 0011″. Note that these two patterns are made up of alternating groups of bits and the bits between each pattern are different. When pattern 3 29 is written then pattern 4 30 is written over pattern 3 29 , each group of 2 bits will have been written as a “1” and then written as a “0”.
Pattern 5 31 contains the hexadecimal value “FF” which has a binary pattern of “1111 1111”. Typically a pattern with all bits in a byte being equal to “1” or “0” will be the final pattern written to the storage media.
The patterns represented here are not to be construed as being the actual over write patterns for any physical media type. The values shown in pattern 1 27 through pattern 5 31 are for the purposes of explaining portions of the embodiments.
FIG. 4 shows the logic flow 50 of the file overwrite software program of the embodiments. In this flow 50 , the file system or operating system of the computer system the embodiments is running, or will call or cause software program 50 to be executed. When software program 50 is started, receive notification 51 starts the execution. Processing block 52 retrieves from the file system entry. The file system entry may have been passed to software program 50 as a function of the calling process or process block 52 may make calls to the operating system to retrieve the entry for the deleted file. Processing block 53 then retrieves the sector/cluster linked list or map of allocated sectors that had been assigned to the file that was deleted. Note that the file system may delete the file prior to calling software program 50 or may call software program 50 prior to actually deleting the file and returning the sectors/clusters to the allocation map or pool.
Processing block 54 interrogates the operating system for the physical media type containing the sectors for the file sectors that are to be security erased. Using the media type provided by the operating system, processing block 55 accesses database 40 . Processing block 56 sets a pointer to pattern 1 47 which is the first overwrite pattern for media type 45 . Processing block 57 retrieves the number of patterns 46 and places the number of patterns into a counter.
The overwrite cycle starts with processing block 58 which overwrites the pattern indicated by the pointer set in processing block 56 . After the pattern has been written on all of the sectors identified by the linked list or map obtained by processing block 53 , processing block 59 will decrement the number of patterns counter set by processing block 57 . Decision block 60 checks to see if the pattern counter is equal to 0. If the pattern counter is equal to 0, then software program 50 will exit at exit point 61 . If the pattern counter is not equal to 0, processing block 62 will move the pattern pointer set by processing block 56 to the next pattern in the sequence of patterns then passes control to processing block 58 which starts the next overwrite pattern write.
FIG. 5 shows the logic flow 70 of the sector/cluster scan overwrite software program of the embodiments. In this flowchart 70 , the operating system of the computer system the will call or cause software program 50 to be executed on some cyclic basis. When software program 70 is started, start sector/cluster scan 71 is the entry point to the software program. Processing block 72 interrogates the operating system for the physical media type of the physical storage device that is to be scanned. Note that software program 70 can be run by the operating system against internal storage devices and externally attached storage devices.
Processing block 72 obtains the physical media type from the operating system and accesses database 40 and sets a pointer to the correct entry 42 , 43 , or 44 . For this example entry 44 media type 45 matches the physical media type obtained from the operating system. Processing block 73 then retrieves the first byte of sector/cluster map for the physical storage device.
From this point on there are three logical processing loops in software program 70 . There is a outer loop ranging from processing block 74 to decision block 78 , an inner loop ranging from processing block 75 to decision block 77 , and one side processing loop ranging from processing block 82 to processing block 85 .
The outer loop begins with processing block 74 which loads a byte size (8 bits) bit mask with a binary pattern of “1000 0000”. Processing block 75 performs a logical AND of the bit mask with the current contents obtained from sector/cluster map 12 for the physical storage device. If the matching bits of sector/cluster map 12 for the physical storage device and the bit mask are both a binary “1”, the resulting value will be a logical TRUE Boolean value. Decision block 78 examines the resulting Boolean value. If it is true, this indicates that the sector/cluster is currently allocated. If the Boolean value is FALSE, this indicates that the sector/cluster is not allocated and control will be pasted to processing block 80 . Assuming that the resulting value of the AND function was TRUE, control will be passed to decision block 77 .
Decision block 77 tests to see if the current bit in the bit mask is the last bit to be tested for this cycle. For this example the last bit position in the mask has the binary value of “0000 0001”. If this is not the case, then control is passed to processing block 87 . Processing block 87 shifts the pattern in the bit mask one position to the right. If the pattern in the bit mask prior to processing block 87 was “0100 0000” it will be shifted one position to the right resulting in the pattern being changed to “0010 0000”. After the bit mask has been shifted one position to the right, control is passed to processing block 75 which is the beginning of the inner loop.
If decision block 77 determines that the pattern in the bit mask is “0000 0001”, then it decides that this was the last bit in the mask to be tested and processing falls through to decision block 78 . Decision block 78 determines if the current byte of sector/cluster map 12 being tested is the last byte of the sector/cluster map 12 control will be passed to exit point 79 . If decision block 78 determines that the current byte of sector/cluster map 12 is not the last byte in sector/cluster map 12 control will be passed to processing block 88 . Processing block 88 retrieves the next byte of the sector/cluster map and passes control to processing block 74 which is the start of the outer processing loop.
If decision block 76 determines that the result of the AND function which tests to see if the current sector/cluster being tested with the bit mask is not allocated, control will be passed to processing block 80 . Processing block 80 accesses database 40 and sets a pointer to pattern 1 47 which is the fist overwrite pattern for media type 45 . Processing block 81 then retrieves the number of patterns 46 and places the number into a counter.
Processing block 82 is the first block of the side processing loop. Processing block 82 overwrites the current pattern pointed to by the pointer initially set by processing block 80 on the sector or cluster identified by the current byte of sector/bluster map 12 . After the sector or cluster identified by the current byte of sector/bluster map has been overwritten, control is passed to processing block 83 . Processing block 83 decrements the number of patterns counter set by processing block 81 .
Decision block 84 then determines is the number of patterns remaining to be written is greater than zero.
If the number of patterns counter is greater than zero, control is passed to processing block 85 which sets the pattern pointer initially set by processing block 80 to the next pattern.
Decision block 84 checks to see if the pattern counter is equal to 0. If the pattern counter is equal to 0 then control is passed to decision block 77 . If the pattern counter is not equal to 0, processing block 85 will move the pattern pointer set by processing block 80 to the next pattern in the sequence of patterns then passes control to processing block 82 which starts the next overwrite pattern write.
Another method of recovering erased or reformatted data from hard disk drives is through the use forensic tools that can micro-step the write/read heads off of the center of the track to an area that is reserved by the disk drive. This area exists between the tracks of hard disk drive to cover the case where the heads may wander off of the center line of a given track. The case also exists that is referred to as “track creep”. Hard disk drives have a tendency to move the track outward or inward depending on the drive. This movement is caused by wear of the various mechanical parts and assemblies in a hard disk drive. Overwriting a given track will normally only overwrite the track on the center of the track. If track creep has developed in the drive, then there exists the possibility of data remaining on the area between the tracks. FIG. 6 shows a flow diagram 90 is intended to cover the possibility of data being present in the areas between tracks.
Software program off-track write 91 is called by another application program such as those depicted in FIG. 4 and FIG. 5 . When software program off-track write is called, the calling program will pass the pattern to be written, the first sector of the sequence to be written and the number of sectors to write.
Process block 92 commands the hard disk drive into a diagnostic mode where additional commands such as micro-step are available. Some hard disk drive may not need to be placed into a diagnostic mode in order for software program off-track write to access the hard disk's ability to be commanded to micro-step.
Processing block 93 will command the write head of the hard disk drive to the center of the current track containing the sectors to be written. Process block 94 then writes the data pattern received from the calling software program to the specified sectors.
Software program off-track write has two basic micro-step loops. The first loop ranges from processing block 96 to decision block 99 . This loop micro-steps the write head inward toward the hub of the hard disk drive. The second loop ranges from processing block 102 to decision block 105 . This loop micro-steps the write head outward from the center of the track toward the outer diameter of the hard disk drive.
The first loop receives control from processing block 95 which sets the number of micro-steps of the write head. Processing block 96 commands the write head inward for a specified distance or number of steps depending on the particular hard disk drive. Processing block 97 then writes the same pattern that had been written on the same sectors on the center of the track.
Processing block 98 then decrements the number of inner micro-steps and passes control to decision block 99 . Decision block 99 checks to see if the number of remaining micro-steps is zero. If the number of remaining micro-steps is greater than zero, it passes control to the beginning of the fist loop at processing block 96 . If the number of remaining micro-steps is zero decision block 99 passes control to processing block 100 .
Processing block 100 will command the write head of the hard disk drive to the center of the current track containing the sectors to be written.
The second loop receives control from processing block 101 which sets the number of micro-steps of the write head. Processing block 102 commands the write head outward for a specified distance or number of steps depending on the particular hard disk drive. Processing block 103 then writes the same pattern that had been written on the same sectors on the center of the track.
Processing block 104 then decrements the number of outer micro-steps and passes control to decision block 105 . Decision block 105 checks to see if the number of remaining micro-steps is zero. If the number of remaining micro-steps is greater than zero it passes control to the beginning of the second loop at processing block 102 . If the number of remaining micro-steps is zero decision block 105 passes control to processing block 106 .
Processing blocks 106 and 107 clean up the track that has just been processed, ensuring that the center of the track contains valid data in the form of the overwrite pattern. Processing block 106 will command the write head of the hard disk drive to the center of the current track containing the sectors to be written. Process block 107 then writes the data pattern received from the calling software program to the specified sectors. Control is then passed to exit off-track write 108 .
Although only a few embodiments have been disclosed in detail above, other embodiments are possible and the inventors intend these to be encompassed within this specification. The specification describes specific examples to accomplish a more general goal that may be accomplished in another way. This disclosure is intended to be exemplary, and the claims are intended to cover any modification or alternative which might be predictable to a person having ordinary skill in the art. The present application describes use of a hard drive in a computer system, operating to execute programs. Other drives and other techniques can be supported in analogous ways.
Those of skill would further appreciate that the various illustrative logical blocks, modules, circuits, and algorithm steps described in connection with the embodiments disclosed herein may be implemented as electronic hardware, computer software, or combinations of both. To clearly illustrate this interchangeability of hardware and software, various illustrative components, blocks, modules, circuits, and steps have been described above generally in terms of their functionality. Whether such functionality is implemented as hardware or software depends upon the particular application and design constraints imposed on the overall system. Skilled artisans may implement the described functionality in varying ways for each particular application, but such implementation decisions should not be interpreted as causing a departure from the scope of the exemplary embodiments of the embodiments.
The various illustrative logical blocks, modules, and circuits described in connection with the embodiments disclosed herein, may be implemented or performed with a general purpose processor, a Digital Signal Processor (DSP), an Application Specific Integrated Circuit (ASIC), a Field Programmable Gate Array (FPGA) or other programmable logic device, discrete gate or transistor logic, discrete hardware components, or any combination thereof designed to perform the functions described herein. A general purpose processor may be a microprocessor, but in the alternative, the processor may be any conventional processor, controller, microcontroller, or state machine. The processor can be part of a computer system that also has a user interface port that communicates with a user interface, and which receives commands entered by a user, has at least one memory (e.g., hard drive or other comparable storage, and random access memory) that stores electronic information including a program that operates under control of the processor and with communication via the user interface port, and a video output that produces its output via any kind of video output format, e.g., VGA, DVI, HDMI, displayport, or any other form.
A processor may also be implemented as a combination of computing devices, e.g., a combination of a DSP and a microprocessor, a plurality of microprocessors, one or more microprocessors in conjunction with a DSP core, or any other such configuration. These devices may also be used to select values for devices as described herein.
The steps of a method or algorithm described in connection with the embodiments disclosed herein may be embodied directly in hardware, in a software module executed by a processor, or in a combination of the two. A software module may reside in Random Access Memory (RAM), flash memory, Read Only Memory (ROM), Electrically Programmable ROM (EPROM), Electrically Erasable Programmable ROM (EEPROM), registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art. An exemplary storage medium is coupled to the processor such that the processor can read information from, and write information to, the storage medium. In the alternative, the storage medium may be integral to the processor. The processor and the storage medium may reside in an ASIC. The ASIC may reside in a user terminal. In the alternative, the processor and the storage medium may reside as discrete components in a user terminal.
In one or more exemplary embodiments, the functions described may be implemented in hardware, software, firmware, or any combination thereof. If implemented in software, the functions may be stored on or transmitted over as one or more instructions or code on a computer-readable medium. Computer-readable media includes both computer storage media and communication media including any medium that facilitates transfer of a computer program from one place to another. A storage media may be any available media that can be accessed by a computer. By way of example, and not limitation, such computer-readable media can comprise RAM, ROM, EEPROM, CD-ROM or other optical disk storage, magnetic disk storage or other magnetic storage devices, or any other medium that can be used to carry or store desired program code in the form of instructions or data structures and that can be accessed by a computer. The memory storage can also be rotating magnetic hard disk drives, optical disk drives, or flash memory based storage drives or other such solid state, magnetic, or optical storage devices. Also, any connection is properly termed a computer-readable medium. For example, if the software is transmitted from a website, server, or other remote source using a coaxial cable, fiber optic cable, twisted pair, digital subscriber line (DSL), or wireless technologies such as infrared, radio, and microwave, then the coaxial cable, fiber optic cable, twisted pair, DSL, or wireless technologies such as infrared, radio, and microwave are included in the definition of medium. Disk and disc, as used herein, includes compact disc (CD), laser disc, optical disc, digital versatile disc (DVD), floppy disk and blu-ray disc where disks usually reproduce data magnetically, while discs reproduce data optically with lasers. Combinations of the above should also be included within the scope of computer-readable media.
Operations as described herein can be carried out on or over a website. The website can be operated on a server computer, or operated locally, e.g., by being downloaded to the client computer, or operated via a server farm. The website can be accessed over a mobile phone or a PDA, or on any other client. The website can use HTML code in any form, e.g., MHTML, or XML, and via any form such as cascading style sheets (“CSS”) or other.
Also, the inventors intend that only those claims which use the words “means for” are intended to be interpreted under 35 USC 112, sixth paragraph. Moreover, no limitations from the specification are intended to be read into any claims, unless those limitations are expressly included in the claims. The computers described herein may be any kind of computer, either general purpose, or some specific purpose computer such as a workstation. The programs may be written in C, or Java, Brew or any other programming language. The programs may be resident on a storage medium, e.g., magnetic or optical, e.g. the computer hard drive, a removable disk or media such as a memory stick or SD media, or other removable medium. The programs may also be run over a network, for example, with a server or other machine sending signals to the local machine, which allows the local machine to carry out the operations described herein.
Where a specific numerical value is mentioned herein, it should be considered that the value may be increased or decreased by 20%, while still staying within the teachings of the present application, unless some different range is specifically mentioned. Where a specified logical sense is used, the opposite logical sense is also intended to be encompassed.
The previous description of the disclosed exemplary embodiments is provided to enable any person skilled in the art to make or use the embodiments. Various modifications to these exemplary embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the embodiments. Thus, the embodiments is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein. | Secure erase of files and unallocated sectors on storage media such that any previous data is non-recoverable. The database contains sets of data patterns used to overwrite the data on different physical media. The software programs manage the overwriting process automatically when a file has been deleted. When de-allocated sectors in the file system are pruned from a file or escaped the file deletion process also finds them. Data will never be found on deleted sectors or on pruned sectors is overwritten. | 6 |
FIELD OF THE INVENTION
The present invention relates to an automatic embroidering machine which produces efficiently beautiful multi-color embroiderings of a plurality of patterns.
BACKGROUND OF THE INVENTION
The invention relates to automatic embroidering machines for producing multi-color embroiderings. Prior art discloses automatic machines for multi-color embroidering.
With respect to forming sequences of embroidered patterns with changing colors with conventional automatic embroidering machines, an explanation will be made referring to with FIGS. 12 and 13.
If patterns shown in FIG. 12 are to be formed, and those data are arranged as shown in FIG. 13, the patterns are formed in following sequences, where C1 to C3 are color changing codes.
A letter C is stitched with a thread of Color C1.
As an embroidering machine stops to change this color at a point "a", the thread is changed to a thread of Color C2.
The next letter O is stitched with the thread of Color C2.
As the machine stops to change this color at a point "b", the thread is changed to a thread of Color C3, and the letter L is formed with the thread of Color C3.
As the machine stops to change this color at a point "c", the thread is changed to Color C2 and the second letter O is formed with the thread of Color C2.
As the machine stops to change this color at a point "d", the thread is changed to Color C1, and the letter of R is stitched with the thread of Color C1.
As it is seen apparently, the machine stops each time to change colors of the embroidering threads. For example, if the colors of the threads are very often changed as C1, C2, C3, C1, C2, C1, C3, C1, C2, C3, C2 . . . , the machine stops at such a time for changing the threads. Therefore, the operation consumes much time inefficiently.
SUMMARY OF THE INVENTION
It is an object of the invention to provide an automatic multi-color embroidering machine which consumes less time in forming a multi-color embroidering pattern than a conventional embroidering machine forming a similar pattern. The object of the invention is achieved with an embroidering machine comprising first control means which, in embroidering data, includes color changing codes and coordinate codes for embroidering patterns of the same colors in sequence by comparing the color changing codes, and a second control means for moving an embroidering frame to a coordinate which shows a color changing code of a different color so as to form patterns of the different colors.
The automatic embroidering machine according to the invention further comprises calculation means, in the first control means, which calculates needle dropping points for moving the embroidering frame such that bridging threads between the formed patterns of the same colors having been skipped by the first control means, are not involved by a subsequent embroidering pattern of the other color.
According to the invention, since it is possible to reduce changing of the embroidering thread to the minimum even when forming embroidering multi-color patterns, the embroidering may be performed efficiently, and in addition since the bridging thread is not involved by the following pattern of the different color, beautiful embroidered patterns may be formed.
The present invention both as to its construction so to its mode of operation, together with additional objects and advantages thereof, will be best understood from the following description of the preferred embodiments with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a flow chart showing embroidering processes for changing colors;
FIGS. 1B-1D is an explanation of steps shown in FIG. 1A.
FIG. 2 is a flow chart showing a sub-routine in response to the step of calculating needle dropping points and moving an embroidering frame according to flow chart of FIG. 1;
FIG. 3 is a block diagram of an automatic embroidering machine;
FIG. 4 shows an example of an embroidered pattern;
FIG. 5 shows embroidering data of the patterns of FIG. 4;
FIGS. 6 and 7 show embroidering sequences;
FIG. 8 shows elements of the embroidering data by figure or device;
FIG. 9 shows modifications of FIG. 8 by figure or device;
FIG. 10 shows an example of the embroidered pattern;
FIG. 11 shows relative positions between needle droppings and embroidered patterns;
FIG. 12 shows an example of a conventional embroidering pattern identical to that of FIG. 4;
FIG. 13 shows embroidering data of the pattern of FIG. 12;
FIG. 14 shows an example of another embroidered pattern;
FIG. 15 shows a condition of a bridging thread when forming embroidered patterns;
FIG. 16 shows a perspective view of an embroidering machine in which the control apparatus of the invention is used.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
An automatic embroidering machine will be described with a reference to the block-diagram of FIG. 3.
A central processing unit (CPU) is connected with a read only memory (ROM) for storing a control program via a data base line (DB) and a random access memory (RAM) for storing embroidering data temporally.
The data base line (DB) is connected, via an input-output device (I/O-1), with a sensor (SEN) for obtaining various control parameters such as phases of a needle bar so as to control the embroidering machine. An input-output device (I/O-2), with operation keys (KEY) serves for receiving orders such as selections of embroidering patterns from a machine operator. An input-output device (I/O-3) has an indicator (DISP) for indicating operations of an operating key such as the selected embroidering patterns. An input-output device (I/O-4), with pulse motors (XM)(YM) carries out X-Y controls of the supporter (SPT) connecting with an embroidering frame 10 movable relative to the needle 12. A machine motor (ZN) drives stitch forming means and an actuator (ACT) such as a solenoid for slacking a thread, to form the patterns. An input-output device (I/O-5), with an external memory (EM) is used for storing a plurality of embroidering data.
The embroidering process with changing the colors will be discussed mainly with reference to the flow chart of FIG. 1. Reference numerals in the following explanation will show respective steps of the control sequence.
Steps (10) to (20) are used for carrying out searches of color changing commands, and Step (21) and following steps are used for controlling the embroidering operation. The performed steps are as follows:
(10): waits for an input from the key (KEY), and goes to a next step on the input therefrom,
(11): goes to (13) if it is an embroidering start key,
(12): carries out other commands than the embroidering start, and goes back to (10),
(13): reads in the data from the memory (RAM),
(14): checks the data obtained at (13), and goes to (18) if the checked data is not a color changing code,
(15): stores in (RAM) the color changing code among the data obtained at (13) and the position coordinate of the embroidering frame,
(16): checks whether the color changing code obtained at (13) has firstly appeared, and if not, goes back to (13) for checking a next data,
(17): if yes as a result of checking (16), stores the position coordinate of the frame in (RAM), and goes back to (13),
(18): checks whether the data obtained at (13) is a final code, and if yes, goes to (21),
(19): checks whether the data obtained at (13) is a control data, and if yes, goes back to (13),
(20): obtains a new position coordinate from data obtained at (13) as a position coordinate of the present embroidering frame, stores it in (RAM) and goes back to (13),
(21): re-sets a read-in pointer of the data, and stores in (RAM) the color changing code of the first embroidering pattern as the present embroidering color from the data stored in (17),
(22): reads in the data from (RAM),
(23): checks the data obtained at (22), and goes to (35) if it is not the color changing code,
(24): if it is the color changing code, compares with the present embroidering color,
(25): goes to (35), if the compared result at (24) is the same color,
(26): if the compared result at (24) is a different color, obtain a position coordinate of the embroidering start of a next pattern of the same color as the present color with reference to the data stored at (15),
(27): goes to (40), if a next embroidering pattern exists in the process at (26),
(28): if the next pattern does not exist in a process of (26), registers the color code of a next pattern as a present pattern, with reference to the data stored at (17),
(29): obtains the position coordinate of an initial embroidering pattern of a next color,
(30): moves the embroidering frame to the position coordinate obtained at (29),
(31): shows in the indicator (DISP) to change the color of the thread,
(32): waits for an input from the key (KEY), and goes to a next step on the input therefrom,
(33): if it is the embroidering start key, goes back to (22) to continue the embroidering,
(34): carries out other processes than the embroidering start, and goes back to (32),
(35): if the data obtained at (22) is not a final code, goes to a next step, and if it is the final code, finishes the embroidering of changing the color,
(36): goes back to (22) after having embroidered,
(40): carries out a calculation of the needle dropping and moves the embroidering frame until the position coordinate of the embroidering start obtained at (26).
With respect to Step (40) of the flow chart corresponding to this sub-routine, an explanation will be made to later in detail.
In the flow chart of FIG. 1, the main steps of the first control means where the patterns of the same colors are formed in sequence, are Steps (35), (36) and Steps (26), (27), (40). Steps (22) to (25) are common steps therebetween. Steps (26) to (30) are the main steps of the second control means which moves the embroidering frame to a coordinate where a color changing code of a different color appears for embroidering the patterns of the different colors. Step (40) is the main step of the calculation means which calculates the needle dropping points of the bridging thread and moves the frame.
With respect to the sequence of forming the patterns with changing the colors, an explanation will be made, referring to FIGS. 4 to 7.
If the embroidering pattern as shown in FIG. 4 and data as shown in FIG. 5, similar to those of FIGS. 12 and 13, the patterns are formed as follows, where C1 to C3 of FIG. 5 are the color changing codes.
(1): stitches the letter of C with the color of C1,
(2): stitches the letter of R with the same color via Step (26), (27), (40) (FIG. 6),
(3): changes to C2, since the stitching stops at the point "a" by Steps (26) to (30) of the second control means,
(4): forms the letter of O with C2,
(5): forms the letter of O with the same color via Steps (26), (27) and (40) of the first control means,
(6): changes to C3, since the forming stops at the point "b" by Steps (26) to (30) of the second control means,
(7): embroiders the letter of L with C3.
In forming of the patterns according to the invention, a consideration will be given to problems of the bridging thread between the produced patterns of the same color which have been skipped by the first control means.
If the letters of "a" and "r" have the same color, and the letters of "fte" have the different colors in FIGS. 14 and 15, the letters of "a" and "r" are firstly stitched in lump.
However, if no attention is paid to that the letters are of different colors, the embroidering thread is drawn as the bridging thread (T) as seen in FIG. 15 between a terminal point "i" of the stitched letter "a" and a start point "n" of the letter "r". If the letters "fte" are stitched with the other threads thereafter, the bridging thread (T) is involved, and it takes much time in removing the involved thread later.
Such problems are solved by the invention as follows. If the letters of "a" and "r" of FIG. 10 have the same color as in FIG. 14 and the letters "fte" have the different color, the embroidering frame is moved such that the needle droppings pass the positions shown with points of i, j, k, l, m, n of FIG. 11 when the embroidering is carried out from the letters "a" to "r" by means of Step (40) of FIG. 1 which is the main step of the moving means.
The operation of the moving means will be explained with FIGS. 2, 8 and 9 wherein (41) to (48) of FIG. 2 show respective steps.
(41): obtains a moving distance until a first needle dropping point (point k of FIG. 11) which is a right upper point of the scope of finishing the embroidering pattern (letter "a"). In general, the embroidering scope is composed of elements shown in FIG. 8, and an actual scope is used by multiplying enlarging rate or reduction rate to this scope.
In FIG. 8,
h: height of the pattern,
w: width of the pattern,
u: height of a part protruded downward from A-D line.
The part "u" is normally zero, and is data prepared for letters such as "f" and "y" having downward protrusions beyond A-D line.
If the actual embroidering scope is assumed as A-B'-C'-D' as shown in FIG. 9, an initial needle dropping point C' is w' (w'=width (w) of pattern x enlarging rate) in X-axis from a reference point A and h' (h'=height (h) of pattern x enlarging rate) in Y-axis from the same.
However, since the embroidering terminates at a point "e" as a result it is sufficient to obtain the distances H, W between e - C'.
H and W are respectively,
H=h'- ey
W=w'- ex.
"ex" and "ey" are coordinate positions from point A in x-axis and y-axis of point "e", which are obtained by multiplying the relative distance from the reference point A.
(42): obtains the distances H, W from points "i" to "k" of FIG. 11,
(43): moves the frame by the amount of the distances H, W obtained at (42), that is, moves to point j on the x-axis by W and then moves to point k on the y-axis by H,
(44): single-stitches at point k,
(45): obtains a moving distance until a next needle dropping point ("l" of FIG. 11). This point is at a left upper point of the embroidering scope of a next embroidering pattern (letter "r"), and is actually obtained by width of letters "fte" x magnifying power + spaces between letters. Since the height on the Y-axis is not changed, the frame is not moved.
(46): moves the frame by the amount of the distance obtained at (45),
(47): one-stitches at point "l" after moving,
(48): finally moves the frame until point "n" of the embroidering start via point "m".
In the above thread bridging process, in FIG. 11, the needle dropping positions are obtained in order of the points j, k, l, m by moving the frame during moving from a stitch termination point "i" of letter "a" to a stitch starting point "n" of letter "r", and the stitchings are formed one-stitch by one-stitch at the points "k" and "l". Instead, it is also sufficient that the needle dropping points are obtained directly in order of the points "k" and "l", and the stitches are formed one-stitch by one-stitch at these points.
While the invention has been illustrated and described as embodied in an automatic embroidering machine, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention.
What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims. | An automatic embroidering machine comprising a stitch forming unit including a vertically reciprocating needle, an embroidering frame for supporting a fabric to be stitched, a drive for effecting X-Y movement of the embroidering frame in accordance with vertical reciprocal movement of the needle, a first control unit for coordinating codes for embroidering patterns of the same color in sequence by comparing color changing codes included in embroidering data, and a second control unit for moving the embroidering frame to a coordinate with a color changing code of a different color to form patterns of different colors. | 3 |
This is a continuation of application Ser. No. 08/825,975, filed on Apr. 4, 1997, now U.S. Pat. No. 5,916,415 which is a continuation of application Ser. No. 08/570,180, filed Dec. 7, 1995, now abandoned.
TECHNICAL FIELD
This invention pertains to improved methods for oxygen delignification and brightening of medium consistency pulp slurry. This method utilizes a two phase reaction design with hydrogen peroxide enhancement.
BACKGROUND OF THE INVENTION
The known methods and apparatii for oxygen delignification of medium consistency pulp slurry consist of the use of high shear mixers and single reactors with retention times of twenty to sixty minutes. These are operated at consistencies of ten to fourteen percent (o.d.) at an alkaline pH of from 10 to 12.5. Oxygen gas and hydrogen peroxide are contacted with the pulp slurry in a turbulent state lasting less than one second. The oxygen gas and hydrogen peroxide are both added prior to the high shear mixer, either simultaneously, or the hydrogen peroxide is added prior to the oxygen by 10-300 seconds. To date, sulfite pulp systems of the aforementioned design have resulted in 60-70% Kappa number reduction and a brightness increase of 20-25% ISO. It has been reported that over half of the Kappa number reduction can occur at the high shear mixer, after the oxygen gas is introduced. Final brightness of 84-86% ISO can be achieved with additional hydrogen peroxide bleaching steps
The disadvantages of the known methods is that high total dosages of hydrogen peroxide, often in excess of 5.0% are required to achieve a mid-80's ISO brightness, and this often requires two separate hydrogen peroxide bleaching stages following the oxygen delignification stage.
It is understood that oxygen delignification reaction proceeds under two distinct orders of reaction kinetics. The fist reaction occurs rapidly, and is responsible for lignin fragmentation (delignification). It is a radical bleaching reaction that is dependent on alkali concentration or pH to proceed. It also consumes alkali (e.g., NaOH) as it proceeds and generates organic acids, causing pH to drop by one-half to one point. This is consistent with prior noted field observations. The second reaction occurs slowly, at a rate estimated to be twenty times slower than the first reaction. This reaction is responsible for the destruction of chromophoric structures (brightness development). It is an ionic bleaching reaction that is dependent on alkali concentration, and pH, to proceed. It also will consume alkali as it proceeds and generate organic acids, causing the pH to drop by one to two points during the reaction time.
The addition of hydrogen peroxide (H 2 O 2 ) to an oxygen delignification stage will increase both orders of the reaction kinetics, resulting in increased delignification and brightness. It will, for sulfite pulps, have the largest impact on the first rapid, delignification reaction. The impact of the peroxide slows dramatically during the second brightening reaction This may be due to the applied hydrogen peroxide reacting as both a delignification and a brightening agent in the fist reaction. This will consume hydrogen peroxide and increase alkali consumption during the first order reaction Corrections in hydrogen peroxide and alkali will be required for the second reaction to proceed efficiently.
SUMMARY OF THE INVENTION
It is a purpose of this invention to set forth a method for delignification and brightening of pulp in a slurry at medium consistency to a level that will improve subsequent totally chlorine free (TCF) brightness response with minimal bleach chemical usage. This invention utilizes a two phase oxygen delignification concept with hydrogen peroxide being added only to the second reaction phase. The invention can be utilized for retrofits to eking medium consistency oxygen delignification systems as well as for new systems.
To effectively accomplish this objective (OOp), the oxygen delignfication system will be designed with two reactors, each with a dedicated mixer. The first mixer will be a high shear or extended time gas mixer for oxygen gas and alkali and the first reactor will have a retention time of 5-10 minutes (O). The second mixer will be an extended time or high shear mixer for oxygen gas, hydrogen peroxide and alkali and will have a retention time of 30-180 minutes (Op).
The aforesaid, and further purposes and features of the invention will become apparent by reference to the following description, taken in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a graphical depiction of an O/Op Reaction Flow Diagram for the delignification and brightening for wood pulp;
FIG. 2 is a plot of Kappa vs. time (min.) showing the effect of 60 minute oxygen delignification (O), in comparison to 60 minute oxygen delignification with the addition of 0.5% H 2 O 2 (Op), and 10 minute oxygen delignification followed by 50 minute (Op) stage with the addition of 0.5% H 2 O 2 (OOp); and
FIG. 3 is a plot of % ISO vs. time (min) making the same comparison as described for FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings wherein the showings are for purposes of illustrating the preferred embodiment of the invention only and not for purposes of limiting the same, FIG. 1 shows a reaction schematic which would be used in a preferred embodiment of this invention. In this schematic, the apparatus 10 shows two mixers, a higher shear mixer 18 and an extended contact gas mixer 28 installed in series. Each mixer has a retention time of from less than one second to 5 minutes. The operating pressure of the apparatus 10 and the method which it practices is preferably from approximately 20 to 200 psig. A source 12 of pulp slurry is fed to the high shear or extended time contact gas mixer 18 having a consistency of from approximately 10 to 16%, at a temperature of from approximately 170-240° F., preferably from 190-220° F. A source of alkali is communicated with the mixer 18 either directly or prior to for thorough mixing thereof with the slurry to effect a pH of the slurry from approximately 11.0 or higher, more preferably 12.0 or higher. A source of oxygen gas 16 is provided to communicate with the mixer 18 either directly or prior to for inclusion in the mixing process. The contents of the first mixer 18 are kept agitated for from less than one second to 5 minutes with subsequent transfer to pressurized reactor 20. A source of steam 34 in communication with mixer 18 will insure that the slurry is maintained in the temperature range described. Downstream of this pressurized reactor is a second mixer 28 with associated inlets for alkali 22, oxygen 26 and peroxide 24. The alkali will return the pH of the slurry to at least 11.0, more preferably 12.0, while the oxygen source will replenish depleted oxygen consumed or partially consumed in the first reaction. Another source of steam 36 or the same source identified previously 34 is provided and communicated with the product to bring the slurry temperature back to approximately 170 to 240° F., more preferably 190 to 220° F. The slurry is then agitated in the mixer 28 for less than one second to five minutes. The product is conducted to a second reactor 30 wherein the slower ionic bleaching reaction takes place at a temperature of from 170° F. to 240° F., preferably from 190 to 220° F. The pressure in the first reactor will range from 60-180 psig, and more preferably from 85-140 psig. The pressure in the second reactor will range from 0-180 psig and in one case, preferably from 85-140 psig.
A series of autoclave reactions were performed on Sulfite pulp (brownstock) which was characterized in having a Kappa number of 10.7, a viscosity of 33.4 cps, a brightness of 51% ISO and a Z-span of 18.7 psi. This material served as the baseline case for all testing, the results of which are summarized in the row designated "base" in Table I.
The laboratory work described below utilized an autoclave type oxygen reactor. Sequences labeled 1 and 2 show the effects of oxygen delignification (O stage), under constant conditions shown in Table 1, after 10 and 60 minutes. The final pHs are 11.7 and 9.9, respectively. Note that 64% of the total Kappa number drop and less than 45% of the total % ISO gain occur in the first 10 minutes of the total 60 minute reaction. These results are also shown in FIGS. 2 and 3. This is typical of the initial radical delignification reactions.
TABLE 1__________________________________________________________________________Oxygen Delignification & Bleaching.sup.(a) Resid.Time Kappa Final Visc Z-span T NaOH NaOH H.sub.2 O.sub.2 H.sub.2 O.sub.2 NaOHStage(min) # ISO pH cps (psi) ° C. #1.sup.b #2.sup.c #1.sup.b #2.sup.c (gpl)__________________________________________________________________________0 base 0 10.7 51.0 33.4 18.71 O 10 6.6 57.0 11.7 32.7 14.3 100 2.5% -- -- -- 0.502 O 60 4.3 64.9 9.9 33.1 13.9 100 2.5% -- -- -- 0.303 Op 10 3.8 65.0 11.4 32.0 12.2 100 3.0% -- 0.5% -- 0.724 Op 60 3.4 68.8 9.5 32.5 14.0 100 3.0% -- 0.5% -- 0.365 O/Op10/50 2.7 74.4 10.0 30.2 13.7 100 2.5% 0.5% -- 0.5% 0.256 O/Op10/50 3.0 71.5 10.0 29.7 12.4 90 2.5% 0.5% -- 0.5% 0.37__________________________________________________________________________ .sup.(a) Conditions included 100 psig O.sub.2 and 0.5% MgSO.sub.4 .sup.b First Reaction (˜10 min.) .sup.c Second Reaction (˜50 min.)
Sequences 3 and 4 show the effects of oxygen delignfication, after 10 and 60 minutes, with the addition of 0.5% H 2 O 2 and an incremental 0.5% NaOH to the 2.5% NaOH base charge (Op), under conditions shown in Table 1. The final pH values were 11.4 and 9.5 respectively. The level of delignification and % ISO gain was enhanced by the addition of H 2 O 2 and NaOH, after 10 and 60 minutes. Lower final pH values, compared to Sequences 1 & 2, indicate increased NaOH consumption. Note that 88% of the total Kappa number drop and 78% of the total ISO gain occur in the first 10 minutes of the total 60 minute reaction.
Both the delignification and brightness gain in the second 50 minutes diminished with the addition of H 2 O 2 , when compared to the second 50 minutes with only O 2 (see the slope of the Op curve of FIGS. 2 and 3). This may be due, in part, to attempting to both delight and brighten during the first rapid delignification reaction. This results in increased NaOH consumption during the initial phase, decreasing the NaOH level and pH during the second phase (11.7 pH for (O) vs. 11.4 pH for (Op) after the initial 10 minutes). This initial phase, with H 2 O 2 added, competed for available NaOH and H 2 O 2 to both brighten and delignify, and the kinetics overlapped. Although the end results were improved, (see Sequences 1 & 2 for comparison of final Kappa and % ISO values), this was due to reaction kinetics improvement during the rapid initial phase, (the easy part). Due to NaOH and H 2 O 2 depletion, the second brightening phase slowed down considerably as shown in Sequence 4 and graphically shown by the essentially flat slope of the final 50 minute part of the Op curve.
H 2 O 2 is primarily a strong alkali dependent, brightening agent. It is best applied, with additional NaOH, to complement the chemistry of the slower second brightening reaction. The rapid initial delignification is efficient without a significant H 2 O 2 boost.
Sequences 3,4 and 5 compare the effects of single stage chemical addition in comparison to splitting the two phases of oxygen delignification, i.e., adding 0.5% H 2 O 2 and the incremental 0.5% NaOH to the second phase only. The total Kappa number drop was increased by 0.7 and the brightness gain was increased by 5.6% ISO. Table 2 shows that single stage peroxide addition in the Op stage reduced the NaOH residual concentration to 0.72 gpl after 10 minutes (Sequence 3), slowing down the secondary reaction to a final 3.4 Kappa number and 68.8% ISO (Sequence 4). The O/Op phase split results in a 1.26 gpl NaoH concentration entering the second 50 minute Op stage. This results in a final Kappa number of 2.7 and 74% ISO (Sequence 5). It can also be concluded from Table 2 that it is beneficial for the final pH after 60 minutes to be above 10.0. It is also noted that Sequences 3,4 and 5 all had overall chemical charges of 3.0% NaOH and 0.5% H 2 O 2 .
TABLE 2______________________________________ Initial Final Final Time NaOH NaOH Final Kappa FinalSeq. Stage (min) (gpl) (gpl) pH No. % ISO______________________________________3 Op 10 4.10 0.72 11.4 4.3 64.94 Op 60 0.72 0.34 9.8 3.4 68.85 O 10 3.40 0.30 11.7 6.6 57.05 Op 50 1.26 0.25 10.0 2.7 74.4______________________________________
Sequence 6 shows that smaller, but significant, gains in delignification and brightness can be made by operating even at a lower temperature of 90° C. Laboratory studies on oxygen delignification of softwood Kraft pulp have shown this method of peroxide reinforcement to be equally as powerful.
TABLE 3______________________________________Delignification response of northern softwood pulp.sup.(1)for O, Op and OOp delignification sequences. Time Kappa Visc. Z-spanSeq..sup.(2) Stage(s) (min) nbr. % ISO (cps) (psi)______________________________________base.sup.(1) 17.4 31.3 39.7 381 O 5 15.4 32.5 28.7 29.42 O 60 10.9 36.6 23.2 263 Op 5 13.8 33.9 27.8 30.84 Op 60 10.5 36.1 23.2 27.45 O 5 15.4 32.5 28.7 29.46 OOp 5/55 9.8 37.2 20.9 26.6______________________________________ .sup.(1) Pulp baseline characteristics .sup.(2) Process variables were: O.sub.2 press. 100 psig Consistency 12.0% NaOH 1.4% H.sub.2 O.sub.2 0.5% (Op only) Temp. 95° C. MgSO.sub.4 0.5%
This two phase design provides for separate delignification and brightening phases, each with independent chemical controls, results in a second phase enhancement that will improve the overall delignification and brightening results.
Peroxide has typically not been considered as an economical method of enhancement for Kraft oxygen delignfication. This conclusion was based on evaluations using conditions similar to those shown in Sequences 3 & 4. This is only a 0.4 Kappa drop improvement over the oxygen delignification Sequences 1 & 2 where no peroxide was added, a performance increase which is too small to be of economic value.
Adding peroxide to the second mixer, allowing the first phase delignification reaction to progress on its own, enhances the delignification by 0.7 Kappa drop (10.5 vs. 9.8) for the same chemical charges. This is an overall Kappa drop improvement of 1.1 (10.9 vs. 9.8) from the oxygen delignification (Sequences 1 and 2).
Table 4 shows that the brightness and delignification gains from utilizing the OOp hardwood sulfite pulp sequence are transferable in the subsequent Z(ozone) P(peroxide) TCF(total chlorine free) bleaching sequence for hardwood sulfite pulp. These benefits result in significantly lower H 2 O 2 usage in the final P(peroxide) stage to attain an 88% ISO brightness (0.5% vs. 1.5%) and a higher final brightness ceiling above 92% ISO.
TABLE 4______________________________________Brightness (% ISO) response of hardwood acid sulfite pulpfor Op/Z/P and O/Op/Z/P sequences Op/Z/P O/Op/Z/P______________________________________Brownstock 51.0 51.0O and/or Op stages 68.8 71.5Z stage (0.4%) 80.0 82.7P stage (0.5%) 88.7 91.0P stage (1.5%) 91.2 92.6______________________________________
The Op and O/Op stages were the same as stated in Table 1, 12.0% cs (od); the Z stage had a pH=2.7, ambient temperature, 40% cs (od) whereas the P stage had a pH=10.2-10.3, 90° C., 3.5 hrs. 0.5% DPTA, 1.0% Na 2 SiO 3 , and 12.0% cs (od).
From these studies, it is concluded that OOp sequence allows optimum control of the second Op stage. For sulfite with no filtrate recycle to the OOp stage, it is initially recommended that the Op stage following a 10 minute O stage operate at a minimum 1.25 gpl NaOH controlled to a final pH≧10.0. Alkali and pH are also critical for control of the OOp sequence for Kraft, but due to the filtrate recycle of these systems, extrapolations are more difficult.
While I have described my invention in connection with specific embodiment thereof, and specific steps of performance, it is to be clearly understood that this is done only by way of example, and not as a limitation to the scope of the invention, as set forth in the purposes thereof and in the appended claims. | A method of oxygen delignification of medium consistency pulp slurry, which includes the steps of providing a pulp slurry of from approximately ten percent to sixteen percent consistency, at a temperature of from approximately 170-240° F., preferably from 190 to 220° F., thoroughly impregnating the slurry with oxygen gas, and with alkali to bring the slurry to a pH of at least 11, more preferably 12, introducing the slurry to oxygen gas in a high shear mixer, for agitating mixing therein, reacting the slurry in a first pressurized reactor for between 5 to 10 minutes, returning the pH of the slurry to at least 11, more preferably 12, with a residual alkali concentration of at least 1.25 gpl, thoroughly impregnating the slurry with H 2 O 2 and oxygen gas, and reacting the slurry in a second reactor for between 30 to 180 minutes. By only employing the hydrogen peroxide during the slower bleaching reaction, a lower Kappa number with higher % ISO is obtained in the product, these beneficial characteristics being retained in subsequent processing steps. | 3 |
CROSS REFERENCE TO RELATED APPLICATION
This is a division of application Ser. No. 457,171, filed Jan. 13, 1983, U.S. Pat. No. 4,486,428 which is a continuation-in-part of application Ser. No. 358,751, filed Mar. 16, 1982, and now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to certain novel bicyclic benzo fused compounds, more particularly to certain 5-hydroxy-7-substituted-3,4-dihydro-2H-benzopyrans which are also substituted at the 3-position or the 4-position, the corresponding tetrahydroquinoline and tetralin analogs and derivatives thereof and pharmaceutically acceptable cationic and acid addition salts thereof, useful as CNS agents, especially as analgesic, antidiarrheals, and antiemetic agents for use in mammals, including man; methods for their use and pharmaceutical compositions containing them.
2. Description of the Prior Art
Despite the current availability of a number of analgesic agents, the search for new and improved agents continues, thus pointing to the lack of an agent useful for the control of broad levels of pain and accompanied by a minimum of side-effects. The most commonly used agent, aspirin, is of no practical value for the control of severe pain and is known to exhibit various undesirable side-effects. Other, more potent analgesics such as d-propoxyphene, codeine, and morphine, possess addictive liability. The need for improved and potent analgesics is, therefore, evident.
A series of analgesic dibenzo[b,d]pyrans, having at the 9-position substituents such as alkyl, hydroxy and oxo, are disclosed in U.S. Pat. Nos, 3,507,885; 3,636,058; 3,649,650; 3,856,821; 3,928,598; 3,944,673, 3,953,603 and 4,143,139. Particularly of interest is dl-trans-1-hydroxy-3-(1,1-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-one, an antiemetic, antianxiety agent with analgesic properties in animals, now generally referred to as nabilone.
U.S. Pat. No. 4,152,450 discloses certain 3-alkyl-1-hydroxytetrahydro and hexahydrodibenzo[b,d]pyrans, having an amino or amido group at the 9-position, which are useful as analgesics, antidepressants, antianxiety agents and hypotensive agents.
U.S. Pat. No. 4,188,495 discloses analgesic 1,9-dihydroxyoctahydrophenanthrenes, 1-hydroxyoctahydrophenanthren-9-ones and derivatives thereof of the formula ##STR4## where X 9 is CHOH or C═O, M 3 is CH 2 and R 1 , R 4 , R 5 , Z and W are as defined above.
U.S. Pat. No. 4,260,764, issued Apr. 7, 1981, discloses compounds of the above formula wherein M 3 is NR 6 and X 9 , R 1 , R 4 , R 5 , R 6 , Z and W are as defined above. They are useful as analgesics, tranquilizers, hypotensives, diuretics and as agents for treatment of glaucoma. U.S. Pat. No. 4,228,169, issued Oct. 14, 1980, discloses the same compounds to be useful as antiemetic agents.
Bergel et al., J. Chem. Soc., 286 (1943) investigated the replacement of the pentyl group at the 3-position of 7,8,9,10-tetrahydro-3-pentyl-6,6,9-trimethyl-6H-dibenzo[b,d]pyran-1-ol by alkoxy groups of four to eight carbon atoms and found that these compounds had little or no hashish activity at 10 to 20 mg/kg.
In a more recent study, Loev et al., J. Med. Chem., 16, 1200-1206 (1973) report a comparison of 7,8,9,10-tetrahydro-3-substituted-6,6,9-trimethyl-6H-dibenzo[b,d]-pyran-1-ols in which the 3-substituent is --OCH(CH 3 )C 5 H 11 ; --CH 2 CH(CH 3 )C 5 H 11 ; or --CH(CH 3 )C 5 H 11 . The ether side chain containing compound was 50% less active in certain nervous system activity than the corresponding compound in which the alkyl side chain is directly attached to the aromatic ring, rather than through an intervening oxygen atom; and 5 times as active as the compound in which oxygen is replaced by methylene.
Mechoulam and Edery in "Marijuana", edited by Mechoulam, Academic Press, New York, 1973, page 127, observe that major structural changes in the tetrahydrocannabinol molecule seem to result in steep reductions in analgesic activity.
U.S. Pat. No. 4,087,545 discloses the antiemetic and antinausea properties of 1-hydroxy-3-alkyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran-9-ones.
Sallan et al., N. E. J. Med. 293, 795 (1975) reported oral delta-9-tetrahydrocannabinol has antiemetic properties in patients receiving cancer chemotherapy.
Delta-9-tetrahydrocannibinol is reported by Shannon et al. (Life Sciences 23, 49-54, 1978) to lack antiemetic effects in apomorphine-induced emesis in the dog. Borison et al., N. England J. of Med. 298, 1480 (1978) report the use of unanesthetized cats as an animal model for determining the antiemetic effect of compounds especially in connection with emesis induced by cancer chemotherapy drugs. They found that pretreatment of unanesthetized cats with 1-hydroxy-3-(1',1'-dimethylheptyl)-6,6-dimethyl-6,6a,7,8,10,10a-hexahydro-9H-dibenzo[b,d]pyran9(8H)-one (nabilone) affords pronounced protection against vomiting per se after injection of antineoplastic drugs.
Starting materials of the formulae below, useful for preparation of the invention compounds of formula (I) are known in the art. ##STR5## where R 1 , R 4 , R 5 , M, Z and W are as defined above. Detailed procedures for the preparation of said starting compounds wherein M is O are set forth in U.S. Pat. No. 4,143,139, issued Mar. 6, 1979 and U.S. Pat. No. 4,235,913, issued Nov. 25, 1980, each of which is hereby incorporated by reference. Similarly, detailed procedures for preparation of the above starting materials wherein M is CH 2 are set forth in U.S. Pat. No. 4,188,495, issued Feb. 12, 1980; and wherein M is NR 6 , and R 6 is as defined herein are set forth in U.S. Pat. No. 4,228,169, issued Oct. 14, 1980, and U.S. Pat. No. 4,260,764, issued Apr. 7, 1981, each of which are also hereby incorporated by reference.
SUMMARY OF THE INVENTION
It has now been found that certain 3,4-dihydro-2H-benzopyrans, 1,2,3,4-tetrahydroquinolines, corresponding tetralins and derivatives thereof of the formula (I) are effective agents, useful in mammals as tranquilizers, anticonvulsants, diuretics, antidiarrheals, antitussives and as agents for treatment of glaucoma. They are particularly effective in mammals, including man, as analgesics, antidiarrheals and as agents for treatment and prevention of emesis and nausea, especially that induced by antineoplastic drugs. Said invention compounds, which are non-narcotic and free of addiction liability, are of the formula ##STR6## and pharmaceutically acceptable cationic and acid addition salts thereof; wherein
M is O, CH 2 or NR 6 ;
R 6 is a member selected from the group consisting of hydrogen, --(CH 2 ) y -- carbalkoxy having from one to four carbon atoms in the alkoxy group and wherein y is 0 or an integer from 1 to 4, carbobenzyloxy, formyl, alkanoyl having from two to five carbon atoms, alkyl having from one to six carbon atoms; --(CH 2 ) x C 6 H 5 wherein x is an integer from 1 to 4; and --CO(CH 2 ) x-1 C 6 H 5 ;
one of A and B is hydrogen and the other is ##STR7## such that when A is hydrogen f is 1 or 2 and when B is hydrogen f is zero or 1; R 2 and R 3 are each hydrogen, methyl or ethyl; Q is selected from the group consisting of CO 2 R 7 , COR 8 , C(OH)R 8 R 9 , CN, CONR 12 R 13 , CH 2 NR 12 R 13 , CH 2 NHCOR 14 , CH 2 NHSO 2 R 17 and 5-tetrazolyl;
A and OR 1 when taken together form ##STR8## where R 10 is hydrogen and R 11 is hydroxy or alkoxy having from one to four carbon atoms or taken together R 10 and R 11 are an oxygen atom;
R 1 is a member selected from the group consisting of hydrogen, benzyl, benzoyl, alkanoyl having from one to five carbon atoms and --CO--(CH 2 ) p --NR 15 R 16 wherein p is 0 or an integer from 1 to 4; each of R 15 and R 16 when taken individually is selected from the group consisting of hydrogen and alkyl having from one to four carbon atoms; R 15 and R 16 when taken together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring selected from the group consisting of piperidino, pyrrolo, pyrrolidino, morpholino and N-alkylpiperazino having from one to four carbon atoms in the alkyl group;
R 4 is hydrogen, alkyl having from 1 to 6 carbon atoms or --(CH 2 ) z --C 6 H 5 wherein z is an integer from 1 to 4;
R 5 is hydrogen, methyl or ethyl;
R 7 is hydrogen, alkyl having from one to four carbon atoms or benzyl;
R 8 and R 9 are each hydrogen, alkyl having from one to four carbon atoms, phenyl or benzyl;
when taken separately, R 12 and R 13 are each hydrogen, alkyl having from one to six carbon atoms, phenyl or benzyl; R 13 and R 13 when taken together with the nitrogen atom to which they are attached form a 5- or 6-membered heterocyclic ring selected from the group consisting of piperidino, pyrrolidino, morpholino and N-alkylpiperazino having from one to four carbon atoms in the alkyl group;
R 14 is hydrogen, alkyl having from one to four carbon atoms, trifluoromethyl, benzyl, furyl, thienyl, pyridyl or R 18 C 6 H 4 where R 18 is H, NH 2 , F, Cl, Br, CH 3 or OCH 3 ;
R 17 is alkyl having from one to six carbon atoms, benzyl or R 18 C 6 H 4 ;
Z is selected from the group consisting of
(a) alkylene having from one to nine carbon atoms;
(b) --(alk 1 ) m --X--(alk 2 ) n -- wherein each of (alk 1 ) and (alk 2 ) is alkylene having from one to nine carbon atoms, with the proviso that the summation of carbon atoms in (alk 1 ) plus (alk 2 ) is not greater than nine; each of m and n is 0 or 1; X is selected from the group consisting of O, S, SO and SO 2 ; and
W is selected from the group consisting of hydrogen, methyl, pyridyl, piperidyl, ##STR9## wherein W 1 is selected from the group consisting of hydrogen, fluoro and chloro; and ##STR10## wherein W 2 is selected from the group consisting of hydrogen and ##STR11## a is an integer from 1 to 5 and b is 0 or an integer from 1 to 5; with the proviso that the sum of a and b is not greater than 5.
Particularly preferred compounds of formula (I) are those
wherein:
R 1 is hydrogen or alkanoyl, especially hydrogen of acetyl;
R 4 is hydrogen or said alkyl,
R 5 is hydrogen or methyl,
M is O, CH 2 or NR 6 where R 6 is hydrogen or said alkyl,
Z is said alkylene or --(alk 1 ) m --O--(alk 2 ) n -- and W is hydrogen or phenyl.
When B is hydrogen and A is R 2 R 3 C(CH 2 ) f Q, particularly preferred compounds of the invention are those
wherein:
f is zero,
R 2 and R 3 are each hydrogen,
Q is COOR 7 , especially those where R 7 is hydrogen, methyl or ethyl; C(OH)R 8 R 9 , especially where R 8 and R 9 are each hydrogen or methyl; CHO or CH 2 NHCOR 14 .
Especially preferred are such compounds wherein R 4 and R 5 are each methyl, Z is alkylene and W is hydrogen or Z is O--(alk 2 ) n -- and W is hydrogen or phenyl. Particularly preferred values for ZW are OCH(CH 3 )(CH 2 ) 3 C 6 H 5 and C(CH 3 ) 2 (CH 2 ) 5 CH. More particularly preferred such compounds are those wherein M is O, R 1 is hydrogen or acetyl and Q and ZW are as tabulated below.
______________________________________Q ZW______________________________________CH.sub.2 NHCOCH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CHO OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.2 OH OCH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5COOCH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CHO C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3C(CH.sub.3).sub.2 OH C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH(CH.sub.3)OH C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH.sub.2 OH C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3______________________________________
Most particularly preferred are the above compounds wherein A is CH 2 CH 2 NHCOCH 3 , R 1 is acetyl, R 4 and R 5 are each methyl and ZW is OCH(CH 3 )(CH 2 ) 3 C 6 H 5 ; and the compound wherein A is CH 2 CH 2 OH, R 1 is hydrogen, R 4 and R 5 are each methyl and ZW is C(CH 3 ) 2 (CH 2 ) 5 CH 3 .
When A is hydrogen and B is R 2 R 3 C(CH 2 ) f Q, particularly preferred compounds of formula (I) are those
wherein:
f is one,
R 2 and R 3 are each hydrogen,
Q is COOR 7 , especially where R 7 is hydrogen, methyl or ethyl;
C(OH)R 8 R 9 , especially where R 8 and R 9 are each hydrogen or methyl.
Of the above group of compounds wherein A is hydrogen, particularly preferred values for the remaining substituents are: R 1 is hydrogen or acetyl, R 4 and R 5 are each methyl and ZW is OCH(CH 3 )(CH 2 ) 3 C 6 H 5 . More particularly preferred are such compounds wherein M is O and Q is COOCH 3 or CH 2 OH; and most particularly the latter compound wherein R 1 is hydrogen, i.e., the compound of formula (I) where A is H, B is CH 2 CH 2 OH, R 1 is H, R 4 and R 5 are each methyl and ZW is OCH(CH 3 )(CH 2 ) 3 C 6 H 5 .
The scope of the present invention also includes valuable analgesic, antidiarrheals and antiemetic agents of the formulae below ##STR12## where Q 3 is 5-tetrazolyl, COOR 7 , CONHOH, CONHCONH 2 , CONR 12 R 13 , CONHCOR 19 , CONHSO 2 R 17 , CH 2 CONHCOR 19 , ##STR13## CONHAr or COCH 2 Q 4 where Ar is ##STR14## Q 4 is CN or COOR 5 ; R 19 is R 7 , phenyl or phenylethyl; and M, R 1 , R 4 , R 5 , R 7 , R 12 , R 13 , R 17 , Z and W are as previously defined.
The invention further provides compounds of the formulae below which are intermediates useful in preparation of the compounds of formula (I) ##STR15## where R 2 , R 3 , R 4 , R 5 , Z and W are as defined above, M 2 is O, CH 2 or NR 60 where R 60 is formyl, alkanoyl having from two to five carbon atoms, alkyl having from one to six carbon atoms or benzyl; Q 2 is CN or COOR 7 where R 7 is as defined above; Y 1 is hydrogen, alkyl having from one to four carbon atoms, benzyl, benzoyl, or alkanoyl having from one to five carbon atoms.
For the valuable intermediates of formula (VI) particularly preferred values are Q 2 is COOR 7 , Y 1 is benzyl. The particularly preferred values for R 2 -R 5 , Z and W are as stated above for compounds of formula (I). A particularly preferred value for M 2 is O.
For the intermediates of formula (VII) a particularly preferred value for Y 1 is hydrogen. Particularly preferred values for Q 2 , M 2 , R 2 -R 5 , Z and W are as stated above for compounds (VI).
Also included in this invention are pharmaceutically acceptable cationic and acid addition salts of the compounds of formulae (I), (XVIII) and (XIX). By pharmaceutically acceptable cationic salts of the compounds of the invention is meant the salts of those compounds of formulae (I), (XVIII) and (XIX), where A or B contains a carboxylic acid group, said salts are formed by neutralization of the carboxylic acid by bases of pharmaceutically acceptable metals, ammonia and amines. Examples of such metals are sodium, potassium calcium and magnesium. Examples of such amines are ethanolamine and N-methylglucamine.
By the term pharmaceutically acceptable acid addition salts is meant the addition salts formed between those compounds of formulae (I), (XVIII) and (XIX), having one or more basic nitrogen atoms in substituents M, R 1 , A, B or Q 3 and a pharmaceutically acceptable acid. Examples of such acids are acetic, benzoic, hydrobromic, hydrochloric, citric, sulfosalicyclic, tartaric, glycolic, malonic, maleic, fumaric, malic, 2-hydroxy-3-naphthoic, pamoic, salicylic, phthalic, succinic, gluconic, mandelic, lactic, sulfuric, phosphoric, nitric and methanesulfonic acids. Of course, when more than one basic nitrogen atom is present in the free base of formula (I), mono-, di- or higher addition salts may bwe obtained by employing one, two or more equivalents of acid to form the desired acid addition salt.
Compounds having the formulae (I), (XVIII) or (XIX) above, contain asymmetric centers at the 3- or 4-position (A, B or Q 3 ). There may be additional asymmetric centers at the 2-position (R 4 , R 5 ), in the 7-position substituent (ZW), in the 1-position substituent (R 6 ) in compounds wherein M is NR 6 , in substituent A or B and in the 2-position substituent (R 4 ). The present invention includes the racemates of formulae (I), (XVIII) and (XIX), the diastereomeric mixtures, pure enantiomers and diastereomers thereof. The utility of the racemic mixtures, the diastereomeric mixtures, as well as of the pure enantiomers and diastereomers is determined by the biological evaluations described below.
As mentioned above, the compounds of the invention are particularly useful as analgesics, antidiarrheals and as antiemetic and antinausea agents for use in mammals, including man. The invention further provides a method for producing analgesia in mammals and a method for prevention and treatment of nausea in a mammal subject to nausea, in each case by oral or parenteral administration of an effective amount of a compound of formula (I), (XVIII), (XIX) or their pharmaceutically acceptable salts
Also provided are pharmaceutical compositions for use as analgesics, as well as those suitable for use in prevention and treatment of nausea, comprising an effective amount of compound of the invention and a pharmaceutically acceptable carrier.
DETAILED DESCRIPTION OF THE INVENTION
The compounds of the invention of formula (I) wherein B is hydrogen are defined by the formula below where f is zero or one; ##STR16## those wherein A is hydrogen by the formula ##STR17## where f is 1 or 2; and R 1 -R 5 , M, Q, Z and W are as defined above, in each case.
The compounds of formula (II) wherein f is zero are prepared, for example, by methods outlined in Flow Charts A and B.
Flow Chart A illustrates methods which are employed to provide compounds of formula (II) wherein f is zero. The requisite starting ketones of formula (IVA) are provided in U.S. Pat. No. 4,143,139 (M 2 ═O), U.S. Pat. No. 4,188,495 (M 2 ═CH 2 ), U.S. Pat. No. 4,228,169 and U.S. Pat. No. 4,260,764 (M 2 ═NR 60 ), which, as noted above, are each incorporated by reference.
FLOW CHART A
For compounds of formula (II) wherein f is zero: ##STR18##
In said starting materials (IVA), Y 1 is an hydroxy protecting group, such as e.g., benzyl or methyl; R 4 , R 5 , M 2 , Z and W are as previously defined. In the first step of the reaction sequence the compound of formula (IVA) is reacted with an alpha-haloester or alpha-halonitrile in the presence of zinc metal, the well known Reformatsky reaction, to provide the corresponding intermediate of formula (VI). Alternatively, this step is carried out by a modification of the Reformatsky reaction employing a lithio acetic acid ester or lithio acetonitrile reagent of formula LiC(R 2 R 3 )Q 2 where Q 2 is COOR 7 or CN and R 2 , R 3 and R 7 are as previously defined. A recent extensive review of the Reformatsky reaction is that of Rathke in Organic Reactions, 22, 423-460 (1975).
When the above mentioned alpha-haloesters or alpha-halonitriles are employed, the preferred reagents are the bromo compounds of formula BrC(R 2 R 3 )Q 2 , wherein R 2 and R 3 are each hydrogen, methyl or ethyl and Q 2 is CN or COOR 7 and R 7 is as previously defined. The reagent, BrC(R 2 R 3 )Q 2 is contacted, for example, with at least an equimolar amount of zinc metal in the presence of a reaction inert organic solvent to provide an organometallic intermediate, BrZnC(R 2 R 3 )Q 2 , which is then reacted with the ketone of formula (IVA) to provide the desired intermediate of formula (VI) after hydrolysis of the reaction mixture with, e.g., ammonium hydroxide or acetic acid. Alternatively, the zinc metal, reagent, BrC(R 2 R 3 )Q 2 and starting ketone (IVA) may be contacted simultaneously in the presence of reaction inert organic solvent to provide the desired intermediate (VI).
Preferred temperatures for carrying out the above reaction between BrC(R 2 R 3 )Q 2 and starting material (IVA) are in the range of from about 0° C. up to the reflux temperature of said solvent. Examples of reaction inert solvents which may be employed are benzene, toluene, ethyl ether, tetrahydrofuran, dimethoxymethane, 1,2-dimethoxyethane, diethyleneglycol dimethylether, trimethylborate and mixtures thereof. Preferred such solvents are benzene, tetrahydrofuran, dimethoxymethane and 1,2-dimethoxyethane. The desired intermediate of formula (VI) is isolated by standard methods known in the art and exemplified herein. The crude intermediates are purified, if desired, by standard methods, e.g., recrystallization or column chromatography.
When lithio reagents LiC(R 2 R 3 )Q 2 are employed to prepare the intermediates of formula (VI), they may be prepared by any of several methods known in the art; see, for example, Fieser, "Reagents for Organic Chemistry", Wiley-Interscience, New York, Vol. 3, 1972. However, a preferred method, exemplified herein, employs a lithium dialkylamide and an acetic acid ester or nitrile of formula CH(R 2 R 3 )Q 2 in reaction inert solvent. A particularly preferred lithium dialkylamide is lithium dicyclohexylamide. The latter compound is prepared, for example, from equimolar amounts of n-butyl lithium and dicyclohexylamine in reaction inert solvent. In a typical reaction the two reagents are contacted under anhydrous conditions and in the presence of an inert atmosphere, e.g., nitrogen, at -80° to -70° C. in reaction inert solvent and to the resulting slurry is added an equimolar amount of reagent of formula CH(R 2 R 3 )Q 2 at the same temperature. The resulting lithio reagent, LiC(R 2 R 3 )Q 2 is then reacted immediately with the starting ketone (IVA) in reaction inert solvent also at a temperature of from about -80° to -70° C. The reaction is ordinarily completed in from about one to ten hours, after which the reaction mixture is quenched by addition of an equivalent amount of weak acid, e.g., acetic acid, to decompose the lithium salt of the desired product. The product is then isolated by standard methods and purified, if desired, as described above. Examples of the reaction inert solvents which may be employed and preferred such solvents are those mentioned above for the reaction employing haloester or halonitrile reagents.
The 4-hydroxy-4-(R 2 R 3 CQ 2 )-substituted compounds of formula (VI), obtained as described above, are then subjected to hydrogenolysis and removal of hydroxy protecting group Y 1 to provide compounds of formula (IX), (X) or a mixture thereof. The hydrogenolysis of compounds of formula (VI) where Q 2 is COOR 7 is ordinarily carried out by means of hydrogen in the presence of a noble metal catalyst. Examples of noble metals which may be employed are nickel, palladium, platinum and rhodium. The catalyst is ordinarily employed in catalytic amounts, e.g., from about 0.1 to 10 weight-percent and preferably from about 0.1 to 2.5 weight-percent, based on the compound of formula (VI). It is often convenient to suspend the catalyst on an inert support, a particularly preferred catalyst is palladium suspended on an inert support such as carbon.
One convenient method of carrying out this transformation is to stir or shake a solution of the compound of formula (VI) under an atmosphere of hydrogen in the presence of one of the above noble metal catalysts. Suitable solvents for this hydrogenolysis reaction are those which substantially dissolve the starting compound of the formula (VI) but which do not themselves suffer hydrogenation or hydrogenolysis. Examples of such solvents include the lower alkanols such as methanol, ethanol and isopropanol; ethers such as diethyl ether, tetrahydrofuran, dioxan and 1,2-dimethoxyethane; low molecular weight esters such as ethyl acetate and butyl acetate; tertiary amides such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; and mixtures thereof. Introduction of the hydrogen gas into the reaction medium is usually accomplished by carrying out the reaction in a sealed vessel, containing the compound of formula (VI), the solvent, the catalyst and the hydrogen. The pressure inside the reaction vessel can vary from about 1 to about 100 kg/cm 2 . The preferred pressure range, when the atmosphere inside the reaction vessel is substantially pure hydrogen, is from about 2 to about 5 kg/cm 2 . The hydrogenolysis is generally run at a temperature of from about 0° to about 60° C., and preferably from about 25° to about 50° C. Utilizing the preferred temperature and pressure values, hydrogenolysis generally takes place in a few hours, e.g., from about 2 hours to about 24 hours.
The product is then isolated by standard methods known in the art, e.g., filtration to remove the catalyst and evaporation of solvent or partitioning between water and a water immiscible solvent and evaporation of the dried extract.
When the starting compound employed in the hydrogenolysis is of formula (VI) wherein Y 1 is hydrogen or benzyl and Q 2 is COOR 7 , the product obtained is ordinarily a mixture of the corresponding carboxylic acid or ester of formula (IX) and the lactone of formula (X) formed by elimination of the elements of R 7 OH from (IX). The mixture thus obtained may be used as is or may be separated by well known methods, e.g., by crystallization and/or chromatography on silica gel.
Of course, when the starting compound for the hydrogenolysis is of formula (VI) wherein Y 1 is alkyl, benzoyl or alkanoyl as defined above and Q 2 is COOR 7 , the only product obtained is the corresponding Y 1 -substituted derivative of the compound of formula (IX). Removal of the hydroxy protecting group Y 1 , e.g., by hydrolysis (when Y 1 is benzoyl or alkanoyl as defined above) or by methods known in the art for cleaving ethers (when Y 1 is alkyl as defined above), e.g., by means of HBr/acetic acid, then affords the desired compound of (IX) or its mixture with lactone (X).
In a preferred method for conversion of compounds of formula (VI) where Q 2 is CN to the corresponding compound of formula (IX), the compound (VI) is first dehydrated to form a 4-cyanomethylene derivative and this is hydrogenated by means of magnesium in methanol to form the hydroxy-protected derivative of (IX) from which the protecting group is then removed. This sequence is outlined below for the case wherein Q 2 ═CN, R 2 and R 3 ═H, R 4 and R 5 ═CH 3 , Y 1 ═CH 2 C 6 H 5 and M 2 ═O. ##STR19##
The dehydration step is carried out in a reaction inert solvent, e.g., benzene, toluene or ethyl ether. To the solution of the starting 4-hydroxy compound is added an absorbent for water, e.g., molecular sieves, and a catalytic amount of methanesulfonic acid and the mixture stirred at room temperature, typically overnight. The dehydrated product is isolated by standard methods and reduced in methanol in the presence of magnesium metal at -10° to 30° C., typically this reaction is complete in from about 4 to 48 hours. The benzyl protecting group is then removed by catalytic hydrogenation as described above. Of course for compounds of formula (VI, Q 2 ═CN) wherein both of R 2 and R 3 are methyl or ethyl, the same method employed for conversion of compounds of formula (VI) where Q 2 ═CO 2 R 7 to compounds of formula (IX), described above, is preferred.
The products of formula (IX, Q 2 ═CO 2 R 7 ) and (X), as well as mixtures thereof, are useful intermediates for production of the corresponding hydroxy compounds of formula (II, Q═CH 2 OH, f=0) by means of known reducing agents, e.g., hydrides such as lithium aluminum hydride or lithium borohydride, aluminum borohydride, borane, aluminum hydride and lithium triethylborohydride and by catalytic hydrogenation over noble metal catalysts. Preferred reducing agents are the above hydrides and especially preferred is lithium aluminum hydride for reasons of economy and efficiency. The reduction is carried out under anhydrous conditions and in the presence of a suitable reaction inert solvent e.g., ethyl ether, tetrahydrofuran, 1,2-dimethoxyethane and diethyleneglycol dimethylether. Typically, the compound of formula (IX, Q 2 ═CO 2 R 7 ), the lactone (X) or mixture thereof dissolved in one of the above reaction inert solvents is added to a solution of an approximately equimolar amount of hydride, e.g., lithium aluminum hydride, in the same solvent and the mixture maintained at a temperature of from about -50° to 50° C., and preferably from about 0° to 30° C. Under these conditions the reduction is substantially complete in from about 2 to 24 hours, after which the excess reducing agent is quenched, e.g., by cautious addition of wet solvent or ethyl acetate and the product isolated by known techniques, e.g., washing the reaction mixture with water and evaporation of the dried organic phase. Purification, if desired, is carried out, e.g., by recrystallization or column chromatography.
The lactones (X) are also useful as intermediates for production of the corresponding lactols of formula (XII) by means of reagents and conditions known to selectively reduce the lactone carbonyl group to a carbinol without ring cleavage. A preferred such reagent is diisobutylaluminum hydride (DIBALH). In a typical reaction, the lactone (X) is dissolved in a reaction inert solvent, such as an aromatic hydrocarbon solvent, preferably toluene, the solution is cooled to a temperature of from about -90° to -50° C., preferably about -80° to -60° C., under anhydrous conditions and in the presence of an inert atmosphere such as nitrogen or argon. An equimolar amount of DIBALH is then added slowly while maintaining the mixture within the preferred temperature range. After the addition is complete, the reaction is allowed to proceed under these conditions until substantially complete, which ordinarily requires from about one to ten hours. The reaction mixture is then quenched, for example, by addition of methanol, then allowed to warm to room temperature. The desired lactol (XII) is then isolated, e.g., by washing with water, drying and evaporation of solvent.
The esters of formula (IX) where Q 2 is COOR 7 and R 7 is alkyl having from one to four carbon atoms or benzyl and the lactones (X) also serve as starting materials for preparation of the tertiary alcohol compounds of the invention of formula (II, f=0) shown in Flow Chart A and below ##STR20##
The ester, lactone or a mixture thereof dissolved in a reaction inert solvent, e.g., ethyl ether, isopropyl ether, tetrahydrofuran or 1,2-dimethoxyethane, is contacted under anhydrous conditions with at least two moles of the appropriate Grignard reagent R 8 MgX, where R 8 is C 1 -C 4 alkyl, phenyl or benzyl and X is Cl, Br or I, at a temperature of from about 0° C. up to the reflux temperature of the solvent, preferably at room temperature. The reaction is ordinarily complete in from about 2-24 hours. The excess Grignard reagent is then decomposed and the product isolated by standard methods well known in the art. For example, water is added, the layers separated, the aqueous phase extracted with a water immiscible solvent, e.g., ethyl ether, and the product isolated from the combined extracts by evaporation of solvent. Purification, if desired, is accomplished by, e.g., recrystallization or column chromatography. Preferred reaction inert solvents for this reaction are ethyl ether and tetrahydrofuran.
Grignard reaction of the above described lactols of formula (XII) employing equimolar amounts of Grignard reagent and lactol under the above described conditions, similarly provides secondary alcohols of formula (II, f=0, Q═CH(OH)R 8 , R 1 ═H).
Oxidation of the secondary alcohols or corresponding primary alcohols of formula (II, f=0) provided above, employing an oxidizing agent known to oxidize primary and secondary alcohols to aldehydes and ketones, respectively, provides the corresponding compounds of formula (II, f=0, Q═COR 8 ) where R 8 is hydrogen, C 1 -C 4 alkyl, phenyl or benzyl. Oxidizing agents which can be employed for this oxidation are well known in the art, see, e.g., Sandler and Karo, "Organic Functional Group Preparations", Academic Press, New York, 1968, pp. 147-173. Preferred oxidizing agents, however, are chromic acid, chromic anyhydride, potassium dichromate, manganese dioxide and lead tetraacetate and particularly preferred is chromic anhydride in pyridine. While the oxidation with the preferred agents above may be carried out over a wide range of temperature, e.g., from about 0° to 100° C., a preferred temperature is from about 10° to 50° C. The alcohol and a molar excess of chromic anhydride, e.g., a 100% molar excess, are contacted in aqueous pyridine. The oxidation is ordinarily complete at a temperature in the preferred range, in from about one to eight hours. After which the product is isolated by pouring the mixture into water, extraction with a water immiscible solvent, e.g., ethyl ether, methylene chloride or chloroform, and evaporation of solvent.
Reaction of the lactols of formula (XII) with alcohols of formula (R 11 )'OH, where (R 11 )' is alkyl having from one to four carbon atoms, under acidic conditions known to convert lactols (hemiacetals) to acetals provides the invention compounds of formula (XIV) as shown in Flow Chart A, above. In a typical reaction, the lactol is dissolved in a large excess, e.g., a solvent amount of the alcohol of formula (R 11 )'OH, dry hydrogen chloride or concentrated sulfuric acid added in from a catalytic amount up to an amount equimolar to the lactol and the mixture maintained at a temperature of from about 0° C. up to the boiling point of the alcohol, preferably room temperature, until acetal formation is complete. The time required for completion is ordinarily about 4-48 hours. After which the acetal is isolated by known methods, e.g., by pouring into water, extracting with ether, drying the extracts and evaporation of solvent. The product thus provided is ordinarily a mixture of the alpha- and beta-anomeric acetals which can be separated, e.g., by chromatography on silica gel.
The lactols of formula (XII) are also useful intermediates for preparation of amines of formula (II, f=0, Q═CH 2 NH 2 ) via an alkoxyamino intermediate, e.g., the methoxyamino compounds for formula (XIII). The lactol is first reacted with an alkoxyamine, preferably methoxyamine. Equimolar amounts of the reactants are contacted in the presence of a suitable solvent such as, for example, methanol, ethanol, tetrahydrofuran, dimethylformamide, pyridine or mixtures thereof. Preferred solvents are ethanol, pyridine or their mixtures. The reaction can be carried out satisfactorily at a temperature in the range of from about -20° to 50° C.; however, a temperature of from about -10° to 25° C. is preferred. Under preferred conditions the reaction is ordinarily complete in from about one to six hours. The product of formula (XIII) is then isolated by standard means, e.g., by evaporation of solvent and partitioning the residue between water and a water immiscible solvent, e.g., ethyl ether.
Catalytic hydrogenolysis of the alkoxyamino intermediate affords the corresponding bicyclic compound of formula (II) where Q is CH 2 NH 2 , f=0 and R 1 is H. The hydrogenolysis is carried out in the presence of hydrogen and a noble metal catalyst under conditions described above for hydrogenolysis of compounds of formula (VI). However, a particularly preferred method employs a nickel/aluminum alloy in the presence of aqueous alkali, e.g., sodium hydroxide or potassium hydroxide. The reaction of the aluminum with alkali produces the requisite hydrogen and continually provides fresh catalyst (nickel) for the reaction at the same time. In a particularly preferred embodiment of this reaction approximately equal weights of the methoxyamino compound (XIII) and Raney alloy (1:1 by weight nickel/aluminum) are contacted in the presence of dilute aqueous alkali, e.g., sodium hydroxide and in the presence of a suitable solvent, e.g., methanol or ethanol. The mixture is heated at a temperature of from about 40° C. up to the reflux temperature of the mixture. The reaction is substantially complete in from about 1 to 10 hours, after which the product (II, Q═CH.sub. 2 NH 2 , f=0, R 1 ═H) is isolated by known methods and purified, e.g., by column chromatography.
The compounds of formula (II, Q═CH 2 NH 2 , f=0, R 1 ═H) can also be prepared by reduction of the compounds of formula (IX, Q 2 ═CN) employing hydrogen in the presence of a noble metal catalyst or by means of hydride reducing agents such as e.g., borane, aluminum hydride, lithium aluminum hydride or lithium triethylborohydride. A particularly preferred method employs lithium aluminum hydride in the presence of a reaction inert solvent, e.g., ethyl ether or tetrahydrofuran under conditions set forth above for reduction of the corresponding esters (IX, Q 2 ═COOR 7 ) with the same reagent to form compounds (II, Q═CH 2 OH, R 1 ═H).
The amides of formula (II, Q═CONR 12 R 13 ) are prepared from the esters or acids of formula (IX, Q 2 ═COOR 7 ) by reaction with ammonia or the appropriate amine of formula R 12 R 13 NH employing standard methods known in the art. Typically, approximately equimolar amounts of the ester of formula (IX, Q 2 ═COOR 7 ) and the above amine or ammonia are contacted in the presence of solvent and at a temperature in the range of from about 0° to 100° C. Examples of solvents which may be successfully employed in this reaction are the lower alkanols such as methanol, ethanol, isopropanol and n-butanol; ethers such as diethylether, tetrahydrofuran, 1,2-dimethoxyethane and diethyleneglycol dimethylether; hydrocarbons such as hexane, benzene and toluene and mixtures thereof. Preferred solvents are methanol, ethanol, isopropanol, tetrahydrofuran, toluene and their mixtures.
When acids of formula (IX, Q 2 ═COOH) are employed to provide amides of formula (II, Q═CONR 12 R 13 ), it is preferable to convert the acid to an activated derivative such as the acid halide or a mixed anhydride prior to reaction with the amine or ammonia of formula R 12 R 13 NH. Typically, the acid is first reacted with an equimolar amount of thionyl chloride to form the corresponding acid chloride by methods well known in the art, and the latter compound reacted with at least an equimolar amount of free base of formula R 12 R 13 NH, but preferably a molar excess of base, e.g., 2-3 moles, in the presence of a reaction inert organic solvent. The resulting amide is then isolated by filtration to remove precipitated amine hydrochloride salt and the product isolated by washing and evaporation of the filtrate. Preferred reaction inert solvents for this procedure are ethyl ether, tetrahydrofuran, chloroform or methylene chloride. It is also preferred that this reaction be carried out with 1-acyloxy compounds of formula (IX, Q 2 ═COOH) in order to prevent unwanted side reaction of the acid halide with the phenolic hydroxy group (R 1 ═H). A preferred acyloxy is acetoxy. The resulting acyloxyamide, e.g., (II, Q═CONR 12 R 13 , R 1 ═CH 3 CO) may then be converted to the corresponding hydroxy compound (R 1 ═H) by contacting the product thus obtained with dilute aqueous alkali, e.g., sodium hydroxide, potassium hydroxide or sodium carbonate.
The amides of formula (II, Q═CONR 12 R 13 ) can be reduced by either catalytic hydrogenation or metal hydrides to prevent the corresponding amine derivatives (II, Q═CH 2 NR 12 R 13 ) as described above for reduction of nitriles (IX, Q 2 ═CN) to provide the primary amines, (II, Q═CH 2 NH 2 ).
Reaction of the latter primary amine compounds with, e.g., an acid halide of formula R 14 COCl, R 14 COBr or a mixed anhydride of formula R 14 COOCOalkyl where alkyl is C 1 -C 4 , employing the same methods and conditions described above for preparation of amides of formula (II, Q═CONR 12 R 13 ), provides the desired amides of formula (II, Q═CH 2 NHCOR 14 ). Similarly, use of a sulfonyl halide of formula R 17 SO 2 Cl or R 17 SO 2 Br affords the corresponding sulfonamide (II, Q═CH 2 NHSO 2 R 17 ) where R 17 is as previously defined.
Flow Chart B, below, illustrates the methods which can be employed to provide the invention compounds of formula (II) wherein f is 1. ##STR21##
A primary alcohol of formula (II) wherein f=0, Q═CH 2 OH, R 1 ═COCH 3 and R 2 , R 3 , R 4 , R 5 , Z and W are as previously defined is first converted to the corresponding alkylsulfonyl or arylsulfonyl ester wherein alkyl is, e.g., of from one to four carbon atoms and aryl is, e.g., phenyl or tolyl. An especially preferred sulfonyl ester is methylsulfonyl for reasons of economy and efficiency. In a typical such reaction the primary alcohol of formula (II), as defined above, and an equimolar amount of methanesulfonyl chloride are contacted in the presence of a solvent amount of pyridine or triethylamine which also acts as an acid acceptor. The resulting mixture is maintained at a temperature of from about -10° to 40° C., preferably from about 0° to 30° C., at which temperature the reaction is complete in from about 15 minutes to four hours. The methanesulfonyl ester is then isolated by standard techniques, e.g., by evaporation of volatiles and partitioning of the residue between water and a water immiscible solvent, washing and evaporation of solvent.
FLOW CHART B
For compounds of formula (II) wherein f is 1: ##STR22##
The mesylate ester thus provided is further reacted with a molar excess, e.g., a 2-20 molar excess, of an alkali metal cyanide, preferably potassium cyanide and preferably in the presence of a catalytic amount of potassium iodide to afford the desired compound of formula (II, f=1, Q═CN, R 1 ═H). This reaction is ordinarily carried out in the presence of a reaction inert polar solvent, preferably dimethylformamide, dimethylsulfoxide, diethyleneglycol dimethyl ether, or their mixtures with water; and at a temperature of from about 50° to 150° C., preferably 75° to 105° C. Under the above mentioned preferred conditions the formation of the desired nitrile is complete in from about one to six hours. The product is isolated by methods well known in the art, e.g., by evaporation of solvent, partitioning the residue between water and water immiscible solvent, e.g., chloroform or methylene chloride and evaporation of the solvent. The residue is purified, if desired, e.g., by chromatography. The nitrile, thus obtained, serves as precursor of the remaining compounds of formula (II, f=1) as shown in Flow Chart B.
Hydrolysis of the nitrile, employing methods and conditions well known in the art for conversion of nitriles to carboxylic acids, affords the acids of formula (II, f=1, Q═COOH). Typically, the nitrile in aqueous alcoholic alkali, e.g., sodium hydroxide is heated at reflux for about 4-24 hours and the product isolated by acidification of the mixture, extraction into a water immiscible solvent, e.g., ethyl ether or chloroform, and evaporation of solvent.
Esterification of the carboxylic acids obtained above with alcohols of the formula R 7 OH provides the corresponding esters of formula (II, f=1, Q═COOR 7 ) where R 7 is alkyl having from one to four carbon atoms. The esterification is typically carried out by contacting the carboxylic acid (II, f=1, Q═COOH) with a molar excess of alcohol, R 7 OH, in the presence of a catalytic amount of a strong acid, e.g., hydrogen chloride or sulfuric acid, at a temperature of from about 25° C. up to the reflux temperature of the mixture, preferably 50° to 110° C., for about 4 to 24 hours. The ester is then isolated by neutralization of the mixture with, e.g., sodium hydroxide, filtration and evaporation of the filtrate.
Reduction of the compounds of formula (II, f=1, Q═COOR 7 ) by means of hydrogen and a noble metal catalyst or employing metal hydride reducing agents, e.g., lithium aluminum hydride, as described above for the corresponding compounds wherein f=0, provides the primary alcohols of formula (II, f=1, Q═CH 2 OH).
The amides of formula (II, f=1, Q═CONR 12 R 13 ) are obtained by reaction of the corresponding acids and esters wherein Q═COOR 7 by the methods previously described for the corresponding compounds wherein f=0. Similarly, the compounds of formula (II, f=1, Q═CH 2 NR 12 R 13 ) are obtained by reduction of the appropriate amide as described above for their counterparts wherein f=0.
The remaining compounds of formula (II, f=1) wherein Q is CH 2 NH 2 , CH 2 NHCOR 14 , CH 2 NHSO 2 R 17 and C(OH)R 8 R 9 are also obtained by corresponding procedures previously defined for their counterparts wherein f=0.
The invention compounds of formula (II, Q═CHO) wherein f=0 or 1 are preferably provided by reaction of the corresponding N,N-dialkylamide of formula (II, Q═CONR 12 R 13 ) with disiamylborane [bis(1,2-dimethylpropyl)borane]. In a typical reaction the tertiary amide, e.g., N,N-dimethylamide, of formula (II) and a molar excess, e.g., a 100% molar excess, of disiamylborane are contacted in a reaction inert solvent, e.g., tetrahydrofuran at a temperature of from about 0° to 50° C., preferably room temperature until the formation of aldehyde is complete, typically from about 2 to 20 hours. The excess reducing reagent is then decomposed by cautious addition of water, the solvent evaporated, the residue isolated by partitioning between water and water immiscible solvent and the solvent evaporated.
Reaction of the aldehydes (II, Q═CHO) wherein f is 0 or 1 with an equimolar amount of Grignard reagent, R 8 MgX, employing methods and conditions previously described for reaction of esters of formula (II, f=0, Q═COOR 7 ) or the corresponding lactones of formula (X), affords secondary alcohols of formula [II, Q═CH(OH)R 8 ] wherein f=0 or 1.
Oxidation of the secondary alcohols of formula (II, Q═CH(OH)R 8 ) wherein f is 0 or 1 employing oxidizing agents and conditions known in the art to convert secondary alcohols to the corresponding ketones, provides the corresponding invention compounds of formula (II, Q═COR 8 ). Examples of oxidizing agents which can be employed in production of these ketones are potassium permanganate, potassium dichromate chromium trioxide and chromium trioxide in the presence of pyridine. In carrying out the oxidation to the starting secondary alcohol in a reaction inert solvent, e.g., dichloromethane, chloroform, benzene, pyridine, water or mixtures thereof, is added at least an equimolar amount, preferably a molar excess, e.g., 100-500% molar excess, of the oxidizing agent and the oxidation allowed to proceed to substantial completion. While this oxidation can be successfully carried out over a wide range of temperatures such as from 0° to 100° C., a preferred temperature when the preferred oxidizing agent is employed is in the range of from 10° to 30° C. Under these conditions the reaction is complete in from about one to six hours, typically two to four hours. A preferred solvent for the oxidation is aqueous pyridine when the oxidizing agent is chromium trioxide in the presence of pyridine. The product is isolated, for example, by pouring the reaction mixture into water, adjusting the mixture to an acidic pH and extraction with a water immiscible solvent, e.g., chloroform, methylene chloride or ethyl ether. Drying the extracts and evaporation of solvent affords the desired ketone.
Reaction of the ketones of formula (II, Q═COR 8 ) wherein f is zero or 1 with an equimolar amount of a Grignard reagent of formula R 9 MgX, whereinR 9 is as previously defined and is the same or different than R 8 , employing methods and conditions described above for the reaction of esters of formula (II, f=0, Q═COOR 7 ) or the lactones of formula (X), affords tertiary alcohols of the invention of formula (II, Q═C(OH)R 8 R 9 ) wherein f is zero or 1.
The 4-hydroxy-4-acetamido compounds of formula (XVIII) are derived from the corresponding esters or nitriles of formula (VI) by methods analogous to those described above for preparing the corresponding amides of formula (II).
The 4-amido and 4-imido compouds of formula (XIX) are obtained, for example, by the reaction sequence below. ##STR23##
Hydrogenolysis of the benzyl group with palladium-on-carbon catalyst can likewise be carried out on any of the above intermediates, except the alpha,beta-unsaturated nitrile, to provide the corresponding 5-hydroxy compounds.
The spiro imides of formula (XIX) where Q 3 is ##STR24## are provided by reacting the corresponding ester, (XIX, Q 3 is COOR 7 ) with e.g. ethyl lithioacetate at -70° C., hydrolysis of the resulting diester, cyclization to form the spiro anhydride and heating this with ammonia or urea at 100°-250° C. to form the desired imide.
Flow Chart C outlines, for example, methods which can be employed to provide the invention compounds of formula (III) wherein f is 1 or 2. The requisite starting 3-hydroxymethylene-2,2-R 4 R 5 -4-keto-5-hydroxy-7-ZW-substituted compounds of formula (VA) where M 1 is e.g., O, CH 2 , NCHO or NCH 3 and R 4 , R 5 , Z and W are as defined above, as well as its derivatives wherein the phenolic hydroxy group is protected, are provided in U.S. Pat. No. 4,143,139 (M 1 ═O), U.S. Pat. No. 4,188,495 (M 1 ═CH 2 ), U.S. 4,228,169 (M 1 ═NCHO or NCH 3 ) and U.S. Pat. No. 4,260,764 (M 1 ═NHCO or NCH 3 ), which, as previously stated, are incorporated herein by reference.
FLOW CHART C
(For compounds of formula (III), f=1 and f=2). ##STR25##
The starting compound of formula (VA) is initially reacted with at least an equimolar amount of acrylate ester of the formula R 2 R 3 C═CHCO 2 R 7 , where R 2 and R 3 are as previously defined and R 7 is alkyl having from one to four carbon atoms or benzyl, to provide intermediate ketoesters of formula (VIII). The reaction is carried out in the presence of a base, for example, an alkali metal hydroxide or alkoxide such as sodium hydroxide, potassium hydroxide, sodium methoxide or potassium ethoxide; or a tertiary organic base such as triethylamine, to effect Michael addition and decarboxylation. The reaction can be carried out in the presence or absence of solvent and at a temperature of from about 0° to 50° C. In a typical reaction, the starting material of formula (VA) and a molar excess, e.g., a 2-6 molar excess, of the above acrylate ester are contacted in the presence of about 1 to 10 moles of triethylamine as base. Under these conditions the reaction is complete in a few days and the product is then isolated and purified by standard techniques.
The ketoester intermediate (VIII) is then hydrolyzed to the corresponding ketoacid (XV). The hydrolysis is conveniently effected by, e.g., an alkali metal hydroxide such as sodium hydroxide at a temperature of from about 0° to 60° C., typically at room temperature. When the starting ester (VIII) is one wherein M 1 is NCHO, the hydrolyses can be carried out to provide either the corresponding acid (XV) wherein M is NCHO, or the free base where M is NH, by suitable selection of hydrolysis conditions. For example, hydrolysis at a low temperature within the above range, e.g., at about 15° C., affords the compound (XV) where M is NCHO. Use of higher temperatures favors hydrolysis of the N-formyl group as well as the ester group to afford the free base of formula (XV).
The ketoacid (XV) is then cyclized to provide the enolic lactone (XVI). This step is carried out under dehydrating conditions employing, for example, sodium acetate and acetic anhydride. In a typical such reaction, the ketoacid (XV) and an equimolar amount of sodium acetate are contacted with 2-200 fold molar excess of acetic anhydride and the mixture heated at about 100° C. in the presence of an inert gas such as argon or nitrogen for from 8 hours up to a few days, after which the reaction mixture is concentrated in vacuo and the residue purified by column chromatography.
Catalytic hydrogenation of the nol-lactones (XVI) provided above, under conditions which affects hydrogenolysis of the benzylic oxygen in the 4-position, is then carried out employing the same catalysts and conditions previously described for hydrogenolysis of compounds of formula (VI) to yield the carboxylic acids of formula (XVII) where R 7 is hydrogen. The corresponding esters, where R 7 is C 1 -C 4 alkyl or benzyl, are then prepared, if desired, by standard esterification methods.
The compounds of formula (XVII) are active CNS agents of the invention and are also useful as intermediates for other invention compounds of formula (III) as is shown in Flow Chart C. For example, they are reduced, e.g., by metal hydrides, to provide the compounds of formula (III, f=1, Q═CH 2 OH, R 1 ═H) employing the same reagents and conditions described above for reduction of compounds of formulae (IX) or (X) to provide the compounds of formula (II, f=1, Q═CH 2 OH, R 1 ═H).
Contacting the esters of formula (XVII) or an activated derivative of the acids of (XVII) wherein R 7 is hydrogen with an equimolar amount of anhydrous ammonia, affords the corresponding primary amide of formula (III, f=1, Q═CONH 2 , R 1 ═H). Further reaction of this amide with thionyl chloride at the reflux temperature affords the corresponding nitrile of formula (III, f=1, Q═CN, R 1 ═H).
In a typical reaction to prepare the above primary amides, the ester of formula (XVII) in a suitable solvent, e.g., methanol, ethanol, isopropanol or acetone, is treated with a molar excess of anhydrous ammonia at or about room temperature. The mixture is then heated at a temperature up to the reflux temperature of the solvent while continuing to introduce ammonia for several hours. The mixture is then allowed to stand overnight at room temperature, the volatiles evaporated and the residue purified, if desired, e.g., by column chromatography.
The amide thus obtained is contacted with thionyl chloride, typically a solvent amount of the latter reagent is employed, and the mixture heated at reflux, typically overnight. The product is isolated by standard methods known in the art, for example, the reaction mixture is poured into water, made alkaline with a strong base, e.g., sodium hydroxide, and extracted with a water-immiscible solvent, e.g., ethyl ether, chloroform or methylene chloride. The nitrile of formula (III, f=1, Q═CN, R 1 ═H) is isolated by evaporation of solvent and, if desired, purified by column chromatography or recrystallization.
The 5-acetoxy alcohols of formula (III, f=1, Q═CH 2 OH, R 1 ═COCH 3 ) and their counterparts of formula (II) are obtained by selective acylation of the corresponding dihydroxy compounds wherein R 1 ═H. In a preferred such method for selective acylation, the dihydroxy compound is mixed with equimolar amounts of a tertiary alkyl amine, e.g., triethylamine, and a dialkylaminopyridine, e.g., 4-dimethylaminopyridine in the presence of a reaction inert organic solvent. An equimolar amount of acetic anhydride is added at a temperature below room temperature, preferably at -10° to 20° C. and especially 0° to 10° C. The mixture is maintained at such temperature, typically for about one to four hours, then allowed to warm to room temperature and the product isolated, e.g., by extraction and evaporation of the extract to obtain a crude product which is purified by column chromatography. Preferred reaction inert solvents for this reaction include methylene chloride, chloroform and ethyl ether.
The homologous nitriles of formula (III, f=2, Q═CN, R 1 ═COCH 3 ) are obtained from the dihydroxy compounds of formula (III, Q=CH 2 OH, R 1 ═H) by acetylation as described above to afford the corresponding monoacetyl compound wherein R 1 ═COCH 3 . The latter compound is then converted to the corresponding alkylsulfonyl or arylsulfonyl ester and this product reacted further with an alkali metal cyanide such as potassium cyanide as employed methods and conditions previously described for the conversion of compounds of formula (II, Q═CH 2 OH, f=0, R 1 ═COCH 3 ) to the corresponding nitriles wherein f=1.
Hydrolysis of the acetoxy nitrile (III, Q═CN, f=2, R 1 ═COCH 3 ) with a weak base, e.g., aqueous sodium carbonate, affords the corresponding hydroxy nitrile wherein R 1 ═H.
Hydrolysis of the nitriles (III, f=2, Q═CN, R 1 ═H or COCH 3 ) with a strong base, e.g., sodium hydroxide, provides the corresponding carboxylic acids of formula (III, f=2, Q═COOH, R 1 ═H). Esterification of the latter compounds with an alcohol of formula R 7 OH, by methods described above for the corresponding compounds of formula (II), affords the esters (III, f=2, Q═COOR 7 , R 1 ═H) where R 7 is C 1 -C 4 alkyl or benzyl.
Employing methods previously described for the corresponding invention compounds of formula (II), the remaining invention compounds of formula (III) are obtained wherein f=1 or 2 and Q is CH 2 OH, CONR 12 R 13 , CH 2 NH 2 , CH 2 NHCOR 14 and CH 2 NHSO 2 R 17 as outlined in Flow Chart C, above.
Compounds of formula (I) wherein --Z--W is --(alk 1 ) m --X--(alk 2 ) n --W and X is --SO-- or --SO 2 --are obtained by oxidation of the corresponding compounds in which X is --S--. Hydrogen peroxide is a convenient agent for oxidation of the thio ethers to sulfoxides. Oxidation of the thio ethers to corresponding sulfones is conveniently accomplished by means of a peracid such as perbenzoic, perphthalic or m-chloroperbenzoic acid. This latter peracid is especially useful since the by-product m-chlorobenzoic acid is easily removed.
Group R 6 , if not already present in compounds of formula (I) where M is NR 6 , can be introduced into said compounds by reaction of the free base (R 6 ═H) with the appropriate Cl--R 6 or Br--R 6 reactant according to known procedures. Of course, for such compounds wherein Q contains an hydroxy group, or a primary or secondary amino group, it is often preferred to introduce the group R 6 prior to formation of said hydroxy or amino group in Q.
Esters of compounds of formula (I) wherein R 1 is benzoyl, alkanoyl or --CO--(CH 2 ) p --NR 15 R 16 are readily prepared by reacting formula (I) compounds wherein R 1 is hydrogen with benzoic acid, the appropriate alkanoic acid or acid of formula HOOC--(CH 2 ) p --NR 15 R 16 in the presence of a condensing agent such as dicyclohexylcarbodiimide. Alternatively, they are prepared by reaction of the formula (I) (R 1 ═H) compound with the appropriate acid chloride or anhydride, e.g., benzoyl chloride, acetyl chloride or acetic anhydride, in the presence of a base such as pyridine.
The presence of a basic group in the ester moiety (OR 1 ) in the compounds of this invention permits formation of acid-addition salts involving said basic group. When the herein described basic esters are prepared via condensation of the appropriate amino acid hydrochloride (or other acid addition salt) with the appropriate compound of formula (I) in the presence of a condensing agent, the hydrochloride salt of the basic ester is produced. Careful neutralization affords the free base. The free base form can then be converted to other acid addition salts by known procedures.
Acid addition salts can, of course, as those skilled in the art will recognize, be formed with the nitrogen of the quinoline compounds of formula (I) wherein M is NR 6 . Such salts are prepared by standard procedures. The basic ester derivatives of these quinoline compounds are, of course, able to form mono- or di-acid addition salts because of their dibasic functionality.
The analgesic properties of the compounds of this invention are determined by tests using thermal nociceptive stimuli, such as the mouse tail flick procedure, or chemical nociceptive stimuli, such as measuring the ability of a compound to suppress phenylbenzoquinone irritant-induced writhing in mice. These tests and others are described below.
Tests Using Thermal Nociceptive Stimuli
(a) Mouse Hot Plate Analgesic Testing
The method used is modified after Woolfe and MacDonald, J. Pharmacol. Exp. Therm., 80, 300-307 (1944). A controlled heat stimulus is applied to the feet of mice on a 1/8" thick aluminum plate. A 250 watt reflector infrared heat lamp is placed under the bottom of the aluminum plate. A thermal regulator, connected to thermistors on the plate surface, programs the heat lamp to maintain a constant temperature of 57° C. Each mouse is dropped into a glass cylinder (61/2" diameter) resting on the hot plate, and timing is begun when the animal's feet touch the plate. At 0.5 and 2 hours after treatment with the test compound, the mouse is observed for the first "flicking" movements of one or both hind feet, or until 10 seconds elapse without such movements. Morphine has an MPE 50 =4-5.6 mg./kg. (s.c.).
(b) Mouse Tail Flick Analgesic Testing
Tail flick testing in mice is modified after D'Amour and Smith, J. Pharmacol. Exp. Ther., 72, 74-79 (1941), using controlled high intensity heat applied to the tail. Each mouse is placed in a snug-fitting metal cylinder, with the tail protruding through one end. This cylinder is arranged so that the tail lies flat over a concealed heat lamp. At the onset of testing, an aluminum flag over the lamp is drawn back, allowing the light beam to pass through the slit and focus onto the end of the tail. A timer is simultaneously activated. The latency of a sudden flick of the tail is ascertained. Untreated mice usually react within 3-4 seconds after exposure to the lamp. The end point for protection is 10 seconds. Each mouse is tested at 0.5 and 2 hours after treatment with morphine and the test compound. Morphine has an MPE 50 of 3.2-5.6 mg./kg. (s.c.).
(c) Tail Immersion Procedure
The method is a modification of the receptacle procedure developed by Benbasset, et. al., Arch. int. Pharmacodyn., 122, 434 (1959). Male albino mice (19-21 g.) of the Charles River CD-1 strain are weighed and marked for identification. Five animals are normally used in each drug treatment group with each animal serving as its own control. For general screening purposes, new test agents are first administered at a dose of 56 mg./kg. intraperitoneally or subcutaneously, delivered in a volume of 10 ml./kg. Preceding drug treatment and at 0.5 and 2 hours post drug, each animal is placed in the cylinder. Each cylinder is provided with holes to allow for adequate ventilation and is closed by a round nylon plug through which the animal's tail protrudes. The cylinder is held in an upright position and the tail is completely immersed in the constant temperature waterbath (56° C.). The endpoint for each trail is an energetic jerk or twitch of the tail coupled with a motor response. In some cases, the endpoint may be less vigorous post drug. To prevent undue tissue damage, the trial is terminated and the tail removed from the waterbath within 10 seconds. The response latency is recorded in seconds to the nearest 0.5 second. A vehicle control and a stardard of known potency are tested concurrently with screening candidates. If the activity of a test agent has not returned to baseline values at the 2-hour testing point, response latencies are determined at 4 and 6 hours. A final measurement is made at 24 hours if activity is still observed at the end of the test day.
Test Using Chemical Nociceptive Stimuli
Suppression of Phenylbenzoquinone Irritant-Induced Writhing
Groups of 5 Carworth Farms CF-1 mice are pretreated subcutaneously or orally with saline, morphine, codeine or the test compound. Twenty minutes (if treated subcutaneously) or fifty minutes (if treated orally) later, each group is treated with intraperitoneal injection of phenylbenzoquinone, an irritant known to produce abdominal contractions. The mice are observed for 5 minutes for the presence or absence of writhing starting 5 minutes after the injection of the irritant. MPE 50 's of the drug pretreatments in blocking writhing are ascertained.
Tests Using Pressure Nociceptive Stimuli
Effect on the Haffner Tail Pinch Procedure
A modification of the procedure of Haffner, Experimentelle Prufung Schmerzstillender. Mittel Deutch Med. Wschr., 55, 731-732 (1929) is used to ascertain the effects of the test compound on aggressive attacking responses elicited by a stimulus pinching the tail. Male albino rats (50-60 g.) of the Charles River (Sprague-Dawley) CD-strain are used. Prior to drug treatment, and again at 0.5, 1, 2 and 3 hours after treatment, a Johns Hopkins 2.5-inch "bulldog" clamp is clamped onto the root of the rat's tail. The endpoint at each trial is clear attacking and biting behavior directed toward the offending stimulus, with the latency for attack reported in seconds. The clamp is removed in 30 seconds if attacking has not yet occurred, and the latency of response is recorded as 30 seconds. Morphine is active 17.8 mg./kg. (i.p.).
Tests Using Electrical Nociceptive Stimuli
The "Flinch-Jump" Test
A modification of the flinch-jump procedure of Tenen, Psychopharmacologia, 12, 278-285 (1968) is used for determining pain thresholds. Male albino rats (175-200 g.) of the Charles River (Sprague-Dawley) CD strain are used. Prior to receiving the drug, the feet of each rat are dipped into a 20% glycerol/saline solution. The animals are then placed in a chamber and presented with a series of 1-second shocks to the feet which are delivered in increasing intensity at 30-second intervals. These intensities are 0.26, 0.39, 0.52, 0.78, 1.05, 1.31, 1.58, 1.86, 2.13, 2.42, 2.72, and 3.04 mA. Each animal's behavior is rated for the presence of (a) flinch, (b) squeak and (c) jump or rapid forward movement at shock onset. Single upward series of shock intensities are presented to each rat just prior to, and at 0.5, 2, 4 and 24 hours subsequent to drug treatment.
Results of the above tests are recorded as percent maximum possible effect (% MPE). The % MPE of each group is statistically compared to the % MPE of the standard and the predrug control values. The % MPE is calculated as follows: ##EQU1##
As mentioned above, the compounds of the invention are especially useful as antiemetic and antinausea agents in mammals. They are particularly useful in preventing emesis and nausea induced by antineoplastic agents.
The antiemetic properties of the compounds of formula (I) are determined in unanesthetized unrestrained cats according to the procedure described in Proc. Soc. Exptl. Biol. and Med., 160, 437-440 (1979).
Antagonism of PGE 2 * Diarrhea in Mice
The antidiarrheal activity of the invention compounds is determined by a modification of the method of Dajani et al., European Jour. Pharmacol., 34, 105-113 (1975). This method reliably elicits diarrhea in otherwise untreated mice within 15 minutes. Pretreated animals in which no diarrhea occurs are considered protected by the test agent. The constipating effects of test agents are measured as an "all or none" response, diarrhea being defined as watery unformed stools, very different from normal fecal matter, which consists of well-formed boluses, firm and relatively dry.
Male albino mice of the Charles River CD-1 strain are used. They are kept in group cages and tested within one week following arrival. The weight range of the animals when tested is between 20-25 g. Pelleted rat chow is available ad libitum until 18 hours prior to testing, at which time food is withdrawn.
Animals are weighed and marked for identification. Five animals are normally used in each drug treatment group. Mice weighing 20-25 g. are housed in group cages, and fasted overnight prior to testing. Water is available ad libitum. Animals are challenged with PGE 2 (0.32 mg/kg i.p. in 5% ETOH) one hour after drug treatment, and immediately placed individually in transparent acrylic boxes of 15×15×18 cm. A disposable cardboard sheet on the bottom of the box is checked for diarrhea on an all or nothing basis at the end of 15 minutes. A vehicle +PGE 2 treatment group and a vehicle treatment gorup serve as controls in each day's testing.
The data are analyzed using weighted linear regression of probit-response onlog dose, employing the maximum likelihood procedure. A computer program prints results in an analysis of linear regression format, including degrees of freedom, sum of squares, mean squares and critical values of F 05 and Chi square. If the regression is significant, the ED 30 , ED 50 , ED 70 , and ED 90 and then 95% confidence limits are calculated.
The compounds of the present invention are active analgesics, antidiarrheals, antiemetics or antinauseants via oral and parenteral administration and are conveniently administered for these uses in composition form. Such compositions include a pharmaceutical carrier selected on the basis of the chosen route of administration and standard pharmaceutical practice. For example, they may be administered in the form of tablets, pills, powders or granules containing such excipients as starch, milk sugar, certain types of clay, etc. They may be administered in capsules, in admixtures with the same or equivalent excipients. They may also be administered in the form of oral suspensions, solutions, emulsions, syrups and elixirs which may contain flavoring and coloring agents. For oral administration of the therapeutic agents of this invention, tablets or capsules containing from about 0.01 to about 100 mg. are suitable for most applications.
Suspensions and solutions of these drugs, particularly those wherein R 1 is hydroxy, are generally prepared just prior to use in order to avoid problems of stability of the drug (e.g. oxidation) or of suspensions or solution (e.g. precipitation) of the drug upon storage. Compositions suitable for such are generally dry solid compositions which are reconstituted for injectable administration.
The physician will determine the dosage which will be most suitable for an individual patient and it will vary with the age, weight and response of the particular patient and the route of administration. Generally, however, the initial analgesic dosage, as well as the initial dosage for prevention or treatment of nausea, in adults may range from 0.01 to 500 mg. per day in single or divided doses. In many instances, it is not necessary to exceed 100 mg. daily. The favored oral dosage range is from about 0.01 to about 300 mg./day; the preferred range is from about 0.10 to about 50 mg./day. The favored parenteral dose is from about 0.01 to above 100 mg./day; the preferred range from about 0.01 to about 20 mg./day.
EXAMPLE 1
dl-5-Hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-one
A one liter, three-necked flask, fitted with mechanical stirrer, thermometer and ether condenser was flushed with dry nitrogen and 8.5 g (36 mmole) of 1,3-dihydroxy-5-(2,2-dimethylheptyl)benzene and 4.6 g (46.0 mmole) of 3,3-dimethylacrylic acid was added. The mixture was stirred vigorously while heating to 135° C. The thermometer was replaced by an addition funnel with condensor and 11.3 ml (107.4 mmole) of boron trifluoride etherate was added quickly via the addition funnel. Heating is continued for ten minutes, the mixture allowed to cool to room temperature and stirred for an additional ten minutes. To this was added 10 ml of cold water followed by 40 ml of 6N sodium hydroxide and the resulting mixture heated at 80° C. for five minutes. Heat was removed, the mixture acidified with five ml of concentrated hydrochloric acid and cooled to 30° C., at which temperature 200 ml of ethyl ether was added. After stirring for five minutes, the layers were separated and the aqueous phase extracted with 2×50 ml of ether. The combined ether layers were washed in succession with 2×80 ml water, 1×100 ml saturated sodium bicarbonate solution, 3×50 ml of 1N sodium hydroxide, 1×100 ml brine and 1×100 ml water, then dried over anhydrous magnesium sulfate. The ether was evaporated in vacuo to provide 11.8 g of residual oil of sufficient purity for use in the next step.
Alternatively, the crude product was chromatographed on a silica gel column, eluting with ether and hexane. Fractions were monitored by silica gel thin-layer chromatography, eluting with 9:1 hexane/ether by volume, (Rf 0.41) to afford 8.9 g (77.7%) of the desired product, 1 H-NMR(CDCl 3 )ppm(delta): 0.80-0.81 (m, 3H), 1.0-1.7 (m, 22H), 2.7 (s, 2H), 6.3-6.7 (m, 2H), 11.6 (s, 1, disappeared upon addition of D 2 O);
Infrared (KBr), cm -1 : 3400(OH), 2899(CH), 1639(C═O).
Mass spectrum (m/e): M + 318.
Analysis: Calc'd for C 20 H 30 O 3 : C, 75.43; H, 9.50. Found: C, 75.40; H, 9.54.
EXAMPLE 1A
The procedure of Example 1 is repeated but using the appropriate acid, R 4 R 5 C═CHCOOH, in place of dimethylacrylic acid and the appropriate 5-ZW-substituted-1,3-dihydroxybenzene (prepared as described in U.S. Pat. No. 4,143,139) to give the following compounds.
__________________________________________________________________________ ##STR26##R.sub.5 R.sub.4 Z W__________________________________________________________________________H H CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H H (CH.sub.2).sub.3 C.sub.6 H.sub.5H H (CH.sub.2).sub.4 C.sub.6 H.sub.5H C.sub.2 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5H H (CH.sub.2).sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 C.sub.6 H.sub.5H H C(CH.sub.3).sub.2 C.sub.6 H.sub.5H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub. 3 C.sub.6 H.sub.5H H (CH.sub.2).sub.6 C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.8 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.7 C.sub.6 H.sub.5H H CH.sub.2 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4H H CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4H C.sub.2 H.sub.5 CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.5H CH.sub.3 CH.sub.2 C.sub.6 H.sub.5H H (CH.sub.2).sub.3 C.sub.5 H.sub.9CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)CH.sub.2 C.sub.5 H.sub.9H H CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.5 H.sub.9H H CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.5 H.sub.9H H CH(CH.sub.3)CH.sub.2 C.sub.3 H.sub.5H H CH(CH.sub.3)CH(CH.sub.3) C.sub.6 H.sub.11H C.sub.2 H.sub.5 CH(CH.sub.3)CH(CH.sub.3) C.sub.6 H.sub.11H H CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11H H (CH.sub.2).sub.4 C.sub.3 H.sub.5H H (CH.sub.2).sub.8 C.sub.6 H.sub.11H C.sub.2 H.sub.5 (CH.sub.2).sub.8 C.sub.6 H.sub.11H H (CH.sub.2).sub.3 CH(CH.sub.3) C.sub.6 H.sub.11H H CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.11H H CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.11H CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.11H H (CH.sub.2).sub.3 2-pyridylH H (CH.sub.2).sub.3 4-pyridylH H (CH.sub.2).sub.4 2-pyridylH CH.sub.3 (CH.sub.2).sub.4 4-pyridylH C.sub.2 H.sub.5 (CH.sub.2).sub.4 3-pyridylH CH.sub.3 CH.sub.2 CH(CH.sub.3 )CH.sub.2 4-pyridylH C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 3-pyridylH CH.sub.3 CH(CH.sub.3)CH(C.sub.2 H.sub.5)CH.sub.2 4-pyridylH H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 3-pyridylH H CH.sub.2 CH(C.sub.2 H.sub.5)CH.sub.2 3-pyridylH H CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylH CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 2-piperidylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) 4-piperidylH CH.sub.3 CH(CH.sub.3)(CH.sub..sub.2).sub.2 C.sub.7 H.sub.13H H CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13H CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.2 C.sub.6 H.sub.5H H (CH.sub.2).sub.4 CH.sub.3H CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HH H CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HH H CH.sub.2 HH CH.sub.3 CH.sub.2 CH.sub.3H H (CH.sub.2).sub.3 CH.sub.3H H (CH.sub.2).sub.6 CH.sub.3H CH.sub.3 (CH.sub.2).sub.6 CH.sub.3H H CH(CH.sub.3) CH.sub.3H CH.sub.3 (CH.sub.2).sub.3 HH H CH(CH.sub.3) C.sub.6 H.sub.11H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3H H (CH.sub.2).sub.3O C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.3O 4-FC.sub.6 H.sub.4H CH.sub.3 (CH.sub.2).sub.3O C.sub.6 H.sub.11H C.sub.2 H.sub.5 (CH.sub.2).sub.3O C.sub.4 H.sub.7H H (CH.sub.2).sub.3O CH.sub.3H CH.sub.3 (CH.sub.2).sub.3O 4-(4-FC.sub.6 H.sub.4)C.sub.6 H.sub.10H C.sub.2 H.sub.5 (CH.sub.2).sub.3O(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4H H (CH.sub.2).sub.3O(CH.sub.2).sub.2 C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.3OCH(CH.sub.3) 4-piperidylH CH.sub.3 (CH.sub.2).sub.3OCH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5H H (CH.sub.2).sub.3OCH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3H H CH(CH.sub.3)(CH.sub.2).sub.2O C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH.sub.2 CH.sub.3H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2O(CH.sub.2).sub.4 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH(CH.sub.3) C.sub.7 H.sub.13H H CH(CH.sub.3)(CH.sub.2).sub.2OCH.sub.2 CH(C.sub.2 H.sub.5) CH.sub.3H CH.sub.3 (CH.sub.2).sub.4O C.sub.6 H.sub.5H H (CH.sub.2).sub.4OCH(CH.sub.3)CH.sub.2 3-piperidylH C.sub.2 H.sub.5 (CH.sub.2).sub.4O(CH.sub.2).sub.5 4-pyridylH C.sub.2 H.sub.5 (CH.sub.2).sub.4OCH.sub.2 4-FC.sub.6 H.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.3O 2-(4-FC.sub.6 H.sub.5)C.sub.2 H.sub.8H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3O(CH.sub.2).sub.2 C.sub.2 H.sub.5H C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.3O(CH.sub.2).sub.2 CH.sub.3H H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O(CH.sub.2).sub.4 C.sub.6 H.sub.5H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2OCH(CH.sub.3) 4-piperidylH H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O(CH.sub.2).sub.2CH(CH.sub.3) 2 C.sub.7 H.sub.13H CH.sub.3 CH(CH.sub.3)OCH.sub.2 C.sub.5 H.sub.9H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O C.sub.3 H.sub.5H H CH(C.sub. 2 H.sub.5)(CH.sub.2).sub.2O 2-(4-FC.sub.6 H.sub.11)C.sub.7 H.sub.12H H (CH.sub.2).sub.3S C.sub.6 H.sub.5H C.sub.2 H.sub.5 (CH.sub.2).sub.3SCH.sub.2 4-FC.sub.6 H.sub.4H CH.sub.3 (CH.sub.2).sub.3S C.sub.5 H.sub.9H C.sub.2 H.sub.5 (CH.sub.2).sub.3S(CH.sub.2).sub.2 CH.sub.3H H (CH.sub.2).sub.3S(CH.sub.2).sub.4 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S 4-piperidylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 S(CH.sub.2).sub.4 4-pyridylH CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S(CH.sub.2).sub.4 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2S C.sub.6 H.sub.11H CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2S(CH.sub.2).sub.2CH(CH.sub.3) . CH.sub.3H H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2SCH(CH.sub.3) 4-ClC.sub.6 C.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.3S(CH.sub.2).sub.4 4-FC.sub.6 H.sub.4H CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3S(CH.sub.2).sub.4 4-pyridylH H CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.6 CH.sub.3H CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.6 C.sub.6 H.sub.5H H CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.4 CH.sub.3H H CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH(CH.sub.3)CH.sub.2OCH(CH.sub.3)CH.sub. 2 C.sub.6 H.sub.5H CH.sub.3 CH(CH.sub.3)CH.sub.2OCH.sub.2 4-FC.sub.6 H.sub.4H CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.2 4-pyridylH H CH(CH.sub.3)CH.sub.2OCH(CH.sub.3) CH.sub.3H H CH.sub.2 CH(CH.sub.3)OCH.sub.2 CH.sub.3H C.sub.2 H.sub.5 CH.sub.2 CH(CH.sub.3)OCH.sub.2 CH.sub.3H CH.sub.3 CH.sub.2 CH(CH.sub.3)O(CH.sub.2).sub.6 CH.sub.3H CH.sub.3 CH.sub.2 CH(CH.sub.3)OCH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H H CH.sub.2 CH(CH.sub.3)O(CH.sub.2).sub.2 4-FC.sub.6 H.sub.4H CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HH C.sub.2 H.sub.5 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.2 H.sub.5 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub. 2).sub.3 C.sub.6 H.sub.5H CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 C.sub.6 H.sub.5H n-C.sub.6 H.sub.13 (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5H (CH.sub.2).sub.4 C.sub.6 H.sub.5 (CH.sub.2).sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.3 C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.6 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.8 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.7 C.sub.6 H.sub.5H n-C.sub.4 H.sub.9 CH.sub.2 C.sub.6 H.sub.5H n-C.sub.4 H.sub.9 CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4CH.sub.3 n-C.sub.6 H.sub.13 CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4H (CH.sub.2).sub.2 C.sub.6 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub. 5H CH.sub.3 CH.sub.2 C.sub.6 H.sub.5H CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 C.sub.5 H.sub.9CH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2 C.sub.5 H.sub.9CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.5 H.sub.9CH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2 C.sub.3 H.sub.5H (CH.sub.2).sub.3 C.sub.6 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11CH.sub.3 n-C.sub.4 H.sub.9 (CH.sub.2).sub.4 C.sub.3 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.9 C.sub.6 H.sub.11CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 2-pyridylCH.sub.3 CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 4-pyridylCH.sub.3 CH.sub.3 (CH.sub.2).sub.4 4-pyridylC.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.4 3-pyridylCH.sub.3 CH.sub.3 CH(CH.sub.3)CH(C.sub.2 H.sub.5)CH.sub.2 4-pyridylH n-C.sub.5 H.sub.11 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 3-pyridylH i-C.sub.3 H.sub.7 CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylCH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 2-piperidylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3) 4-piperidylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13H n-C.sub.4 H.sub.9 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13CH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.4 CH.sub.3CH.sub.3 CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.5 HCH.sub.3 CH.sub.3 CH.sub.2 HCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.3 CH.sub.3H n-C.sub.6 H.sub.13 (CH.sub.2).sub.6 CH.sub.3CH.sub.3 (CH.sub.2).sub.3 C.sub.6 H.sub.5 CH(CH.sub.3) CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 HH n-C.sub.4 H.sub.9 CH(CH.sub.3) C.sub.6 H.sub.11CH.sub.3 CH.sub.3 (CH.sub.2 ).sub.3O C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.3O 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 (CH.sub.2).sub.3O C.sub.6 H.sub.11C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3O C.sub.4 H.sub.7H CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3O CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.3O 4-(4-FC.sub.6 H.sub.4)C.sub.6 H.sub.10C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3O(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH.sub.3 CH.sub.3 (CH.sub.2).sub.3OCH(CH.sub.3) 4-piperidylH n-C.sub.5 H.sub.11 CH(CH.sub.3)(CH.sub.2).sub.2O C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH.sub.2 CH.sub.3CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2O(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2OCH(CH.sub.3) C.sub.7 H.sub.13CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub. 2OCH.sub.2CH(C.sub.2 H.sub.5) CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.4O C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.4OCH(CH.sub.3)CH.sub.2 3-piperidylCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.4OCH.sub.2 4-FC.sub.6 H.sub.4H n-C.sub.3 H.sub.7 CH(CH.sub.3)(CH.sub.2).sub.3O 2-(4-FC.sub.6 H.sub.5)C.sub.2 H.sub.8CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3O(CH.sub.2).sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2OCH(CH.sub.3) 4-piperidylCH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O C.sub.3 H.sub.5CH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2O 2-(4-FC.sub.6 H.sub.11)C.sub.7 H.sub.12CH.sub.3 CH.sub.3 (CH.sub.2).sub.3S C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3SCH.sub.2 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 (CH.sub.2).sub.3S C.sub. 5 H.sub.9CH.sub.3 CH.sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3S(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S 4-piperidylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S(CH.sub.2).sub.4 4-pyridylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2S(CH.sub.2).sub.4 C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2SO C.sub.6 H.sub.11H n-C.sub.6 H.sub.13 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2SCH(CH.sub.3) 4-ClC.sub.6 H.sub.4CH.sub.3 n-C.sub.4 H.sub.9 CH(CH.sub.3)(CH.sub.2).sub.3S(CH.sub.2).sub.4 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3S(CH.sub.2).sub.4 4-pyridylCH.sub.3 CH.sub.3 CH(CH.sub.3)CH.sub.2O(CH.sub.2).sub.6 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HC.sub.2 H.sub.5 C.sub.2 H.sub.5 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H__________________________________________________________________________
Alternate methods for preparing the above compounds are described in U.S. Pat. No. 4,143,139.
EXAMPLE 1B
dl-5-Hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-4-one
A mixture of 5-phenyl-2-pentanol (16.4 g, 100 mM), triethylamine (28 ml, 200 mM) and dry tetrahydrofuran (80 ml) under a nitrogen atmosphere is cooled in an ice/water bath. Methanesulfonyl chloride (8.5 ml, 110 mM) in dry tetrahydrofuran (20 ml) is added dropwise at such a rate that the temperature holds essentially constant. The mixture is allowed to warm to room temperature and is then filtered to remove triethylamine hydrochloride. The filter cake is washed with dry tetrahydrofuran and the combined wash and filtrate evaporated under reduced pressure to give the product as an oil. The oil is dissolved in chloroform (100 ml) and the solution washed with water (2×100 ml) and then with saturated brine (1×20 ml). Evaporation of the solvent affords 21.7 g (89.7%) yield of 5-phenyl-2-pentanol mesylate which is used in the next step without further purification.
A mixture of 2,2-dimethyl-5,7-dihydroxy-4-chromanone (2.08 g, 10 mM), potassium carbonate (2.76 g, 20 mM), N,N-dimethylformamide (10 ml) and 5-phenyl-2-pentanol mesylate (2.64 g, 11 mM), under a nitrogen atmosphere, is heated to 80°-82° C. in an oil bath for 1.75 hours. The mixture is cooled to room temperature and then poured into ice/water (100 ml). The aqueous solution is extracted with ethyl acetate (2×25 ml) and the combined extracts washed successively with water (3×25 ml) and saturated brine (1×25 ml). The extract is then dried (MgSO 4 ), decolorized with charcoal and evaporated to give the product as an oil which crystallizes upon seeding with pure product; m.p. 83°-84° C. Yield=quantitative.
In like manner, the following compounds are prepared from appropriate 2,2-R 4 R 5 -5,7-dihydroxy-4-chromanones and appropriate alkanols. The necessary alkanol reactants not previously described in the literature are prepared from appropriate aldehydes or ketones via the Wittig reaction as described in U.S. Pat. No. 4,143,139. The same reference describes the preparation of the above 4-chromanone starting materials.
__________________________________________________________________________ ##STR27##R.sub.4 R.sub.5 alk.sub.2 W__________________________________________________________________________CH.sub.3 CH.sub.3 CH.sub.2 C(CH.sub.3).sub.2 (CH.sub.2).sub.4 CH.sub.3CH.sub.3 CH.sub.3 CH.sub.2 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3CH.sub.3 H CH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.2 CH(CH.sub.3) CH.sub.3CH.sub.3 H (CH.sub.2).sub.2 CH(CH.sub.3)CH.sub.2 CH(CH.sub.3) CH.sub.3H H CH(CH.sub.3)(CH.sub.2).sub.2 C(CH.sub.3).sub.2 CH.sub.3C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CH(CH.sub.3) C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.4 C.sub.6 H.sub.5H H (CH.sub.2).sub.4 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5H CH.sub.3 (CH.sub.2).sub.7 C.sub.6 H.sub.5H H CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.5C.sub.2 H.sub.5 H (CH.sub.2).sub.9 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 (CH.sub.2).sub.9 CH.sub.3H CH.sub.3 CH(CH.sub.3)CH.sub.2 2-pyridylH C.sub.2 H.sub.5 CH.sub.2 C(CH.sub.3).sub.2 2-pyridylH CH.sub.3 (CH.sub.2).sub.3 2-pyridylC.sub.2 H.sub.5 CH.sub.3 (CH.sub.2).sub.2 2-pyridylH H (CH.sub.2).sub.2 4-pyridylCH.sub.3 CH.sub.3 (CH.sub.2).sub.3 3-pyridylCH.sub.3 H (CH.sub.2).sub.3 4-pyridylCH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.4 2-pyridylH H (CH.sub.2).sub.3 2-piperidylCH.sub.3 H (CH.sub.2).sub.3 4-piperidylCH.sub.3 CH.sub.3 (CH.sub.2).sub.3 4-FC.sub.6 H.sub.4H H (CH.sub.2).sub.3 4-ClC.sub.6 H.sub.4C.sub.2 H.sub.5 H (CH.sub.2).sub.4 C.sub.6 H.sub.5C.sub.2 H.sub.5 H (CH.sub.2).sub.4 4-FC.sub.6 H.sub.4H H CH(CH.sub.3)(CH.sub.2).sub.2 2-pyridylC.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 3-pyridylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 4-pyridylCH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylH CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 2-pyridylCH.sub.3 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-pyridylC.sub.2 H.sub.5 CH.sub.3 CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-piperidylH C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.2 4-FC.sub.6 H.sub.4CH.sub.3 H CH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH.sub.3 CH.sub.3 CH.sub.2 C.sub.6 H.sub.5H H CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH.sub.2 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 -- C.sub.6 H.sub.5CH.sub.3 CH.sub.3 -- 4-FC.sub.6 H.sub.4C.sub.2 H.sub.5 H -- 4-ClC.sub.6 H.sub.4C.sub.2 H.sub.5 C.sub.2 H.sub.5 -- C.sub.6 H.sub.5H H -- 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 -- C.sub.3 H.sub.5H H -- C.sub.3 H.sub.5CH.sub.3 CH.sub.3 -- C.sub.4 H.sub.7CH.sub.3 H -- C.sub.4 H.sub.7C.sub.2 H.sub.5 C.sub.2 H.sub.5 -- C.sub.5 H.sub.9CH.sub.3 CH.sub.3 -- C.sub.5 H.sub.9CH.sub.3 H -- C.sub.6 H.sub.11CH.sub.3 H -- C.sub.7 H.sub.13CH.sub.3 CH.sub.3 -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4CH.sub.3 CH.sub.3 -- 1-(C.sub.6 H.sub.5)C.sub.4 H.sub.6CH.sub.3 CH.sub.3 -- 2-(C.sub.6 H.sub.5)C.sub.5 H.sub.8CH.sub.3 H -- 2-(C.sub.6 H.sub.5)C.sub.5 H.sub.8CH.sub.3 CH.sub.3 -- 2-(C.sub.6 H.sub.5)C.sub.6 H.sub.10C.sub.2 H.sub.5 C.sub.2 H.sub.5 -- 3-(C.sub.6 H.sub.5)C.sub.6 H.sub.10CH.sub.3 CH.sub.3 -- 4-pyridylCH.sub.3 CH.sub.3 -- 4-piperidylCH.sub.3 H -- 2-(C.sub.6 H.sub.5)C.sub.6 H.sub.10H H -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10CH.sub.3 CH.sub.3 -- 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.12CH.sub.3 CH.sub. 3 CH.sub.2 CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.3 CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.6 CH.sub.3CH.sub.3 CH.sub.3 (CH.sub.2).sub.9 CH.sub.3CH.sub.3 H (CH.sub.2).sub.6 CH.sub.3C.sub.2 H.sub.5 C.sub.2 H.sub.5 (CH.sub.2).sub.3 CH.sub.3CH.sub.3 CH.sub.3 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH.sub.3 CH.sub.3 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3__________________________________________________________________________
EXAMPLE 1C
dl-5-Hydroxy-2,2-dimethyl-7-(2-heptylmercapto)-3,4-dihydro-2H-benzopyran-4-one
To a solution of 5-hydroxy-7-mercapto-2,2-dimethyl-4-chromanone (19.7 g, 87.1 mM) and potassium hydroxide (2.44 g, 43.5 mM) in N,N-dimethylformamide (58 ml) is added with stirring 2-bromoheptane (15.77 g, 88.0 mM). The mixture is heated for four days at 100° C., cooled to room temperature and then added to a mixture of aqueous sodium hydroxide (110 ml of 1N), water (45 ml) and chloroform (150 ml). The mixture is agitated, the phases separated and the aqueous layer extracted with more chloroform (150 ml). The combined chloroform layers are washed with 1N sodium hydroxide (2×100 ml), dried over sodium sulfate and concentrated to an oil. The unreacted 2-bromoheptane is removed by distillation and the residue purified by silica gel chromatography to give the title product.
The following compounds are similarly prepared from appropriate reactants of the formula Br-(alk 2 ) n -W from the appropriate 5-hydroxy-7-mercapto-2,2-R 4 R 5 -substituted-4-chromanone, preparation of which is described in U.S. Pat. No. 4,143,139.
______________________________________ ##STR28##R.sub.4R.sub.5 n (alk.sub.2) W______________________________________H CH.sub.3 1 CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3C.sub.2 H.sub.5C.sub.2 H.sub.5 1 CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3CH.sub.3CH.sub.3 1 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H CH.sub.3 1 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.3CH.sub.3 1 CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5CH.sub.3CH.sub.3 1 CH(CH.sub.3)(CH.sub.2).sub.3 4-pyridylH H 1 CH(CH.sub.3)(CH.sub.2).sub.3 4-pyridylCH.sub.3CH.sub.3 1 CH.sub.2 C.sub.6 H.sub.5CH.sub.3CH.sub.3 1 (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub. 3C.sub.2 H.sub.5 1 (CH.sub.2).sub.7 C.sub.6 H.sub.5CH.sub.3CH.sub.3 1 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH.sub.3H 1 C(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH.sub.3CH.sub.3 1 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3H CH.sub.3 1 CH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3CH.sub.3CH.sub.3 1 (CH.sub.2).sub.3 3-pyridylCH.sub.3H 1 (CH.sub.2).sub.3 4-pyridylH CH.sub.3 1 CH(CH.sub.3)CH.sub.2 2-pyridylH H 1 (CH.sub.2).sub.2 4-pyridylC.sub.2 H.sub.5CH.sub.3 1 CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylCH.sub.3CH.sub.3 0 -- C.sub.6 H.sub.5CH.sub.3CH.sub.3 0 -- C.sub.6 H.sub.11H CH.sub.3 0 -- 4-FC.sub.6 H.sub.4C.sub.2 H.sub.5H 0 -- 4-ClC.sub.6 H.sub.4C.sub.2 H.sub.5C.sub.2 H.sub.5 0 -- C.sub.6 H.sub.5CH.sub.3CH.sub.3 0 -- C.sub.3 H.sub.5H H 0 -- C.sub.3 H.sub.5CH.sub.3H 0 -- C.sub.4 H.sub.7CH.sub.3CH.sub.3 0 -- C.sub.5 H.sub.9CH.sub.3H 0 -- C.sub.7 H.sub.13CH.sub.3CH.sub.3 0 -- 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4CH.sub.3CH.sub.3 0 -- 2-(C.sub.6 H.sub.5)C.sub.5 H.sub.8CH.sub.3CH.sub.3 0 -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10CH.sub.3CH.sub.3 0 -- 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.12H H 0 -- 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10CH.sub.3CH.sub.3 0 -- 4-pyridylCH.sub.3CH.sub.3 0 -- 4-piperidyl______________________________________
EXAMPLE 2
dl-5-Benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-one
To a flask containing 3.52 g (45 mmole) of potassium hydride, 50% oil suspension, which had been washed five times with pentane to remove the oil by decantation was added 50 ml of N,N-dimethylformamide (DMF) which had been purified by stirring overnight with calcium hydride and distillation. The mixture was stirred and cooled to 0° C., 11.8 g (36 mmole) of crude 5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-one in 100 ml of purified DMF was added dropwise at such a rate that the temperature of the reaction mixture did not exceed 6° C. (about 20 minutes). The mixture was then allowed to warm to room temperature and stirred for one hour. The reaction mixture was cooled to 3° C., a solution of 4.4 ml (37 mmole) benzyl bromide in 50 ml of DMF was added dropwise over ten minutes while maintaining the mixture below 8° C. The mixture was allowed to warm to room temperature and stirred for four hours. The reaction was quenched by slow, dropwise addition of 10 ml of water, diluted with 500 ml of ethyl ether, washed with 1×150 ml water, 3×150 ml 0.1N hydrochloric acid, 1×100 ml water, 1×150 ml saturated sodium bicarbonate solution, 1×150 ml brine and 1×150 ml water. The washed ethereal solution was dried over anhydrous magnesium sulfate, the solvent evaporated in vacuo and the residual oil (15 g) purified by chromatography on 200 g of silica gel (40-63 microns) eluting with pentane and ethyl acetate. Evaporation of the product containing fractions afforded 8.8 g (60%) of solid material. Recrystallization from hexane or pentane afforded crystals, m.p. 52°-52.5° C.
1 H-NMR(CDCl 3 )ppm(delta): 0.85 (s, 3H), 1.0-1.8 (m, 22H), 2.7 (s, 2H), 6.5 (s, 2H), 7.2-7.8 (m, 5H); Mass spectrum (m/e): M + 408.
Analysis: Calc'd for C 27 H 30 O 3 : C, 79.37; H, 8.88. Found: C, 79.22; H, 8.74.
EXAMPLE 3
dl-5-Benzyloxy-4-ethoxycarbonylmethyl-4-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A. To a 200 ml, three-necked flask equipped with a magnetic stirrer, addition funnel and nitrogen inlet, was charged 11.36 ml (25 mmole) of 2.2 molar n-butyl lithium in hexane at -78° C. The solution was diluted with 12 ml of tetrahydrofuran (THF) which had been treated with sodium metal and distilled. A solution of 4.52 g (25 mmole) of dicyclohexylamine in 12 ml of the same THF was added dropwise via the addition funnel. To the resulting slurry was added dropwise 2.44 ml (25 mmole) of ethyl acetate and the resulting mixture stirred at -78° C. for 15 minutes. To this was added dropwise 10.01 g (24.5 mmole) of 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-one dissolved in 30 ml of the same THF. The resulting mixture was stirred at -78° C. for three hours after which the reaction was quenched by addition of 2 ml (35 mmole) of glacial acetic acid. The mixture was allowed to warm to room temperature, 50 ml of saturated sodium bicarbonate solution followed by 50 ml of ethyl ether was added. The layers were separated, the organic layer washed with 3×35 ml of cold 1N hydrochloric acid, 1×30 ml of saturated sodium bicarbonate solution, 1×30 ml of water and the organic layer dried over anhydrous magnesium sulfate. Evaporation of solvent afforded 12.5 g of residual oil. This was purified by chromatography on 200 g of silica gel (40-63 microns), eluting with 4 liters of ethyl ether/low boiling petroleum ether (2:23 by volume) and 2 liters of the same solvents mixed in a ratio of 5:20 by volume. The combined product fractions were evaporated to afford 9.0 g (74.5%) of purified product. Rf 0.22 on silica gel TLC using a 1:1 by volume ether/hexane solvent system.
1 H-NMR(CDCl 3 )ppm(delta): 0.72 (s, 3H), 0.90 (t, 3H), 1.03 (s, 6H), 1.12 (s, 3H), 1.18 (s, 3H), 1.70 (d, 1H), 2.05 (d, 1H), 2.42 (d, 1H), 2.57 (d, 1H), 3.07 (s, 1H), 3.30 (q, 2H), 4.28 (s, 2H), 5.42 (s, 2H), 6.08-6.38 (m, 5H); Infrared spectrum (film), cm -1 : 3560(OH), 3030(CH, aromatic), 2925 (CH, aliphatic), 1710(C═O); Mass spectrum (m/e): M + 496, 478 (M-18, base peak).
B. Alternatively, this product is made by the following procedure.
Zinc metal (13 g, 0.2 mole) is covered with a small amount of dimethoxymethane. The mixture is heated at reflux and a solution of 16.7 g (0.1 mole) ethyl bromoacetate in 75 ml of dimethoxymethane is added over 20 minutes. After refluxing for 30 minutes, the mixture is cooled to 0°-5° C. and 40.85 g (0.10 mole) dl-5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-one is added dropwise. The mixture is stirred at 0°-5° C. for one hour, allowed to warm to room temperature and stirred overnight. Ammonium hydroxide, 25 ml, is added, the mixture extracted with ethyl ether and isolated as described in Part A above, to afford the desired product.
Use of the appropriate acetate ester in place of ethylacetate in the above procedures affords the following compounds in like manner. ##STR29## where R 7 is methyl, isopropyl, n-propyl, n-butyl or isobutyl.
EXAMPLE 3A
dl-4,5-Dihydroxy-4-methoxycarbonylmethyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A mixture of 655 mg (1.37 mmole) 5-benzyloxy-4-ethoxycarbonylmethyl-4-hydroxy-2,2-dimethyl-7(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran, 133 mg 5% palladium-on-calcium carbonate and 50 ml methanol was hydrogenated at 38 psi (2.7 kg/cm 2 ) until hydrogen uptake ceased. The mixture was filtered, the filtrate evaporated in vacuo and the residual oil taken up in hexane. Upon cooling, crystals formed which were collected by filtration, 66 mg. The mother liquor was evaporated in vacuo to an oil, pentane added and the mixture refrigerated overnight. Filtration gave an additional 179 mg of product. 1 H-NMR(CDCl 3 )ppm(delta): 3.00 (dd, 2H), 3.20 (s, 2H), 3.70 (s, 3H), 4.90 (s, 1H), 6.35 (m, 2H), 7.65 (s, 1H).
EXAMPLE 4
dl-5-Hydroxy-4-methoxycarbonylmethyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran and its corresponding lactone ##STR30##
In a 500 ml pressure bottle was placed a solution of 8.55 g (17.2 mmole) of 5-benzyloxy-4-ethoxycarbonylmethyl-4-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran in 250 ml of methanol. One gram of 5% palladium-on-carbon catalyst was added and the mixture was shaken under hydrogen at 40 psi. (2.8 kg/cm 2 ) for 17 hours. The reaction mixture was filtered through anhydrous magnetism sulfate and the solvent evaporated in vacuo. The residue was partitioned between 100 ml of ethyl ether and 50 ml of water, the aqueous layer extracted again with 50 ml of ether and the combined ether extracts washed with 30 ml saturated sodium bicarbonate solution and 30 ml water. The ether was dried over anhydrous magnesium sulfate and the solvent evaporated in vacuo to obtain a mixture of methyl ester and lactone from which the former product crystallizes upon standing. After recrystallization from low boiling petroleum ether, purified methyl ester was obtained, m.p. 72°-73° C. 1 H-NMR(CDCl 3 )ppm(delta): 0.82 (s, 3H), 1.0-1.5 (m, 20H), 1.53-2.6 (m, 4H), 3.1-3.6 (m, 3H), 3.68 (s, 3H), 5.8 (s, 1 H), 6.2-6.4 (m, 2H); Infrared spectrum (KBr), cm -1 : 3390(OH), 2924(CH, aliphatic), 1745(C═O); Mass spectrum (m/e): M + 376, base peak 260.
Analysis: Calc'd for C 23 H 36 O 4 : C, 73.36; H, 9.64. Found: C, 73.38; H, 9.51.
Purification of the mother liquors by silica gel chromatography afforded the lactone: 2,2-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran-5-one.
1 H-NMR(CDCl 3 )ppm(delta): 0.85 (s, 3H), 1.03-1.83 (m, 20H), 1.87-3.17 (m, 5H), 3.2-3.7 (m, 2H), 6.4 (s, 1H), 6.6 (s, 1H); Infrared spectrum (film), cm -1 : 3025(CH, aromatic), 2925(CH, aliphatic), 1660(C═O); Mass spectrum (m/e): 343 M + , base peak 260.
Analysis: Calc'd for C 22 H 32 O 3 : C, 76.70; H, 9.31. Found: C, 76.38; H, 9.54.
The remaining homologous esters provided in Example 3 are employed to obtain the following compounds in like manner when the above hydrogenation is carried out in the corresponding alcohol, R 7 OH, where R 7 has the values given in Example 3. ##STR31##
EXAMPLE 4A
By employing the procedure of Example 2, but with the appropriate benzopyran-4-one selected from those provided in Examples 1A, 1B and 1C, and carrying the product thus obtained through the procedure of Example 3, but employing an ester R 2 R 3 CHCOOR 7 in place of ethyl acetate, followed by hydrogenolysis of the hydroxyester in an alcohol of formula R 7 OH in place of methanol in the procedure of Example 4, compounds of the formulae below are similarly obtained from each of the starting benzopyran-4-ones.
______________________________________ ##STR32##R.sub.2 R.sub.3 R.sub.7______________________________________H CH.sub.3 C.sub.2 H.sub.5CH.sub.3 CH.sub.3 -n-C.sub.3 H.sub.7CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH(CH.sub.3).sub.2C.sub.2 H.sub.5 C.sub.2 H.sub.5 -n-C.sub.4 H.sub.9H C.sub.2 H.sub.5 CH(CH.sub.3)CH.sub.2 CH.sub.3______________________________________
EXAMPLE 5
dl-5-Hydroxy-4-(2-hydroxyethyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A 125 ml, round-bottomed flask equipped with a magnetic stirrer and nitrogen inlet was thoroughly flushed with dry nitrogen. Lithium aluminum hydride, 158 mg (4.2 mmole) and 50 ml of dry ethyl ether were added and the suspension stirred and cooled in an ice bath. To the cooled mixture was added slowly 1.44 g (4.2 mmole) of 5-hydroxy-4-methoxycarbonylmethyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran dissolved in 20 ml of ether. The cooling bath was removed and the reaction mixture stirred at room temperature for 12 hours. Ethyl acetate, 50 ml, was cautiously added to quench the reaction. The resulting mixture was washed with 50 ml each of saturated sodium bicarbonate solution, brine and water. The organic layer was dried over anhydrous magnesium sulfate, solvent evaporated in vacuo and the crude oil (1.5 g) was purified by chromatography on 25 g of silica gel (48-63 microns), eluting with pentane and ethyl acetate. The desired product, Rf 0.125 on silica gel TLC employing 1:1 ether/toluene by volume, amounted to 1.0 g (69%). 1 H-NMR(CDCl 3 )ppm(delta): 0.83 (s, 3H), 1.0-1.67 (m, 23H), 1.7-2.1 (m, 2H), 2.7-3.3 (m, 2H), 3.83 (t, 2H), 6.4 (s, 2H), 7.4-7.9 (s, broad, 1H); Infrared spectrum (film), cm 1 : 3333(OH), 2545(CH); Mass spectrum (m/e): M + 348, 264, base peak.
Analysis: Calc'd for C 22 H 36 O 3 : C, 76.70; H, 9.36. Found: C, 77.36; H, 9.67.
When the lactone: 5,5-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran-2-one or its mixtures with the methyl ester employed above were reduced by the above procedure the title compound was obtained in a like manner.
When 1,3-dihydroxy-5-(5-phenyl-2-pentyloxy) benzene is used in place of 1,3-dihydroxy-5-(2,2-dimethylheptyl) benzene in the procedure of Example 1 and the resulting product treated according to the procedures of Examples 2-5, dl-5-hydroxy-4-(2-hydroxyethyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloy)-3,4-dihydro-2H-benzopyran is similarly obtained.
1 H-NMR(CDCl 3 )ppm(delta): 1.2-1.5 (m, 9H), 1.52-2.3 (m, 8H), 2.4-2.8 (m, 2H), 2.9-3.2 (m, 1H), 3.8 (t, 2H), 4.1-4.5 (m, 1H), 6.0 (s, 2H), 7.2 (s, 5H); Infrared spectrum (film) cm -1 : 3400(OH), 2980(CH); Mass spectrum: M + 384, base peak 191.
EXAMPLE 5A
Employing the procedure of Example 5, but starting with the appropriate 7-ZW-substituted-5-hydroxy-4-(R 2 R 3 -substituted-alkoxycarbonyl)-2,2-R 4 R 5 -substituted-3,4-dihydro-2H-benzopyran provided in Example 4A, the following compounds are obtained in like manner: ##STR33## where R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Example 4A.
EXAMPLE 6
dl-2-Hydroxy-5,5-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran
A solution of 1.80 g (5.2 mmole) 5,5-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran-2-one in 25 ml of dry toluene is cooled to -78° C. with stirring. To this was added dropwise 5.2 ml of 1.0M diisobutyl aluminum hydride at such a rate that the temperature of the mixture did not exceed -60° C. (ca. 20 minutes). The resulting mixture was stirred at -78° C. for one hour, after which 4 ml of methanol was added and the mixture allowed to warm to room temperature. Ethyl ether, 75 ml, was added and the mixture was washed with 3×30 ml of sodium potassium tartarate solution, 30 ml of brine and 30 ml of water. The organic phase was dried (MgSO 4 ) and the solvent evaporated in vacuo to afford 1.80 g (100%) of the title hemiacetal.
1 H-NMR(CDCl 3 )ppm(delta): 0.83 (s, 3H), 1.0-1.4 (m, 22H), 1.6-2.3 (m, 4H), 2.8-3.3 (m, 1H), 3.5 (s, broad, 1H), 5.4-5.8 (m, 1H), 6.4 (m, broad, 2H); Infrared spectrum (film), cm -1 : 3450(OH), 2925(CH); Mass spectrum (m/e): M + 346, 146 base peak.
Analysis: Calc'd for C 22 H 34 O 3 : C, 76.26; H, 9.89. Found: C, 75.40; H, 9.45.
When 5,5-dimethyl-8-(5-phenyl-2-pentyloxy)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran-2-one was reduced by the above procedure, 2-hydroxy-5,5-dimethyl-8-(5-phenyl-2-pentyloxy)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran was obtained in 95% yield as an oil. It was identified by 1 H-NMR spectroscopy; Rf 0.47 upon chromatography on a silic gel plate, solvent system: cyclohexane/ethyl ether, 1:1 v/v, vanillin spray.
In like manner compounds of the following formula are obtained from the corresponding lactones provided in Example 4A. ##STR34## where R 4 , R 5 , Z and W have the values given in Examples 1, 1A, 1B and 1C.
EXAMPLE 6A
2-Methoxyamino-5,5-dimethyl-8-(5-phenyl-2-pentyloxy)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran
In a stirred flask, under nitrogen, was placed (0.045 mole) 2-hydroxy-5,5-dimethyl-8-(5-phenyl-2-pentyloxy)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran, 250 ml ethanol and 250 ml pyridine. The solution was cooled to 0° C. and 3.94 g (0.047 mole) methoxyamine was added. The resulting mixture was stirred at 0° C. for 2.5 hours, the solvent evaporated in vacuo, the residue taken up in 500 ml ethyl ether and washed twice with water. The aqueous phase was backwashed with ether and the combined ether layers washed with brine and dried over anhydrous magnesium sulfate. The solvent was evaporated in vacuo to obtain 19 g of residual oil. The structure of the product was verified by 1 H-NMR. Mass spectrum (m/e): 411 (M 30 ), 380 (M-OCH 3 ), 364 (M-NH 2 OCH 3 ).
A portion of the crude product was purified by column chromatography on silica gel, eluting with ethyl ether. The product-containing fractions were combined and evaporated to afford purified product which showed only one spot on silica gel TLC, Rf 0.58, isopropyl ether solvent, vanillin spray.
EXAMPLE 6B
4-(2-Aminoethyl)-5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
In a stirred flask, under nitrogen, was placed 17.5 g (0.043 mole) 2-methoxyamino-5,5-dimethyl-8-(5-phenyl-2-pentyloxy)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran in 1800 ml methanol. The mixture was warmed to 40° C. and 1080 ml 1N sodium hydroxide was added in portions over ten minutes. The mixture was heated to 55° C. and 20.4 g Raney Alloy (nickel/aluminum 1:1 by weight) was added in portions over ten minutes (foaming-). The resulting mixture was stirred at 55° C. for one hour, allowed to cool to room temperature and the catalyst removed by filtration. The filtrate was evaporated in vacuo to an oil which was combined with water and 6N hydrochloric acid added to adjust the mixture of pH 6-7. The neutralized mixture was extracted with ethyl acetate, the organic layer backwashed with brine, dried (MgSO 4 ), filtered and the solvent evaporated at reduced pressure to provide 16.4 g crude product as an oil.
The crude product was purified by column chromatography on silica gel, 150 g, eluting with two column volumes of chloroform, then with ethyl acetate/triethylamine, 95:5 v/v. Fractions no. 8 through 20 were combined and evaporated to dryness to provide 6.5 g of starting material. Fractions no. 2 through 5 were evaporated to provide 1.2 g of the desired product, Rf 0.79 on silica gel TLC, ethylacetate/triethylamine, 95:1 v/v, FastBlue spray. 1 H-NMR(CDCl 3 )ppm(delta): 7.2 (m, 5H, aromatic, 6.0 (s, 2H, aromatic), 4.8 (s, broad, 3H, NH 2 and OH), 4.4 (m, 1H) 1-3 (aliphatic protons).
EXAMPLE 6C
Acylation of the product obtained in Example 6B with a 100% molar excess of 2-furoyl chloride in dichloromethane in the presence of a molar excess of triethylamine at 0° C. for 1.5 hours, followed by evaporation of solvent, dissolving the residue in ethylacetate, washing with water and aqueous sodium bicarbonate solution, drying and evaporation to dryness afforded a crude product. This was stirred at room temperature in methanol containing 1.5 equivalents (based on starting hydroxyamine) of 1N sodium hydroxide for 24 hours. The solvent was evaporated, the residue partitioned between ethyl acetate and water, the organic layer dried (MgSO 4 ) and solvent evaporated to provide 4-[2-(2-furoyl)ethyl]-5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran as an oil in 66% yield; Rf 0.58; Mass spectrum (m/e) parent peak 487.
In like manner the following 4-acylaminoethyl analogs were obtained as oils.
______________________________________ ##STR35##R.sub.14 R.sub.f Comment______________________________________CH.sub.3 * 0.43 55% yield, .sup.1 HNMR(CDCl.sub.3), ppm(delta): 7.0 (5Haromatic), 6.0 (2Haromatic), 4.2 (1H).CF* -- 28% yield, .sup.1 HNMR(CDCl.sub.3), ppm(delta): 7.2 (6H, 5-aromatic plus OH), 6.5 (broad, NH), 6.0 (2Haromatic).C.sub.6 H.sub.5 * 0.63 63% yield, Mass spectrum (m/e): 477 (parent).OC.sub.2 H.sub.5 0.77 78% yield, Mass spectrum (m/e): 455 (M.sup.+), 404 (MHOC.sub.2 H.sub.5).______________________________________ *Prepared from acid anhydride rather than acid chloride and employed pyridine in place of triethylamine.
EXAMPLE 7
dl-5-Hydroxy-4-(2-hydroxy-2-methylpropyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A solution of 344 mg (1 mmole) of 2,2-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran-5-one in 10 ml of ethyl ether was cooled in an ice bath for 15 minutes. To the cold solution was added slowly by injection 0.80 ml of 2.9 molar methylmagnesium iodide in ethyl ether. The resulting mixture was allowed to warm to room temperature and stirred for 14 hours. Crystalline ammonium chloride (ca. 100 mg) was added, the mixture stirred for 20 minutes, water (5 ml) added and the layers separated. The aqueous layer was extracted with 10 ml of ether and the combined ether layers were washed with 30 ml of saturated sodium bicarbonate solution, 30 ml of brine and 30 ml of water. The washed organic layer was dried (MgSO 4 ) and solvent evaporated in vacuo to afford 348 mg of an oil which crystallized upon standing. Recrystallization from pentane afforded 250 mg (66.5%) of purified product, m.p. 101°-103° C.
1 H-NMR(CDCl 3 )ppm(delta): 0.83 (s, 3H), 1.0-1.5 (m, 28H), 1.53-2.5 (m, 5H), 2.9-3.2(m, 1H), 6.3 (d, 1H), 6.4 (d, 1H), 7.8-8.6 (m, 1H); Infrared spectrum (KBr), cm -1 : 3333(OH), 2899(CH); Mass spectrum (m/e): M + 376, base peak 274.
Analysis: Calc'd for C 24 H 40 O 3 : C, 76.55; H, 10.71. Found: C, 76.61; H, 10.45.
EXAMPLE 7A
By the procedure of Example 7, but employing one of the esters, lactones or mixtures thereof provided in Examples 4 and 4A as starting material and use of the appropriate Grignard reagent of formula R 8 MgHal where Hal is Cl, Br or I in place of methylmagnesium iodide, the following compounds are obtained in like manner.
______________________________________ ##STR36##R.sub.2 R.sub.3 R.sub.8 R.sub.9______________________________________H H C.sub.6 H.sub.5 C.sub.6 H.sub.5H H C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2H H -n-C.sub.4 H.sub.9 -n-C.sub.4 H.sub.9H CH.sub.3 CH.sub.3 CH.sub.3H CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3CH.sub.3 CH.sub.3 -n-C.sub.3 H.sub.7 -n-C.sub.3 H.sub.7CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 C.sub.6 H.sub.5CH.sub.3 C.sub.2 H.sub.5 CH.sub.2 CH(CH.sub.3).sub.2 CH.sub.2 CH(CH.sub.3).sub.2CH.sub.3 C.sub.2 H.sub.5 C.sub.6 H.sub. 5 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2H C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5H C.sub.2 H.sub.5 C.sub.6 H.sub.5 C.sub.6 H.sub.5H C.sub.2 H.sub.5 CH.sub.3 CH.sub.3H C.sub.2 H.sub.5 CH(CH.sub.3).sub.2 CH(CH.sub.3).sub.2______________________________________
EXAMPLE 8
dl-5-Hydroxy-4-(2-hydroxypropyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
The hemiacetal obtained in Example 6, dl-5-hydroxy-2,2-dimethyl-8-(1,1dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran, (491 mg, 1.42 mmole) was dissolved in 10 ml of diethyl ether and cooled in an ice bath for 15 minutes. From a syringe 1.58 ml of 2.9M methylmagnesium iodide was added slowly with stirring. The reaction mixture was allowed to warm to room temperature and stirred for three hours. Ammonium chloride cyrstals (ca. 100 mg) was added to consume the unreacted Grignard reagent and the mixture stirred for 20 minutes. Ethyl acetate, 75 ml, and water, 50 ml, were added, the mixture stirred for a few minutes, and the layers separated. The aqueous layer was extracted with 50 ml of ethyl acetate and the combined organic layers washed with 50 ml each of water, brine and water again. The organic layer was dried over anhydrous magnesium sulfate and solvent evaporated in vacuo to provide 525 mg of crude oil. The oil was chromatographed on a pair of 2 mm thickness silica gel plates employing an ethyl acetate/pentane (1:3 by volume) solvent system. The region with Rf 0.09-0.21 was extracted with 200 ml of ethyl acetate for 2-3 hours to afford 300 mg of product (58.3%).
1 H-NMR(CDCl 3 )ppm(delta): 0.70 (s, 3H), 0.78-1.35 (m, 25H), 1.40-1.87 (m, 4H), 2.41-2.77 (m, 1H), 2.85-3.50 (m, 1H), 6.44-6.60 (m, 2H), 7.52-8.35 (broad 1H); Infrared spectrum (film), cm -1 : 3350(OH, very broad), 2925(CH); Mass spectrum (m/e): M + 362, base peak 44.
Analysis: Calc'd for C 23 H 38 O 3 : C, 76.19; H, 10.57. Found: C, 75.97; H, 10.16.
EXAMPLE 8A
Employing the appropriate lactol provided in Example 6 as starting material in each case, the compounds of the formula shown below are obtained by the procedure of Example 8 but employing the appropriate Grignard reagent, R 8 MgHal where Hal is Cl, Br or I.
______________________________________ ##STR37##R.sub.2 R.sub.3 R.sub.8______________________________________H H C.sub.2 H.sub.5H H C.sub.6 H.sub.5 CH.sub.2H H CH(CH.sub.3)CH.sub.2 CH.sub.3H CH.sub.3 -n-C.sub.3 H.sub.7H CH.sub.3 CH(CH.sub.3).sub.2H CH.sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 -n-C.sub.4 H.sub.9CH.sub.3 CH.sub.3 CH.sub.3CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5CH.sub.3 C.sub.2 H.sub.5 C.sub.6 H.sub.5 CH.sub.2C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.2 CH(CH.sub.3).sub.2C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5H C.sub.2 H.sub.5 C.sub.6 H.sub.5H C.sub. 2 H.sub.5 -n-C.sub.4 H.sub.9H C.sub.2 H.sub.5 C.sub.2 H.sub.5H C.sub.2 H.sub.5 C.sub.6 H.sub.5 CH.sub.2______________________________________
EXAMPLE 9
5-Methoxy-2,2-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran, the 5-alpha-methoxy and 5-beta-methoxy diastereomers thereof
In a 500 ml pressure bottle was placed 346 mg (1 mmole) of dl-5-hydroxy-2,2-dimethyl-8-(1,1-dimethylheptyl)-3,3a,4,5-tetrahydro-2H-pyrano[4,3,2-de]benzopyran, 700 mg (13 mmole) of ammonium chloride, 250 ml of methanol and 350 mg of 5% palladium-on-carbon catalyst. The mixture was shaken with hydrogen at 40 psi (2.8 kg/cm 2 ) for 14 hours, filtered through anhydrous magnesium sulfate and solvent evaporated in vacuo. The residue was partitioned between 25 ml each of ethyl ether and water, the layers separated and the aqueous layer extracted with 2×25 ml of ether. The combined ether layers were dried (MgSO 4 ) and solvent evaporated in vacuo to afford 270 mg of oil which contained a mixture of diastereomeric products. The oil was purified by column chromatography on 10 g of silica gel (48-60 micron) eluting with 100 ml of pentane followed by 300 ml of 99:1 (by volume) pentane/ethyl acetate. The first product eluted was the 5-alpha-methoxy diastereomer (115 mg) followed by a mixture of diastereomers (111 mg) and the 5-beta-methoxy diastereomer (25 mg). Combined yield 251 mg (69.7%). The Rf of the 5-alpha and 5-beta isomers on silica gel TLC using ethyl acetate/pentane (3:22 by volume) were 0.71 and 0.61, respectively. Physical properties were determined for the 5-alpha-methoxy diastereomer as follows:
1 H-NMR(CDCl 3 )ppm(delta): 0.7-1.0 (m, 3H), 1.1-1.5 (m, 22H), 1.6-2.4 (m, 4H), 2.7-3.4 (m, 1H), 3.6 (s, 3H), 5.1-5.3 (m, 1H), 6.4 (s, 2H); Infrared spectrum (KBr), cm -1 : 3333(OH), 2930(CH); Mass spectrum (m/e): M + 360, base peak 329.
Analysis: Calc'd for C 23 H 36 O 3 : C, 76.62; H, 10.07. Found: C, 76.41; H, 10.09.
Physical properties of the 5-beta-methoxy diastereomer were:
1 H-NMR(CDCl 3 )ppm(delta): 0.86-1.0 (m, 3H), 1.1-1.4 (m, 22H), 1.6-2.5 (m, 4H), 2.67-3.4 (m, 1H), 3.67 (s, 3H), 5.3 (q, 1h, J=10, J=4), 6.4-6.6 (m, 2H).
When the above procedure is repeated but without the use of hydrogen, catalyst or pressure and addition of a catalytic amount of anhydrous hydrogen chloride, and the resulting mixture stirred at room temperature and pressure overnight, the same products are obtained in like manner.
EXAMPLE 9A
In a similar manner the compounds below are obtained from the appropriate alkanol, R 11 OH, and the appropriate lactone by the procedure of Example 9. ##STR38## where R 4 , R 5 , Z and W have the values assigned in Examples 1, 1A, 1B and 1C and R 2 , R 3 and R 11 are as shown below.
______________________________________R.sub.2 R.sub.3 R.sub.11______________________________________H H C.sub.2 H.sub.5H H -n-C.sub.4 H.sub.9H CH.sub.3 CH.sub.3H CH.sub.3 CH.sub.2 CH(CH.sub.3).sub.2CH.sub.3 CH.sub.3 -n-C.sub.3 H.sub.7CH.sub.3 CH.sub.3 CH.sub.3CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5CH.sub.3 C.sub.2 H.sub.5 CH(CH.sub.3).sub.2C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 -n-C.sub.4 H.sub.9H C.sub.2 H.sub.5 CH.sub.3H C.sub.2 H.sub.5 -n-C.sub.3 H.sub.7______________________________________
EXAMPLE 10
dl-5-Benzyloxy-4-cyanomethyl-4-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
n-Butyl lithium, 0.68 ml of 2.2M in hexane, (1.48 mmole) was mixed with 0.68 ml of tetrahydrofuran (THF) which had been distilled from sodium metal. The resulting solution was cooled to -78° C. with stirring and 0.077 ml (1.48 mmole) of acetonitrile added. The resulting slurry was stirred for one hour at -78° C., then a solution of 604 mg (1.48 mmole) of 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-one in 4 ml of the same THF was added dropwise to the stirred suspension by a syringe. When the addition was completed, the resulting mixture was stirred for 5 minutes, allowed to warm to room temperature, stirred 10 minutes and the reaction quenched by addition of 0.1 ml of acetic acid. The mixture was diluted with ethyl ether, washed with 2×20 ml of saturated sodium bicarbonate solution, 20 ml water, dried (MgSO 4 ) and the solvent removed in vacuo to provide 660 mg of the desired product as an oil.
1 H-NMR(CDCl 3 )ppm(delta): 0.83-1.0 (m, 3H), 1.1-1.6 (m, 22H), 2.1 (s, broad, 2H), 2.8 (d, 1H, J=15), 3.4 (d, 1H, J=15), 5.16 (s, 2H), 6.54 (s, 2H), 7.4 (s, 5H); Infrared spectrum (film) cm -1 : 2941(CH).
In the same manner dl-5-benzyloxy-4-cyanomethyl-4-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)3,4-dihydro-2H-benzopyran was obtained from the appropriate starting material by the above procedure. A quantitative yield of crude product was obtained as a yellow oil. It was used in the next step without purification.
EXAMPLE 11
dl-5-Hydroxy-4-cyanomethyl-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
A. dl-5-Benzyloxy-4-cyanomethylene-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
To a solution of 11.5 g (23.7 mmole) dl-5-benzyloxy-4-cyanomethyl-4-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran in 100 ml dry toluene was added a few grams of molecular sieves and 5 drops of methanesulfonic acid. The mixture was stirred for 16 hours at room temperature, washed with 30 ml water, 2×30 ml saturated sodium bicarbonate solution, dried (MgSO 4 ), filtered and the filtrate evaporated in vacuo to afford a yellow oil. Trituration with ethyl ether, filtration gave 2.60 g colorless solid. Evaporation of the mother liquor to half-volume and addition of petroleum ether afforded a second crop, 3.75 g. Total yield: 6.35 g (60.4%).
1 H-NMR(CDCl 3 )ppm(delta): 5.10 (s, 2H, OCH 2 C 6 H 5 ), 6.10 (m, 2H, aromatic), 6.43 (1H, NCCH═C), 7.25 (s, 5H phenyl), 7.45 (s, 5H, --CH 2 C 6 H 5 ).
B. dl-5-Benzyloxy-4-cyanomethyl-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
In a flask equipped with magnetic stirrer, thermometer and nitrogen inlet capillary, 1.0 g of the product of Part A, above, 20 ml anhydrous methanol and 2.08 g magnesium turnings were combined. Three crystals of iodine was added at ambient temperature and the mixture stirred until the temperature reached 30° C. It was then cooled to 4° C. and stirred at this temperature for 1.5 hours, then overnight at room temperature. An NMR spectrum of a sample at this time showed the reaction to be incomplete. An additional 2.0 g of magnesium turnings and 20 ml methanol were added. After adding an iodine crystal, the reaction mixture was stirred until the temperature reached 20° C. and gas evolution was well underway. After cooling to -10° C., stirring was continued at -10° to -4° C. for one hour. The cooling bath was removed, the temperature allowed to reach 40° C., then cooled to 20° C. and stirred for four hours. The reaction mixture was cooled to -4° C., 40 ml of 6N hydrochloric acid and 20 ml methanol were added over 20 minutes while maintaining the temperature below 10° C. When the bulk of the magnesium was consumed, the temperature was allowed to rise to ambient temperature and 20 ml ethyl ether added. The mixture was poured into a separatory funnel, 250 ml ether added and after shaking, the layers were separated. The aqueous phase was extracted again with 125 ml ether and the combined ether layers were washed successively with water (100 ml), saturated sodium bicarbonate solution (100 ml) and water (100 ml). The extracts were dried (MgSO 4 ) and solvent evaporated to afford 0.95 g of the product as an oil.
1 H-NMR(CDCl 3 )ppm(delta): 5.10 (s, 2H, OCH 2 C 6 H 5 ), 6.10 (m, 2H, aromatic), 7.23 (s, 5H, phenyl), 7.42 (s, 5H, OCH 2 C 6 H 5 ).
C. The product of Part B, above, 1.6 g (3.4 mmole) was dissolved in 150 ml anhydrous ethanol and 1.1 g 5% Pd/C was added. The mixture was hydrogenated at 45 psi (3.1 kg/cm 2 ) for 16 hours, filtered and the filtrate evaporated in vacuo to afford 1.0 g of an oily foam. This was taken up in 100 ml methylene chloride, 5 g of silica gel was added and the slurry evaporated. The residual solid was placed on top of a column of 100 g silica gel and eluted with 1.7 liters 4:1 hexane/ethyl ether (v/v) then with 2 liters of 3:1 hexane/ethyl ether. Like fractions were combined and evaporated to dryness in vacuo to provide 590 mg of the desired product.
1 H-NMR(CDCl 3 )ppm(delta): 5.98 (m, 2h, aromatic), 7.23 (5H, phenyl).
EXAMPLE 12
dl-5-Acetoxy-4-(2-hydroxyethyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A solution of 3.48 g (0.01 mole) dl-5-hydroxy-4-(2-hydroxyethyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran in 50 ml methylene chloride and containing 1.01 g (0.01 mole) triethylamine is cooled to 0° C. while stirring in a nitrogen atmosphere. To this is added a solution of 1.22 g (0.01 mole) 4-dimethylaminopyridine in 5 ml of methylene chloride followed by 1.02 g (0.01 mole) acetic anhydride. After stirring at 0°-5° C. for one hour, the mixture is allowed to warm to room temperature, extracted with methylene chloride and the extracts washed with sodium bicarbonate. After drying over anhydrous magnesium sulfate and evaporation of solvent, the desired product is obtained. It can be purified by column chromatography on silica gel if desired.
The dihydroxy compounds provided in Examples 5A, 7, 7A, 8 and 8A are converted to the corresponding 5-acetoxy derivatives of the following formula in like manner. ##STR39## The substituents R 2 , R 3 , R 4 , R 5 , R 8 , R 9 , Z and W are as defined in Examples 5A, 7, 7A, 8 and 8A.
Substitution of acetic anhydride by benzoic anhydride, propionic anhydride, butyric anhydride or valeryl anhydride in this procedure affords the corresponding 5-benzoyloxy, 5-propionyloxy, 5-butyryloxy and 5-valeryloxy derivatives.
EXAMPLE 13
dl-5-Hydroxy-4-(1-methyl-2-cyanoethyl)-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran
A. dl-5-Acetoxy-4-(1-methyl-2-methanesulfonyloxyethyl)-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran
To 4.11 g (0.01 mole) dl-5-acetoxy-4-(1-methyl-2-hydroxyethyl)-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran dissolved in 45 ml pyridine under a nitrogen atmosphere at 0°-5° C. is added with stirring 1.25 g (0.011 mole) methanesulfonyl chloride. The resulting mixture is stirred at 5° C. for 30 minutes, warmed to room temperature and stirred for an additional hour. The reaction mixture is concentrated in vacuo, the residue taken up in ethyl acetate, washed with water, brine and dried over anhydrous magnesium sulfate. Evaporation of solvent gives the desired mesylate of sufficient purity for use in the next step.
B. A mixture of 4.57 g (0.01 mole) of the mesylate obtained in Part A, above, 6.5 g (0.01 mole) potassium cyanide, 800 mg potassium iodide, 90 g dimethylformamide and 10 ml water is heated at 85°-95° C. for two hours. The solvent is evaporated in vacuo, the residue extracted with chloroform, the extracts washed with water, brine and dried (MgSO 4 ). Evaporation of solvent affords the desired nitrile which is purified by chromatography on a silica gel column.
In like manner the remaining dihydroxy compounds provided in Examples 5 and 5A are converted to the 5-acetoxy derivatives by the procedure of Example 12 and the 5-acetoxy derivative, in turn, converted to a nitrile of the formula shown below. ##STR40## where R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 5 and 5A.
EXAMPLE 14
dl-3-[5-Hydroxy-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran-4-yl]butyric acid
To a mixture of 125 ml of methanol and 75 ml 1N sodium hydroxide is added 3.77 g (0.01 mole) dl-5-hydroxy-4-(1-methyl-2-cyanoethyl)-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran and the resulting mixture is heated at reflux overnight. The methanol is evaporated and the residue is extracted between chloroform, backwashing with dilute sodium hydroxide solution. The aqueous alkaline layers are combined, acidified with hydrochloric acid and extracted with chloroform. The extracts are dried over anhydrous magnesium sulfate and the solvent evaporated to provide the desired product.
In like manner the remaining nitriles provided in Examples 11 and 13 are hydrolyzed to the corresponding acid of the formula ##STR41## where f is 0 or 1, R 7 is hydrogen, R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 5, 5A and 11.
Heating the above acids, dissolved in a molar excess of alkanol, R 7 OH, at 50°-110° C. for 4-24 hours in the presence of a catalytic amount of hydrogen chloride or concentrated sulfuric acid provides the corresponding esters of the above formula wherein R 7 is methyl, ethyl, n-propyl, isobutyl, n-butyl or benzyl.
Acetylation of the above 5-hydroxy-carboxylic acids and esters by the Example 12 affords the corresponding 5-acetoxy derivatives.
EXAMPLE 14A
Lithium aluminum hydride reduction of the 4-[C(R 2 R 3 )CH 2 COOR 7 ]benzopyran esters provided in Example 14 by the procedure of Example 5 affords the following primary alcohols: ##STR42## where f is 0 or 1 and R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 5, 5A and 11.
EXAMPLE 14B
Reaction of the 4-[C(R 2 R 3 )CH 2 COOR 7 ]benzopyran esters provided in Example 14 with Grignard reagents (R 8 MgCl or R 8 MgBr) by the procedure of Example 7 affords the following tertiary alcohols: ##STR43## where f is 0 or 1 and R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 5, 5A and 11 and R 8 and R 9 are as defined in Example 7A.
EXAMPLE 15
dl-4-(4-Amino-2-butyl)-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran
Under anhydrous conditions and a nitrogen atmosphere, to a solution of 190 mg (5 mmole) lithium aluminum hydride in 50 ml tetrahydrofuran at 10° C. is added dropwise a solution of 1.885 g (5 mmole) dl-5-hydroxy-4-(1-methyl-2-cyanoethyl)-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran in 25 ml of tetrahydrofuran. After the addition is complete, the mixture is stirred at room temperature for 6 hours. Ethyl acetate is added to consume the unreacted hydride. The reaction mixture is evaporated to dryness, the residue partitioned between water and methylene chloride and the organic layer dried over anhydrous magnesium sulfate. The solvent is evaporated to provide the title compound as the free base.
The hydrochloride salt of the title compound is obtained by adding an ethereal solution of hydrogen chloride to a solution of the free base in anhydrous ethanol. The precipitated salt is collected by filtration, washing with ether and air drying.
When the above procedure is repeated, but using dl-5-hydroxy-4-cyanomethyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran as starting material, the product obtained as dl-4-(2-aminoethyl)-5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl-3,4-dihydro-2H-benzopyran.
In like manner the remaining nitriles provided in Example 11 are converted to amines of the formula shown below wherein f is zero. Similarly, the remaining compounds of Example 13 are reduced to amines of the formula below wherein f is 1. ##STR44## R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 11 and 13.
EXAMPLE 16
dl-5-Acetoxy-4-(4-acetylamino-2-butyl)-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran
To a solution of 3.81 g (0.01 mole) dl-4-(amino-2-butyl)-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran in 25 ml of chloroform and 18 ml dry pyridine at 10° C. is added 2.36 ml (0.032 mole) acetyl chloride which is dissolved in 10 ml chloroform. The resulting solution is stirred overnight at room temperature, poured onto ice/water, the organic layer separated and the aqueous phase extracted with chloroform. The combined organic layers are washed with saturated sodium bicarbonate, water, brine and dried over anhydrous magnesium sulfate. Evaporation of solvent affords the title compound which is purified, if desired, by column chromatography on silica gel.
When the above procedure is repeated, but using dl-4-(2-aminoethyl)-5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran, the product obtained is dl-5-acetoxy-4-(2-acetylaminoethyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran.
When acetyl chloride is replaced by an equimolar amount of benzoyl chloride, propionyl chloride, isobutyryl chloride, valeryl chloride, 2-phenylacetyl bromide, trifluoroacetic anhydride or 2-furoyl chloride, the corresponding amido ester compounds are obtained.
In like manner the remaining compounds provided in Example 15 are converted to compounds of the formula shown below. ##STR45## wherein f is zero or one, R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 1A, 1B, 1C and 4A, and R 14 is as shown below.
______________________________________ R.sub.14______________________________________ CH.sub.3 C.sub.2 H.sub.5 .sub.-i-C.sub.4 H.sub.9 -n-C.sub.5 H.sub.11 CF.sub.3 C.sub.6 H.sub.5 CH.sub.2 2-furyl 3-thienyl 4-pyridyl 3-furyl 2-thienyl C.sub.6 H.sub.5 4-NH.sub.2 C.sub.6 H.sub.4 2-ClC.sub.6 H.sub.4 3-BrC.sub.6 H.sub.4 3-CH.sub.3 C.sub.6 H.sub.4 4-CH.sub.3 OC.sub.6 H.sub.4 4-FC.sub.6 H.sub.4______________________________________
EXAMPLE 17
dl-4-(4-Acetylamino-2-butyl)-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran
A solution of 156 mg (0.335 mmole) dl-5-acetoxy-4-(4-acetylamino-2-butyl)-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran and 46 mg (0.333 mmole) potassium carbonate in 40 ml of methanol is stirred at room temperature for two hours. After neutralization with acetic acid the mixture is evaporated in vacuo and the residue taken up in ethyl ether. The ether solution is washed successively with water, saturated sodium bicarbonate, brine and dried over magnesium sulfate. Evaporation of ether affords the title amide.
In like manner the remaining 5-acyloxy amides provided in Example 16 are hydrolyzed to the corresponding 5-hydroxy amides of the formula ##STR46## where f, R 2 , R 3 , R 4 , R 5 , R 14 , Z and W are as defined in Example 16.
EXAMPLE 18
dl-4-(4-Acetylamino-2-butyl)-2-methyl-7-(5-phenyl-2-pentyl)-5-(4-N-piperidylbutyryloxy)-3,4-dihydro-2H-benzopyran hydrochloride
To a solution of 1.06 g (2.5 mmole) dl-4-(4-acetylamino-2-butyl)-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran in 20 ml methylene chloride is added 0.52 g (2.5 mmole) 4-N-piperidylbutyric acid hydrochloride, 0.573 g (2.78 mmole) dicyclohexylcarbodiimide and the mixture stirred at room temperature for six hours. It is cooled at 0° C. overnight, filtered, the filtrate evaporated and the residue triturated with ethyl ether to afford the desired hydrochloride salt.
Alternatively, the above filtrate is extracted with dilute hydrochloric acid. The aqueous phase is washed with ether, then neutralized with potassium hydroxide solution and extracted with ether. Evaporation affords the free base of the title compound.
Repetition of this procedure but using the appropriate 5-hydroxy compound selected from those of Example 17 and the appropriate alkanoic acid or acid of formula R 15 R 16 N(CH 2 ) p --COOH.HCl affords the following compounds ##STR47## wherein f, R 2 , R 3 , R 4 , R 5 , R 14 , Z and W are as defined in Example 17 and R 1 is as defined below.
______________________________________ R.sub.1______________________________________ COCH.sub.2 CH.sub.3 CO(CH.sub.2).sub.2 CH.sub.3 CO(CH.sub.2).sub.3 CH.sub.3 COCH.sub.2 NH.sub.2 CO(CH.sub.2).sub.2 NH.sub.2 CO(CH.sub.2).sub.4 NH.sub.2 CO(CH.sub.2)N(CH.sub.3).sub.2 CO(CH.sub.2).sub.2 NH(C.sub.2 H.sub.5) CO(CH.sub.2).sub.4 NHCH.sub.3 CONH.sub.2 CON(C.sub.2 H.sub.5).sub.2 CON(C.sub.4 H.sub.9).sub.2 CO(CH.sub.2).sub.3 NH(C.sub.3 H.sub.7) CO(CH.sub.2).sub.2 N(C.sub.4 H.sub.9).sub.2 COCH.sub.2 --piperidino COCH.sub.2 --pyrrolo CO(CH.sub.2).sub.2 --morpholino CO(CH.sub.2).sub.2 --N--butylpiperazino CO(CH.sub.2).sub.3 --pyrrolidino CO--piperidino CO--morpholino CO--pyrrolo CO--N--(methyl)piperazino CO--C.sub.6 H.sub.5 COCH(CH.sub.3)(CH.sub.2).sub.2 --piperidino CHO______________________________________
Basic esters are obtained as their hydrochloride salts. Careful neutralization with sodium hydroxide affords the free basic esters.
EXAMPLE 19
dl-4-(4-Methanesulfonylamino-2-butyl)-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyl)-3,4-dihydro-2H-benzopyran
Sulfonylation employing the procedure of Example 16, but replacing the acetyl chloride used therein with an equimolar amount of methanesulfonyl chloride and hydrolysis of the product thus obtained by the procedure of Example 17 provides the title compound.
In like manner the remaining amino compounds provided in Example 15 are sulfonylated with acid chlorides or acid bromides of formula R 17 SO 2 Cl (or Br) to provide compounds of the formula ##STR48## where f, R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Example 15 and R 17 is methyl, ethyl, n-propyl, isopropyl, n-butyl, isoamyl, phenyl, p-tolyl or benzyl.
Esterification of the above 5-hydroxy compounds by the procedure of Example 18 affords the corresponding 5-OR 1 compounds where R 1 is as defined in Example 18.
EXAMPLE 20
dl-5-Hydroxy-4-carboxamidomethyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A solution of 3.76 g (0.01 mole) dl-5-hydroxy-4-methoxycarbonylmethyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran (or its mixture with the corresponding lactone as obtained in Example 4) in 100 ml toluene is saturated with anhydrous ammonia at 10° C. The resulting mixture is placed in a sealed tube and heated at 95°-100° C. for 6 hours. The reaction mixture is cooled in ice, the tube opened and the mixture evaporated to dryness under reduced pressure to obtain the crude title compound which is purified by chromatography on silica gel.
When the above procedure is repeated but employing methylamine, ethylamine, isopropylamine, n-butylamine, 2-ethylbutylamine aniline or benzylamine in place of ammonia and/or one of the ester compounds provided in Example 14 as starting material in place of the above methyl ester, the following amides are obtained in like manner. ##STR49## where R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 4 and 14, and f is zero or one and R 12 is methyl, ethyl, isopropyl, n-butyl, isobutyl, n-hexyl or benzyl.
Esterification of the 5-hydroxyamides, thus obtained, by the procedure of Example 18 affords the corresponding 5-OR 1 -substituted compounds wherein R 1 is as defined in Example 18.
EXAMPLE 21
dl-5-Acetoxy-4-(N,N-dimethylaminocarboxamidomethyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
To a solution of 2.01 g (5 mmole) dl-2-[5-acetoxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-yl] acetic acid in 50 ml of chloroform is added dropwise with stirring 0.83 g (7 mmole) thionyl chloride in 10 ml of the same solvent. The resulting mixture is stirred at room temperature for one hour, evaporated to dryness at reduced pressure and the residue taken up in 35 ml ethyl ether. The ethereal solution of acid chloride is added dropwise to a cold solution of 1 gram of dimethylamine in 50 ml of ethyl ether. The resulting mixture is stirred for 30 minutes at 10° C., then filtered with suction. The filtrate is washed successively with dilute hydrochloric acid, water, sodium bicarbonate, water, brine and dried over magnesium sulfate. Evaporation of solvent affords the desired amide.
Hydrolysis of the 5-acetoxy amide thus obtained by procedure of Example 17 affords the corresponding 5-hydroxyamide in like manner.
When the remaining 5-acetoxy carboxylic acids provided in Example 14 are reacted with dimethylamine or other amine of the formula R 12 R 13 NH by the above procedure, compounds of the following formula are obtained in like manner: ##STR50## where f is zero or 1, R 1 is H or acetyl, R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Example 14 and R 12 and R 13 are as defined below.
______________________________________R.sub.12 R.sub.13______________________________________CH.sub.3 CH.sub.3(C.sub.2 H.sub.5).sub.2 CHCH.sub.2 C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 .sub.-i-C.sub.3 H.sub.7 .sub.-i-C.sub.3 H.sub.7 -n-C.sub.3 H.sub.7 CH.sub.3 -n-C.sub.6 H.sub.13 -n-C.sub.4 H.sub.9 -n-C.sub.6 H.sub.13 -n-C.sub.6 H.sub.13C.sub.6 H.sub.5 HC.sub.6 H.sub.5 CH.sub.3C.sub.6 H.sub.5 C.sub.6 H.sub.5C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5 CH.sub.2C.sub.6 H.sub.5 CH.sub.2 CH.sub.3______________________________________
or alternatively, NR 12 R 13 taken together form: ##STR51##
EXAMPLE 21A
Lithium aluminum hydride reduction of the amides provided in Examples 20 and 21 by the procedure of Example 15 provides the corresponding amine of the formula below in like manner: ##STR52## where f is zero or 1, R 2 , R 3 , R 4 , R 5 , R 12 , R 13 , Z and W are as defined in Examples 20 and 21.
EXAMPLE 22
dl-5-Hydroxy-4-formylmethyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
To a solution of 80 ml 0.5M disiamylborane (40 mmole) in tetrahydrofuran under dry nitrogen is added dropwise a solution of 7.78 g (0.02 mole) N,N-dimethyl-2-[5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-yl]acetamide in 50 ml tetrahydrofuran and the resulting mixture stirred at ambient temperature for six hours. A mixture of 50 ml each of glycerine and water is added and stirring continued until gas evolution is complete. The tetrahydrofuran is evaporated in vacuo, the residue extracted with ethyl ether, the extracts washed with water, dried (MgSO 4 ) and evaporated to provide the title compound. The product is purified by chromatography on silica gel.
In like manner compounds of the following formula are obtained from the corresponding N,N-dimethylamide obtained as described in Example 21: ##STR53## where f, R 1 , R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Example 21.
EXAMPLE 23
Treatment of the aldehydes provided in Example 22 with a molar excess of Grignard reagent by the procedures of Examples 8 and 8A provides secondary alcohols of the formula below. ##STR54## wherein f is zero or 1 and R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 5, 5A and 11 and R 8 is as defined in Example 8A.
Alternatively, the starting aldehyde is converted to its 5-acetoxy derivative prior to reaction with the Grignard reagent as described above.
EXAMPLE 24
dl-5-Hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-4-(2-oxopropyl)-3,4-dihydro-2H-benzopyran
A solution of 5.0 g (0.02 mole) chromic anhydride in 5.0 ml water is added with stirring and ice cooling to 50 ml pyridine. To this is added at 10° C. 4.04 g (0.01 mole) dl-5-acetoxy-4-(2-hydroxypropyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran and the resulting mixture stirred at room temperature for three hours. The reaction mixture is poured into water, made alkaline (pH 8.5-9.0) with sodium carbonate, stirred for 20 minutes then acidified with dilute hydrochloric acid and extracted with methylene chloride. The organic layer is washed with sodium bicarbonate solution, water, brine, dried over magnesium sulfate and the solvent evaporated, the last of the solvent being removed in vacuo. The residue is purified by column chromatography on silica gel to obtain the desired ketone.
In like manner the secondary alcohols provided in Examples 8A and 23 are converted to their 5-acetoxy derivatives by the procedure of Example 12 and oxidized by the above method to provide compounds of the formula ##STR55## wherein f is zero or 1, R 2 , R 3 , R 4 , R 5 , R 8 , Z and W are as defined in Example 23.
EXAMPLE 25
The 5-hydroxy ketones provided in Example 24 are converted to the corresponding 5-acetyl ketones by the procedure of Example 12, the products thus obtained are reacted with 3-4 moles of Grignard reagent, R 9 MgCl or R 9 MgBr, by the procedure of Example 7 to provide 5-hydroxy-tertiary alcohols of the formula ##STR56## where R 2 , R 3 , R 4 , R 5 , Z and W are as defined in Examples 5A and 11, and f, R 8 and R 9 are as defined below.
______________________________________f R.sub.8 R.sub.9______________________________________0 CH.sub.3 C.sub.2 H.sub.50 C.sub.2 H.sub.5 C.sub.6 H.sub.5 CH.sub.20 -n-C.sub.4 H.sub.9 CH.sub.30 CH.sub.2 CH(CH.sub.3).sub.2 C.sub.6 H.sub.50 -n-C.sub.4 H.sub.9 -n-C.sub.4 H.sub.91 CH.sub.3 C.sub.6 H.sub.51 -n-C.sub.3 H.sub.7 .sub.-i-C.sub.4 H.sub.91 C.sub.2 H.sub.5 C.sub.6 H.sub.51 -n-C.sub.4 H.sub.9 C.sub.6 H.sub.5 CH.sub.21 C.sub.6 H.sub.5 CH.sub.2 C.sub.6 H.sub.5______________________________________
EXAMPLE 26
dl-1-Benzyl-5-benzyloxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline
To a mixture of 0.30 mole of potassium hydride and 500 ml freshly distilled N,N-dimethylformamide (DMF) cooled to 0° C. under nitrogen and anhydrous conditions, is added dropwise a solution of 33.9 g (0.10 mole) dl-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline in 350 ml of purified DMF at 0°-10° C. When the addition is complete, the mixture is allowed to warm to room temperature and stirred for one hour. The mixture is then cooled to 0° C., a solution of 18.81 g (0.11 mole) benzylbromide in 150 ml DMF is added slowly at 0°-10° C., the resulting mixture stirred at 5° C. for 30 minutes, then allowed to warm to room temperature and stirred overnight. The reaction is quenched by cautious addition of water, diluted with five liters ethyl ether, washed with water, brine, dried over anhydrous magnesium sulfate and the solvent evaporated in vacuo to obtain the crude product. It is purified, if desired, by column chromatography on silica gel.
EXAMPLE 27
Ethyl dl-2-[1-benzyl-5-benzyloxy-4-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-1,2,3,4-tetrahydroquinolin-4-yl]-2-methylpropionate
[VI, Q 2 ═COOC 2 H 5 , R 2 , R 3 ; R 4 ═CH 3 ; R 5 ═H; M═NCH 2 C 6 H 5 ; Y 1 ═CH 2 C 6 H 5 ; ZW═OCH(CH 3 )(CH 2 ) 3 C 6 H 5 ].
A. Under a nitrogen atmosphere at -78° C. to 45.5 ml (0.10 mole) of 2.2M n-butyl lithium in hexane is added 45 ml of dry tetrahydrofuran (THF). A solution of 18.08 g (0.10 mole) dicyclohexylamine in 45 ml THF is added dropwise, followed by 11.6 g (0.01 mole) ethyl 2-methylpropionate and the resulting mixture stirred at -78° C. for 30 minutes. A solution of 51.9 g (0.10 mole) dl-1-benzyl-5-benzyloxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline in 200 ml THF is slowly added and the resulting mixture is stirred five hours at -78° C. The reaction is quenched by addition of 8 ml acetic acid, allowed to warm to room temperature and 200 ml saturated sodium bicarbonate is added followed by 200 ml ethyl ether. The layers are separated, the ether layer washed with dilute hydrochloric acid, bicarbonate solution, water and dried (MgSO 4 ). Evaporation of solvent provides the crude product which is purified by silica gel chromatography.
B. A mixture of 4.2 g (0.065 mole) activated zinc, a small crystal of iodine and 500 ml of tetrahydrofuran is stirred and heated to reflux. A solution of 18.7 g (0.036 mole) dl-1-benzyl-5-benzyloxy-2-methyl-7-(5-phenyl-2-pentyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline and 10.7 g (0.055 mole) ethyl 2-bromo-2-methylpropionate in 250 ml tetrahydrofuran is added slowly (about 30 minutes) and the resulting mixture refluxed for an additional hour. The tetrahydrofuran is removed by evaporation in vacuo, the residue partitioned between 0.1N hydrochloric acid and ethyl ether. The ether is discarded, the aqueous phase made alkaline with sodium hydroxide and extracted with ether. The ether extracts was washed with water, dried (MgSO 4 ) and evaporated to dryness to afford the desired product.
EXAMPLE 28
Ethyl dl-2-[5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-1,2,3,4-tetrahydroquinolin-4-yl]-2-methylpropionate and its corresponding lactone
[IX, Q 2 ═COOC 2 H 5 , R 2 , R 3 ; R 4 ═CH 3 ; R 5 ═H; M═NH; ZW═OCH(CH 3 )(CH 2 ) 3 C 6 H 5 ]
A mixture of 6.35 g (0.01 mole) ethyl dl-2-[1-benzyl-5-benzyloxy-4-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-1,2,3,4-tetrahydroquinolin-4-yl]-2-methylpropionate, 250 ml ethanol and 2 g 5% palladium-on-carbon is hydrogenated at 50 psi (3.52 kg/cm 2 ) overnight. The resulting mixture is filtered and the filtrate evaporated in vacuo. The residue is taken up in ethyl ether, washed with water, the water wash extracted with ether and the combined ether layers washed with saturated sodium bicarbonate, brine, and dried over magnesium sulfate. Evaporation of solvent affords a mixture of the title compounds which is separated by crystallization and the products purified by chromatography on silica gel by the procedure of Example 4.
EXAMPLE 29
When 3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-8-benzyloxy-1-tetralone (prepared as described in U.S. Pat. No. 4,188,495) is employed in place of the tetrahydroquinoline used as starting material in the procedures of Example 27A or 27B, ethyl dl-2-[8-benzyloxy-1-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-tetralin-1-yl]-2-methylpropionate is obtained in like manner. Hydrogenolysis of the product thus obtained by the method of Example 28 affords ethyl dl-2-[8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-tetralin-1-yl]-2-methylpropionate in admixture with the corresponding lactone of the formula below. ##STR57##
EXAMPLE 30
When the procedures of Examples 26-28 or Example 29 are repeated with the appropriate starting material in each case, products of the formulae below where M is NH or CH 2 , respectively, are obtained in like manner.
__________________________________________________________________________ ##STR58## ##STR59##R.sub.2 R.sub.3 R.sub.4 R.sub.5 Z W__________________________________________________________________________H H CH.sub.3 H OCH.sub.2 C(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3CH.sub.3 H CH.sub.3 H OCH.sub.2 CH(CH.sub.3)(CH.sub.2).sub.2 CH(CH.sub.3)CH.sub. 2 CH.sub.3C.sub.2 H.sub.5 H CH.sub.3 H OCH(CH.sub.3)CH.sub.2 CH(CH.sub.3)CH.sub.2 CH(CH.sub.3) CH.sub.3CH.sub.3 CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.2 C(CH.sub.3).sub.2 CH.sub.3CH.sub.3 C.sub.2 H.sub.5 C.sub. 2 H.sub.5 H OCH.sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH.sub.3 H OCH.sub.2 CH.sub.2 CH(CH.sub.3) C.sub.6 H.sub.5C.sub.2 H.sub.5 H CH.sub.3 H O(CH.sub.2).sub.7 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 H H OCH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C.sub.2 H.sub.5 H O(CH.sub.2).sub.9 C.sub.6 H.sub.5H H H H O(CH.sub.2).sub.9 CH.sub.3H H H H OCH(CH.sub.3)CH.sub.2 2-pyridylCH.sub.3 H C.sub.2 H.sub.5 H O(CH.sub.2).sub.2 2-pyridylC.sub.2 H.sub.5 H C.sub.2 H.sub.5 H O(CH.sub.2).sub.4 2-pyridylC.sub.2 H.sub.5 C.sub.2 H.sub.5 H H O(CH.sub.2).sub.3 2-piperidylCH.sub.3 CH.sub.3 CH.sub.3 H O(CH.sub.2).sub.3 4-piperidylH H H CH.sub.3 O(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4H H H H O(CH.sub.2).sub.3 4-ClC.sub.6 H.sub.4CH.sub.3 H H H OCH(CH.sub.3)(CH.sub.2).sub.2 2-pyridylCH.sub.3 H H CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 4-pyridylC.sub.2 H.sub.5 H H C.sub.2 H.sub.5 OCH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 4-piperidylC.sub.2 H.sub.5 H H CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.2 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 H CH.sub.3 O 4-FC.sub.6 H.sub.4CH.sub.3 H H C.sub.2 H.sub.5 O 4-ClC.sub.6 H.sub.4CH.sub.3 H H CH.sub.3 O C.sub.3 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH.sub.3 O C.sub.4 H.sub.7C.sub.2 H.sub.5 C.sub.2 H.sub.5 H C.sub.2 H.sub.5 O C.sub.5 H.sub.9H H H CH.sub.3 O C.sub.6 H.sub.11H H H CH.sub.3 O C.sub.7 H.sub.13H H H CH.sub.3 O 2-(C.sub.6 H.sub.5)C.sub.3 H.sub.4H H H CH.sub.3 O 1-(C.sub.6 H.sub.5)C.sub.4 H.sub.6H H H CH.sub.3 O 2-(C.sub.6 H.sub.5)C.sub.5 H.sub.8CH.sub.3 H H CH.sub.3 O 4-(C.sub.6 H.sub.5)C.sub.6 H.sub.10CH.sub.3 H H CH.sub.3 O 2-(C.sub.6 H.sub.5)C.sub.6 H.sub.10CH.sub.3 H H CH.sub.3 O 3-(C.sub.6 H.sub.5)C.sub.7 H.sub.12CH.sub.3 H H CH.sub.3 OCH.sub.2 CH.sub.3CH.sub.3 H H CH.sub.3 O(CH.sub.2).sub.3 CH.sub.3CH.sub.3 H H CH.sub.3 O(CH.sub.2).sub.6 CH.sub.3CH.sub.3 H H CH.sub.3 O(CH.sub.2).sub.9 CH.sub.3CH.sub.3 H H C.sub.2 H.sub.5 O(CH.sub.2).sub.3 CH.sub.3CH.sub.3 H H CH.sub.3 OC(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH.sub.3 H H CH.sub.3 OCH(CH.sub.3)CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3CH.sub.3 H CH.sub.3 CH.sub.3 O(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 H CH.sub.3 CH.sub.3 OC(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 H CH.sub.3 CH.sub.3 O C.sub.6 H.sub.5H H H H O(CH.sub.2).sub.9 HH H CH.sub.2 C.sub.6 H.sub.5 CH.sub.3 OCH(CH.sub.3)(CH.sub.2).sub.3 3-pyridylCH.sub.3 CH.sub.3 -n-C.sub.4 H.sub.9 CH.sub.3 O C.sub.6 H.sub.5CH.sub.3 H (CH.sub.2).sub.3 C.sub.6 H.sub.5 CH.sub.3 O 4-FC.sub.6 H.sub.4CH.sub. 3 H CH.sub.3 CH.sub.3 OC(CH.sub.3).sub.2 (CH.sub.2).sub.5 CH.sub.3CH.sub.3 CH.sub.3 H H CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH.sub.3 H CH(CH.sub.3)(CH.sub.2).sub.4 C.sub.6 H.sub.5H H H H (CH.sub.2).sub.3 C.sub.6 H.sub.5H H C.sub.2 H.sub.5 H (CH.sub.2).sub.4 C.sub.6 H.sub.5H H CH.sub.3 H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.3 C.sub.6 H.sub.5H H H H C(CH.sub.3).sub.2 C.sub.6 H.sub.5H H CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.3 C.sub.6 H.sub.5H H CH.sub.3 H (CH.sub.2).sub.8 C.sub.6 H.sub.5H H H H CH(CH.sub.3)(CH.sub.2).sub.7 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 H H CH.sub.2 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 H H CH(CH.sub.3)(CH.sub.2).sub.3 4-FC.sub.6 H.sub.4C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH(CH.sub.3)CH.sub.2 4-FC.sub.6 H.sub.4C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH(CH.sub.3 )(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4CH.sub.3 CH.sub.3 H H (CH.sub.2).sub.3 C.sub.5 H.sub.9CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5H H H H CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.5 H.sub.9H H H H CH(CH.sub.3)CH.sub.2 C.sub.3 H.sub.5H H H H OH(CH.sub.3)CH(CH.sub.3) C.sub.6 H.sub.11CH.sub.3 H CH.sub.3 H CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11CH.sub.3 CH.sub.3 H H (CH.sub.2).sub.8 C.sub.6 H.sub.11CH.sub.3 CH.sub.3 H H (CH.sub.2).sub.4 2-pyridylCH.sub.3 H CH.sub.3 H CH.sub.2 CH(CH.sub.3)CH.sub.2 4-pyridylC.sub.2 H.sub.5 H C.sub.2 H.sub.5 H CH(CH.sub.3)(CH.sub.2).sub.2 3-pyridylC.sub.2 H.sub.5 H CH.sub.3 H CH(CH.sub.3)CH(C.sub.2 H.sub.5)CH.sub.2 4-pyridylH H H H CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylCH.sub.3 H CH.sub.3 H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 2-piperidylCH.sub.3 H CH.sub.3 H CH(CH.sub.3)(CH.sub.2).sub.2 C.sub.7 H.sub.13H H H H CH(CH.sub.3 )(CH.sub.2).sub.2 C.sub.7 H.sub.13CH.sub.3 H CH.sub.3 H CH(CH.sub.3)CH.sub.2 O(CH.sub.2).sub.2 C.sub.6 H.sub.5H H H H (CH.sub.2).sub.4 CH.sub.3H H CH.sub.3 H CH(CH.sub.3)CH(CH.sub.3)(C.sub.2 H.sub.5) HH H H H CH.sub.2 HH H CH.sub.3 H CH.sub.2 CH.sub.3H H H H (CH.sub.2).sub.6 CH.sub.3CH.sub.3 H CH.sub.3 H (CH.sub.2).sub.3 HCH.sub.3 CH.sub.3 H H CH(CH.sub.3) C.sub.6 H.sub.11C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 H CH(CH.sub.3)(CH.sub.2).sub.4 CH.sub.3H H H H (CH.sub.2).sub.3 O C.sub.6 H.sub.5H H CH.sub.3 H (CH.sub.2).sub.3 O 4-FC.sub.6 H.sub.4CH.sub.3 CH.sub.3 H H (CH.sub.2).sub.3 O CH.sub.3H H CH.sub.3 H (CH.sub.2).sub.2 O 4-(4-FC.sub.6 H.sub.4)C.sub.6 H.sub.10H H C.sub.2 H.sub.5 H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 4-ClC.sub.6 H.sub.4H H H H (CH.sub.2).sub.3 O(CH.sub.2).sub.2 C.sub.6 H.sub.5H H CH.sub. 3 H (CH.sub.2).sub.3 OCH(CH.sub.3) 4-piperidylCH.sub.3 H CH.sub.3 H (CH.sub.2).sub.3 OCH(CH.sub.3)(CH.sub.2).sub.2 C.sub.6 H.sub.5H H H H (CH.sub.2).sub.3 OCH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3H H H H CH(CH.sub.3)(CH.sub.2).sub.2 O C.sub.6 H.sub.5H H CH.sub.3 H CH(CH.sub.3)(CH.sub.2).sub.2 OCH.sub.2 CH.sub.3CH.sub.3 H CH.sub.3 H CH(CH.sub.3)(CH.sub.2).sub.2 O(CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 H CH.sub.3 H CH(CH.sub.3)(CH.sub.2).sub.2 OCH(CH.sub.3) C.sub.7 H.sub.13H H H H CH(CH.sub.3)(CH.sub.2).sub.2 OCH.sub.2 CH(C.sub.2 H.sub.5) CH.sub.3H H CH.sub.3 H (CH.sub.2).sub.4 O C.sub.6 H.sub.5C.sub.2 H.sub.5 H C.sub.2 H.sub.5 H (CH.sub.2).sub.4 O(CH.sub.2).sub.5 4-pyridylC.sub.2 H.sub.5 H C.sub.2 H.sub.5 H (CH.sub.2).sub.4 OCH.sub.2 4-FC.sub.6 H.sub.4H H H H CH(CH.sub.3)(CH.sub.2).sub.3 O 2-(4-FC.sub.6 H.sub.4)C.sub.5 H.sub.8H H CH.sub.3 H CH(CH.sub.3 )(CH.sub.2).sub.3 O(CH.sub.2).sub.2 C.sub.6 H.sub.5CH.sub.3 H H H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 O(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.7 H.sub.13H H CH.sub.3 H CH(CH.sub.3)OCH.sub.2 C.sub.5 H.sub.9H H CH.sub.3 H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 O C.sub.3 H.sub.9H H H H CH(C.sub.2 H.sub.5)(CH.sub.2).sub.2 O 2-(4-FC.sub.6 H.sub.4)C.sub.7 H.sub.12H H H H CH(CH.sub.3)CH.sub.2 O(CH.sub.2).sub.6 CH.sub.3H H CH.sub.3 H CH(CH.sub.3)CH.sub.2 O(CH.sub.2).sub.6 C.sub.6 H.sub.5H H H H CH(CH.sub.3)CH.sub.2 OCH.sub.2 (CH.sub.3)CH.sub.2 C.sub.6 H.sub.5H H CH.sub.3 H CH(CH.sub.3)CH.sub.2 OCH.sub.2 4-FC.sub.6 H.sub.4H H CH.sub.3 H CH(CH.sub.3)CH.sub.2 O(CH.sub.2).sub.2 4-pyridylH H H H CH(CH.sub.3)CH.sub.2 OCH(CH.sub.3) CH.sub.3C.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5 H CH.sub.2 CH(CH.sub.3)OCH.sub.2 CH.sub.3C.sub.2 H.sub.5 CH.sub.3 CH.sub.3 H CH.sub.2 CH(CH.sub.3)O(CH.sub.2 ).sub.6 CH.sub.3CH.sub.3 CH.sub.3 CH.sub.3 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 H C(CH.sub.3).sub.2 (CH.sub.2).sub.6 HCH.sub.3 CH.sub.3 C.sub.2 H.sub.5 C.sub.2 H.sub.5 CH(CH.sub.3)(CH.sub.2).sub.3 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 C.sub.6 H.sub.5 CH.sub.2 H (CH.sub.2).sub.3 C.sub.6 H.sub.5H H -n-C.sub.4 H.sub.9 H (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 C.sub.2 H.sub.5 CH.sub.3 C.sub.2 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5CH.sub.3 C.sub.2 H.sub.5 C.sub.6 H.sub.5 (CH.sub.2).sub.4 H (CH.sub.2).sub.2 CH(C.sub.2 H.sub.5) C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 (CH.sub.2).sub.8 C.sub.6 H.sub.5CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3)(CH.sub.2).sub.7 C.sub.6 H.sub.5H H -n-C.sub.4 H.sub.9 H CH.sub.2 C.sub.6 H.sub.5CH.sub.3 H C.sub.6 H.sub.5 (CH.sub.2).sub.2 H CH(CH.sub.3 )(CH.sub.2).sub.2 CH(CH.sub.3) C.sub.6 H.sub.5H H CH.sub.3 H CH.sub.2 C.sub.6 H.sub.5C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.6 H.sub.5 CH.sub.2 H (CH.sub.2).sub.3 C.sub.5 H.sub.9H H C.sub.6 H.sub.5 (CH.sub.2).sub.3 H CH(CH.sub.3)(CH.sub.2).sub.5 C.sub.6 H.sub.11CH.sub.3 H CH.sub.3 CH.sub.3 (CH.sub.2).sub.9 C.sub.6 H.sub.11H H .sub.-i-C.sub.3 H.sub.7 H CH(CH.sub.3)(CH.sub.2).sub.2 4-piperidylC.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C.sub.2 H.sub.5 C(CH.sub.3).sub.2 (CH.sub.2).sub.6 H__________________________________________________________________________
EXAMPLE 30A
When the procedure of Example 27 is repeated but starting with a corresponding 4-oxoquinoline compound in which the N-CH 2 C 6 H 5 group is replaced with NR 6 , where R 6 is as defined below, and the products thus obtained hydrogenated by the procedure of Example 28, compounds of the following formulae are obtained in like manner. The requisite starting materials are provided in U.S. Pat. No. 4,260,764. ##STR60## where R 2 -R 5 , Z and W are as defined in Example 30.
______________________________________ R.sub.6______________________________________ CH.sub.3 C.sub.2 H.sub.5 -n-C.sub.4 H.sub.9 (CH.sub.3).sub.2 CH(CH.sub.2).sub.2 -n-C.sub.6 H.sub.13 (CH.sub.3).sub.2 CH CH.sub.2 CO.sub.2 CH.sub.3 CH.sub.2 CO.sub.2 CH.sub.2 CH(CH.sub.3).sub.2 CO.sub.2 C.sub.2 H.sub.5 CH.sub.2 CH.sub.2 CO.sub.2 C.sub.2 H.sub.5 (CH.sub.2).sub.3 CO.sub.2 CH.sub.3 (CH.sub.2).sub.4 CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 CHO CH.sub.3 CO CH.sub.3 CH.sub.2 CO (CH.sub.3).sub.2 CHCO CH.sub.3 (CH.sub.2).sub.3 CO (CH.sub.2).sub.2 C.sub.6 H.sub.5 (CH.sub.2).sub.3 C.sub.6 H.sub.5 (CH.sub.2).sub.4 C.sub.6 H.sub.5 C.sub.6 H.sub.5 CO C.sub.6 H.sub.5 (CH.sub.2).sub.2 CO C.sub.6 H.sub.5 (CH.sub.2).sub.3 CO CO.sub.2 CH.sub.3 CO.sub.2 (CH.sub.2).sub.3 CH.sub.3 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.3 CH.sub.2 CH(CH.sub.3)(CH.sub.2).sub.2 CH.sub.3 (CH.sub.2).sub.2 CO______________________________________
EXAMPLE 31
dl-5-Hydroxy-4-(3-hydroxy-2-methyl-2-propyl)-2-methyl-7-(5-phenyl-2-pentyloxy)-1,2,3,4-tetrahydroquinoline
To a mixture of 418 mg (0.011 mole) lithium aluminum hydride and 200 ml dry ethyl ether under nitrogen, is added dropwise with stirring at 5°-10° C., a solution of 4.39 g (0.01 mole) ethyl dl-2-[5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-1,2,3,4-tetrahydroquinoline-4-yl]-2-methylpropionate in 50 ml dry ethyl ether. The mixture is then allowed to warm to room temperature and stirred overnight. The reaction is quenched by cautious addition of ethyl acetate, the mixture washed with water, brine and dried over anhydrous magnesium sulfate. Evaporation of solvent affords the crude product which may be purified, if desired, by column chromatography on silica gel.
When the corresponding lactone: dl-3,3,5-trimethyl-8-(5-phenyl-2-pentyloxy)-2,3,3a,4,5,6-hexahydropyrano[4,3,2-de]quinoline or its mixtures with the above ester are employed as starting material in the above procedure, the title compound is obtained in like manner.
In a similar manner the compounds provided in Examples 29 and 30 are reduced by the above method to obtain compounds of the formula ##STR61## where R 2 , R 3 , R 4 , R 5 , M, Z and W are as defined in Examples 29 and 30.
Similarly, the compounds provided in Example 30A wherein R 6 is alkyl or aralkyl as defined therein provide the corresponding compounds of the above formula wherein M is NR 6 and R 6 is said alkyl or aralkyl.
EXAMPLE 32
Reduction of the lactones prepared in Examples 28-30 and by the procedure of Example 6 provides the corresponding lactols of the formula below ##STR62## where R 2 , R 3 , R 4 , R 5 , M, Z and W are as defined for the lactone starting materials. Similarly, the lactones provided in Example 30A wherein R 6 is alkyl or aralkyl afford the corresponding lactols of the above formula where M is NR 6 and R 6 is said alkyl or aralkyl.
EXAMPLE 33
Reactions of the lactones or esters provided in Examples 28-30, or those of Example 30A wherein R 6 is alkyl or aralkyl, with a Grignard reagent R 8 MgX where X is Cl, Br or I, by the procedure of Example 7 affords the corresponding tertiary alcohols of the formula ##STR63## where R 2 , R 3 , R 4 , R 5 , M, Z and W are as defined in Examples 28-31; R 8 and R 9 are the same and are as defined in Example 7A.
EXAMPLE 34
Treatment of the lactols provided in Example 32 with Grignard reagents, R 8 MgX (X=Cl, Br or I) by the procedure of Examples 8 and 8A affords the corresponding secondary alcohols of the formula ##STR64## where R 2 , R 3 , R 4 , R 5 , M, Z and W are as defined in Example 32 and R 8 is as defined in Example 8A.
EXAMPLE 35
The following compounds are obtained by employing the lactols provided in Example 32 in the procedures of Examples 9 and 9A ##STR65## where R 2 , R 3 , R 4 , R 5 , M, Z and W are as defined in Example 32 and R 11 is as defined in Example 9A.
EXAMPLE 36
By employing the appropriate 1-benzyl-5-benzyloxy-2,2-(R 4 , R 5 )-7-(ZW)-4-oxo-tetrahydroquinoline or 8-benzyloxy-3,3-(R 4 , R 5 )-6-(ZW)-1-tetralone as starting material and either a lithio derivative, LiC(R 2 R 3 )CN, in the procedure of Example 27A, or a bromoacetonitrile, BrC(R 2 R 3 )CN in the Reformatsky reaction as described in Example 27B and reduction of the resulting product by the procedure of Example 28, the following nitriles are obtained ##STR66## where R 2 , R 3 , R 4 , R 5 , M, Z and W are as defined in Examples 28-30.
EXAMPLE 37
The dihyroxy compounds obtained in Example 31 are monoacetylated by the method of Example 12, the resulting acetoxy compounds are then reacted by the procedure of Example 13 to provide the corresponding nitriles of the formula below ##STR67## where R 2 , R 3 , R 4 , R 5 , M, Z and W are as defined in Examples 28-30.
EXAMPLE 38
The cyano compounds provided in Example 36 and 37 are hydrolyzed by the method of Example 14 to provide carboxylic acids of the formula below where R 7 is hydrogen ##STR68## f is 0 or 1 and R 2 -R 5 , M, Z and W are as defined in Examples 28-30. The acids in turn are esterified to provide the above compounds where R 7 is C 1 -C 4 alkyl or benzyl also as described in Example 14.
EXAMPLE 39
Lithium aluminum hydride reduction of the esters provided in Example 38 by the method of Example 5 affords primary alcohols of the formula ##STR69## where f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 40
Lithium aluminum hydride reduction of the nitriles provided in Example 36 and 37 by the method of Example 15 provides primary amines of the formula below ##STR70## where f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 41
The primary amines provided in Example 40 are acylated by the method of Example 16 to provide the corresponding amino esters of the formula below by the procedure of Example 16. ##STR71## where R 14 is as defined in Example 16 and f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 42
In similar manner compounds of the formula below are obtained from the above amido esters by the procedure of Example 17. ##STR72##
EXAMPLE 43
When the procedure of Example 18 is carried out starting with the hydroxy amides provided in Example 42, the following compounds are obtained in like manner. ##STR73## where R 1 is as defined in Example 18 and f, R 2 -R 5 , R 14 , M, Z and W are as defined in Example 41.
EXAMPLE 44
Sulfonylation of the primary amines provided in Example 40 by the method of Example 19 provides compounds of the formula below ##STR74## where R 17 is as defined in Example 19 and f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 45
Reaction of the esters or lactones provided in Examples 28-30 with ammonia or an amine of formula R 12 NH 2 by the procedure of Example 20 similarly provides compounds of the formula ##STR75## where R 12 is as defined in Example 20 and f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 46
Acetylation of the hydroxy carboxylic acids provided in Example 38 by the procedure of Example 12, conversion of the resulting acetoxy carboxylic acid to the acid chloride and subsequent reaction with amine of the formula R 12 R 13 NH by the method of Example 21 affords compounds of the formula ##STR76## where R 1 , R 12 and R 13 are as defined in Example 21 and f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 47
Reaction of the N,N-dimethylamides provided in Example 46 with disiamylborane in tetrahydrofuran under the anhydrous conditions described in Example 22 provides the corresponding aldehydes of the formula ##STR77## where f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 48
Treatment of the above aldehydes with a molar excess of Grignard reagent, R 8 MgBr or R 8 MgCl, by the procedures of Examples 8 and 8A provides secondary alcohols of the formula ##STR78## where R 8 is as defined in Example 8A and f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 49
Oxidation of the secondary alcohols obtained in Example 48 with chromic anhydride in pyridine by the method of Example 24 provides the corresponding ketones of the formula ##STR79##
EXAMPLE 50
The ketones provided above are reacted with molar excess of Grignard reagent by the procedure of Example 25 to provide tertiary alcohols of the formula ##STR80## where R 8 and R 9 are as defined in Example 25 and f, R 2 -R 5 , M, Z and W are as defined in Example 38.
EXAMPLE 51
dl-3-(2-Carbonyloxymethyl)ethyl-5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-4-one
To 30.1 g (78 mmole) dl-5-hydroxy-3-hydroxymethylene-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-4-one was added 84 ml triethylamine and 210 ml (2.34 mole) methyl acrylate and the mixture was stirred at room temperature for two days. Additional methyl acrylate (210 ml) and triethylamine (30 ml) was added and stirring continued for two more days. The reaction mixture was concentrated in vacuo to obtain a residual oil which was chromatographed on a silica gel column taking 50 ml fractions. Twenty fractions were collected eluting with 4:1 (v/v) methylene chloride/hexane, elution was continued with methylene chloride for an additional 27 fractions, 9:1 (v/v) methylene chloride ethyl acetate for 11 fractions and ethyl acetate for 7 fractions. Fractions 18-50, containing the 3-formyl derivative of the desired product as determined by mass spectroscopy, were combined and evaporated to provide 23.0 g as an oil.
Fractions 51-58 were combined and evaporated to obtain 8.44 g of impure 3-formyl derivative which was purified further by chromatography on silica gel eluting with 7:3 (v/v) methylene chloride hexane (16 fractions), chloroform (20 fractions), and ethyl acetate (3 fractions). Fractions 10-25 were combined and evaporated to provide an additional 6.75 g of 3-formyl derivative.
The combined 3-formyl derivatives, 29.75 g, were dissolved in 200 ml of methanol, 3 ml of triethylamine was added and the mixture stirred for one hour at room temperature. The solution was evaporated to dryness, taken up in ethyl ether, washed with water, brine, dried over anhydrous magnesium sulfate and the ether evaporated to provide 27.8 g of the desired formylated product. 1 H-NMR(CDCl 3 )ppm(delta): 1.4 (d, 3H), 3.55 (s, 3H), 4.3 (m, broad, 1H), 5.85 (m, 2H), 7.08 (s, 5H), 11.2 (s, broad, 1H).
EXAMPLE 52
A. Repeating the procedure of Example 51 but employing either an analogous tetralone or N-protected tetrahydroquinoline, specifically 2-hydroxymethylene-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-8-hydroxy-1-tetralone or 1-formyl-5-hydroxy-3-hydroxymethylene-2-methyl-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline, provides analogous compounds. The former starting material, which is provided in U.S. Pat. No. 4,188,495, affords 2-(2-carbonyloxymethyl)ethyl-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-8-hydroxy-1-tetralone. The latter starting material, which is provided in U.S. Pat. No. 4,228,169, affords 3-(2-carbonyloxymethyl)-1-formyl-5-hydroxy-2-methyl-7-(2-heptyloxy)-4-oxo-1,2,3,4-tetrahydroquinoline.
In like manner compounds of the formula below are obtained from the appropriate starting materials. ##STR81## where R 4 , R 5 , Z and W are as defined in Examples 1A, 1B, 1C and M 1 is O, CH 2 or NCHO.
B. Employing the procedure of Example 51 with the appropriate starting alpha-hydroxymethylene-3,4-dihydrobenzopyran-4-one, alpha-hydroxy-methylene-1-tetralone or alpha-hydroxymethylene-1-formyl-4-oxo-1,2,3,4-tetrahydroquinoline and the appropriate acrylate, R 2 R 3 C═CH--Q, the following compounds are obtained ##STR82## where R 4 , R 5 , Z and W are as defined in Examples 1A, 1B and 1C, M 1 is O, CH 2 or NCHO and R 2 , R 3 and Q are as defined below.
______________________________________R.sub.2 R.sub.3 Q______________________________________H H CNCH.sub.3 H COOC.sub.2 H.sub.5C.sub.2 H.sub.5 H COOCH.sub.2 CH.sub.2 CH.sub.3CH.sub.3 CH.sub.3 COO(CH.sub.2).sub.3 CH.sub.3C.sub.2 H.sub.5 C.sub.2 H.sub.5 COOCH.sub.3______________________________________
EXAMPLE 53
dl-3-[5-Hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-4-one-3yl]propionic acid
To a solution of 27.8 g (0.057 mole) dl-3-(2-carbonyloxymethyl)ethyl-5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-4-one in 200 ml of methanol was added 50 ml of 5N sodium hydroxide solution and the mixture stirred at room temperature for 30 minutes. The mixture was evaporated, the residue taken up in water, washed with ether and the aqueous phase acidified (pH 4) with 6N hydrochloric acid. The product was extracted with ether, the extracts dried (MgSO 4 ) and evaporated to provide 26.1 g of crude product. The crude material was purified by chromatography on silica gel (230 g) eluting with 1:1 (v/v) hexane/ethyl ether to afford 23.9 g of purified product.
1 H-NMR(CDCl 3 )ppm(delta): 4.40 (m, 1H), 5.95 (m, 2H), 7.20 (s, 5H), 10.10 (s, 1H), 11.80 (s, 1H). Mass spectrum (m/e): 426 (M + ), 280 (M-146).
EXAMPLE 54
Employing the carboxylate esters provided in Example 52 as starting material in the procedure of Example 53, the compounds of the formula below are obtained in like manner. ##STR83## where R 2 -R 5 , Z and W are as defined in Example 52 and M is O, CH 2 or NH.
For starting materials wherein M is NCHO the methanolic sodium hydroxide reaction mixture is heated at reflux for six hours, the solvent evaporated, the residue taken up in water, washed with ether and the aqueous phase adjusted to the isoelectric point (pH 4-6) with hydrochloric acid and the precipitated product collected by filtration. If desired, it was purified by recrytallization or chromatography.
EXAMPLE 55
dl-10-Acetoxy-5,5-dimethyl-8-(5-phenyl-2-pentyloxy)-3,4-dihydro-pyrano[3,2-c]-5H-benzopyran-2-one (enol lactone)
A mixture of 1.55 g (3.3 mmole) dl-3-[5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-4-one-3-yl]propionic acid, 270 mg (3.3 mmole) sodium acetate and 20 ml acetic anhydride was heated at 100° C. under a nitrogen atmosphere for 36 hours. The mixture was concentrated to dryness in vacuo, the residue triturated with ethyl ether and filtered. The filtrate was washed with water (2×1 ml), brine (2×1 ml), dried over anhydrous magnesium sulfate and evaporated to dryness to obtain 1.6 g of crude product contaminated with acetic acid; a one gram portion was purified by chromatography on 75 g of florisil (activated magnesium silicate) eluting with 1:1 (v/v) hexane/ethyl ether to afford 1.0 g of the desired enol lactone.
1 H-NMR(CDCl 3 )ppm(delta): 1.30 (d, 3H), 1.50 (s, 6H), 2.30 (s, 3H), 6.20 (m, 2H), 7.20 (s, 5H). Mass spectrum (m/e): 450 (M + ), 435 (M-15).
EXAMPLE 56
Employing the compounds provided in Example 54 in the procedure of Example 55, the following compounds are similarly obtained. ##STR84## where R 2 -R 5 , M, Z and W are as defined in Example 54.
EXAMPLE 57
dl-3-[5-Acetoxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]propionic acid
A mixture of 3.622 g 10-acetoxy-5,5-dimethyl-8-(5-phenyl-2-pentyloxy)-3,4-dihydropyrano[3,2-c]-5H-benzopyran-2-one, 3.0 ml of acetic acid and 3.5 g 10% Pd/C catalyst was hydrogenated at atmospheric pressure overnight. The catalyst was removed by filtration, washed with ethyl acetate and the filtrate evaporated in vacuo. To the residue was added 25 ml portions of dioxane and this evaporated to remove residual acetic acid as the azeotrope. The resulting residual oil, 3.8 g, was purified by chromatography on a silica gel column eluting with methylene chloride, taking 25 ml fractions. After 35 fractions were collected, elution with ethyl ether was employed for 5 fractions. The product containing fractions (#4-30) were combined and evaporated to dryness to obtain 843 mg of product.
1 H-NMR(CDCl 3 )ppm(delta): 2.25 (s, 3H), 4.20 (m, 1H), 6.20 (broad s, 2H), 7.20 (s, 5H), 8.60 (s, 1H). Mass spectrum (m/e): 454 (M + ).
EXAMPLE 58
In like manner the lactones provided in Example 56 are hydrogenated by the procedure of Example 57 and purified, if desired, by column chromatography to obtain compounds of the formula ##STR85## where R 2 -R 5 , M, Z and W are as defined in Example 54.
EXAMPLE 59
Methyl dl-3-[5-acetoxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]propionate
To a solution of 130 mg of dl-[5-acetoxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]propionic acid in 10 ml of ethyl ether was added a freshly prepared solution of diazomethane in ether until the color of the reaction mixture remained yellow. The mixture was then stirred for a few minutes, quenched with acetic acid and evaporated to an oil. The oil was purified by column chromatography on silica gel eluting with methylene chloride for 17 fractions (25 ml per fraction) then with 9:1 methylene chloride/ethyl acetate for 6 fractions. The product fractions (#4-18) were combined and evaporated to provide 137 mg of the desired methyl ester.
1 H-NMR(CDCl 3 )ppm(delta): 2.20 (s, 3H), 3.70 (s, 3H), 4.20 (m, 1H), 6.22 (broad s, 2H), 7.25 (s, 5H). Mass spectrum (m/e): 468 (M + ).
Similarly, the carboxylic acids provided in Example 58 are converted to methyl esters of the formula below ##STR86## where R 2 -R 5 , M, Z and W are as defined in Example 54.
EXAMPLE 60
dl-5-Hydroxy-3-(3-hydroxypropyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
To a solution of 100 mg (0.21 mmole) methyl dl-3-[5-acetoxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]propionate in 3.0 ml tetrahydrofuran was added 25 mg (0.66 mmole) lithium aluminum hyddride in increments. The resulting mixture was stirred (nitrogen atmosphere) for 40 minutes, the reaction quenched with water, evaporated to dryness and the residue dissolved in ethyl acetate. The solution was washed with water (2×15 ml), brine (1×15 ml), dried over anhydrous magnesium sulfate and evaporated in vacuo to provide a residual oil, 66 mg. An additional 11 mg of oil was obtained by reworking the aqueous washes. The combined residual oils, 77 mg, were chromatographed on a column of silica gel, eluting with methylene chloride for seven fractions (15 ml/fraction), the same eluant containing 5% by volume ethyl acetate (10 fractions), 10% ethyl acetate (5 fractions) and ethyl acetate along (7 fractions). Fractions 20-27 were combined and evaporated to dryness to afford 54 mg of the desired product.
1 H-NMR(CDCl 3 )ppm(delta): 3.60 (t, 2H), 4.20 (m, 1H), 5.90 (s, 2H), 7.10 (s, 5H). Mass spectrum (m/e): 398 (M + ).
The remaining methyl esters provided in Example 59 are reduced with lithium aluminum hydride by the above procedure to provide dihydroxy compounds of the formula ##STR87## where R 2 -R 5 , M, Z and W are defined in Example 54.
EXAMPLE 61
dl-5-Acetoxy-3-(3-hydroxypropyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
To a solution of 3.177 g (7.96 mmole) dl-5-hydroxy-3-(3-hydroxypropyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran in 40 ml methylene chloride, under a nitrogen atmosphere, was added ;b 805 mg (7.96 mmole) triethylamine, the mixture stirred for 15 minutes and cooled to 0° C. At this temperature, 970 mg (7.79 mmole) 4-dimethylaminopyridine in 3 ml methylene chloride followed by 813 mg (7.96 mmole) acetic anhydride was added and the resulting mixture stirred at 0°-5° C. for one hour. After allowing the mixture to warm to room temperature, it was extracted three times with 30 ml portions methylene chloride. The extracts were washed with saturated sodium bicarbonate solution, dried (MgSo 4 ) and evaporated to obtain 4.158 g of crude oil. The crude product was purified by column chromatography on silica gel eluting with ethyl ether/methylene chloride 3:97 (v/v) for 7 fractions and ;b 1:9 (v/v) for 43 fractions. Fractions 18-27 contained the diacetate. Fractions 28-45 containing desired monoacetate were combined and evaporated to afford 1.823 g of the title compound.
1 H-NMR(CDCl 3 )ppm(delta): 2.20 (s, 3H), 3.50 (t, 2H), 6.20 (m, 2H), 7.10 (s, 5H).
Employing the above procedure the remaining dihydroxy compounds of Example 60 are monoacetylated to provide compounds of the formula ##STR88## where R 2 -R 5 , M, Z and W are as defined in Example 54.
EXAMPLE 62
dl-3-(3-Cyanopropyl)-5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
A. dl-5-Acetoxy-3-(3-methanesulfonyloxypropyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran.
To 1.823 g (4.15 mmole) dl-5-acetoxy-3-(3-hydroxypropyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran was added 20 ml of pyridine, the mixture stirred under nitrogen to affect solution and cooled to 5° C. Methanesulfonyl chloride, 520 mg (4.56 mmole), was added, the resulting mixture stirred at 5°-10° C. for 20 minutes, then allowed to warm to room temperature and stirred for an additional 50 minutes. The mixture was concentrated in vacuo and the residual oil taken up in ethyl acetate, washed twice with water, once with brine and the organic layer dried over anhydrous magnesium sulfate. After evaporation of solvent in vacuo the desired product was obtained as an oil, 1.999 g.
1 H-NMR(CDCl 3 )ppm(delta): 2.20 (s, ;b 2H), 2.95 (s, 3H), 4.20 (m, 1H), 6.20 (m, 2H), 7.20 (s, 5H).
B. A mixture of 1.857 g (4.22 mmole) of the mesylate obtained in Part A, above, 2.8 g (43.0 mmole) potassium cyanide, 43.5 mg (0.252 mmole) potassium iodide and 40 ml of dimethylformamide/water (9:1 by weight) was heated at 90° C. for 1.5 hours. The solvent was evaporated in vacuo, the residue extracted three times with methylene chloride, the extracts washed with water, brine and dried over anhydrous magnesium sulfate. After evaporation of solvent 1.655 g of oil was obtained. The oil was purified on a short silica gel column, eluting with ethyl acetate. The product-containing fractions were combined and evaporated to provide 1.407 g (82%) of the title compound as an oil Rf 0.62 on silica gel TLC, solvent-ethyl ether, develop with vanillin/heat. Mass spectrum (m/e): 407 (M + ), 261 (M-146), 139 (base).
Employing the above procedures the remaining compounds provided in Example 61 are converted to nitriles of the formula ##STR89## where R 2 -R 5 , M, Z and W are as defined in Example 54.
EXAMPLE 63
dl-4-[5-Hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]butyric acid
A mixture of 1.407 g (3.45 mmole) dl-3-(3-cyanopropyl)-5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran, 50 ml methanol and 26 ml 1N sodium hydroxide was heated at reflux overnight. The methanol was evaporated and the aqueous residue washed with methylene chloride. The methylene chloride washings were extracted with 10 ml 1N sodium hydroxide, the combined aqueous layers acidified with hydrochloric acid, extracted with methylene chloride and the organic extracts dried over anhydrous magnesium sulfate. The solvent was evaporated in vacuo to obtain 1.189 g of the title acid as a foam. Mass spectrum (m/e): 426 (M + ) 280 (M-146), 139 (base).
By means of the above procedure the remaining compounds provided in Example 62 form carboxylic acids of the formula ##STR90## where R 2 -R 5 , M, Z and W are as defined in Example 54. The products wherein M is NH are isolated by isoelectric precipitation as described in Example 54.
EXAMPLE 64
dl-5-Hydroxy-3-(4-hydroxybutyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
To a solution of 1.238 g (2.9 mmole) dl-3-[5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]butyric acid in 20 ml tetrahydrofuran under a nitrogen atmosphere was added, in increments, 165 mg (4.35 mmole) lithium aluminum hydride and the resulting mixture stirred for 30 minutes at room temperature. The reaction was quenched by addition of Glauber's salt (Na 2 SO 4 .10H 2 O), 20 ml ethyl acetate and about one gram of a filter aid was added. After stirring for 30 minutes the mixture was filtered, the solids washed with cold ethyl acetate. The filter cake was slurried with hot ethyl acetate, filtered and the combined filtrates evaporated in vacuo to provide 852 mg of residual oil. The oil was purified by chromatography on a silica gel column, eluting with ethyl acetate to provide 653 mg of the title compound, Rf 0.75 on silica gel TLC (solvent-ethyl acetate, developed with vanillin/heat). Mass spectrum (m/e): 412 (M + ), 266 (M-146), 139 (base).
Similarly the remaining acids provided in Example 64 are reduced to dihydroxy compounds of the formula ##STR91## where R 2 -R 5 , M, Z and W are as defined in Example 54.
EXAMPLE 65
dl-3-(2-Cyanoethyl)-5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran
A. Methyl dl-3-[5-acetoxy,2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]propionate, 4.68 g (0.01 mole), is dissolved in methanol and anhydrous ammonia is passed through the mixture at room temperature. The resulting mixture is heated at reflux for two hours while passing ammonia through it. After standing overnight the volatiles are removed by evaporation and the residue purified by column chromatography on silica gel to provide dl-3-[5-hydroxy-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran-3-yl]propionamide.
B. The amide obtained above and 100 ml of thionyl chloride are heated at reflux for 18 hours. The reaction mixture is poured into ice-water, made alkaline by addition of sodium hydroxide solution, extracted with ether, the extracts dried (MgSO 4 ) and evaporated to dryness. The crude nitrile is purified by column chromatography on silica gel.
The remaining esters provided in Example 59 are converted to nitriles of the formula below in similar manner ##STR92## where R 2 -R 5 , M, Z and W are as defined in Example 54.
EXAMPLE 66
Lithium aluminum hydride reduction of the nitriles provided in Examples 62 and 65 by the procedure of Example 15 provides the corresponding primary amines of the formula ##STR93## where f is 1 or 2 and R 2 -R 5 , M, Z and W are as defined in Examples 62 and 65.
EXAMPLE 67
Acylation of the above primary amines by the method of Example 16 and hydrolysis of the resulting amido ester by the method of Example 17 provides amides of the formula below ##STR94## where R 1 is hydrogen, R 14 is as defined in Example 16 and f, R 2 -R 5 , M, Z and W are as defined in Example 66. The corresponding compounds wherein R 1 is defined in Example 18 are prepared from the above compounds by the procedure of Example 18.
EXAMPLE 68
5-Hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3-(2-p-toluenesulfonylaminoethyl)-1,2,3,4-tetrahydroquinoline
To 20 ml of methylene chloride is added 346 mg (1 mmole) dl-5-hydroxy-3-(2-aminoethyl)-7-(1,1-dimethylheptyl)-2,2-dimethyl-1,2,3,4-tetrahydroquinoline and 0.166 ml (1.2 mmole) triethylamine. The solution is cooled to -20° C. and a solution of ;b 191 mg (1 mmole) p-toluenesulfonyl chloride in 10 ml methylene chloride is added dropwise over ten minutes. The mixture is allowed to warm to 0° C., poured into ice/water and the layers separated. The aqueous layer is extracted with fresh methylene chloride, the combined organic layers washed with water, saturated sodium bicarbonate solution, brine and dried over anhydrous magnesium sulfate. Evaporation of solvent affords the crude product which is purified by chromatography on silica gel.
In like manner the remaining amines provided in Example 66 are reacted with sulfonyl chlorides of the formula R 17 SO 2 Cl to provide compounds of the formula ##STR95## where f, R 2 -R 5 , M, Z and W are as defined in Example 66 and R 17 is as defined below.
______________________________________ R.sub.17______________________________________ CH.sub.3 C.sub.2 H.sub.5 (CH.sub.3).sub.2 CH -n-C.sub.4 H.sub.9 -n-C.sub.5 H.sub.11 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 C.sub.6 H.sub.5 4-NH.sub.2 C.sub.6 H.sub.4 3-FC.sub.6 H.sub.4 2-ClC.sub.6 H.sub.4 4-BrC.sub.6 H.sub.4 4-ClC.sub.6 H.sub.4 4-CH.sub.3 OC.sub.6 H.sub.4 3-CH.sub.3 C.sub.6 H.sub.4______________________________________
EXAMPLE 69
Reaction of the methyl esters provided in Example 59 with ammonia or an amine, R 12 NH 2 , by the procedure of Example 20 provides amides of the formula below in which R 13 is hydrogen. Acetylation of the hydroxy carboxylic acids provided in Examples 54 and 63 by the procedure of Example 12 followed by conversion of the acetoxy acid to the corresponding acetoxy acid chloride and reaction of the latter with an amine R 12 R 13 NH by the method of Example 21 affords amides of the formula below wherein f is 1 or 2, R 2 -R 5 , M, Z and W are as defined in Example 54 and R 12 and R 13 are as defined below
______________________________________ ##STR96##
______________________________________R.sub.12 R.sub.13______________________________________H HCH.sub.3 H(CH.sub.3).sub.2 CH H(CH.sub.3).sub.2 CHCH.sub.2 H -n-C.sub.6 H.sub.13 HC.sub.6 H.sub.5 HC.sub.6 H.sub.5 CH.sub.2 HCH.sub.3 CH.sub.3CH.sub.3 C.sub.2 H.sub.5 -n-C.sub.3 H.sub.7 -n-C.sub.3 H.sub.7(CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 -n-C.sub.6 H.sub.13 C.sub.2 H.sub.5C.sub.2 H.sub.5 C.sub.6 H.sub.5C.sub.6 H.sub.5 C.sub.6 H.sub.5CH.sub.3 C.sub.6 H.sub.4 CH.sub.2______________________________________ NR.sub.12 R.sub.13______________________________________ morpholino piperidino pyrrolidino Nmethylpiperazino Nethylpiperazino Nisopropylpiperazino Nsec-butylpiperazino N -n-butylpiperazino______________________________________
EXAMPLE 70
The amides provided in Example 69 are reduced with lithium aluminum hydride by the method of Example 21A to provide amines of the formula ##STR97## where f, R 2 -R 5 , R 12 , R 13 , M, Z and W are as defined in Example 69.
EXAMPLE 71
The N,N-dimethylamides provided in Example 69 are reacted with disiamylborane in tetrahydrofuran by the method of Example 22 to provide aldehydes of the formula ##STR98## where f, R 2 -R 5 , M, Z and W are as defined in Example 69.
EXAMPLE 72
Treatment of the above aldehydes with a molar excess of Grignard reagent of formula R 8 MgBr, R 8 MgCl or R 8 MgI by the methods of Examples 8 and 8A provides secondary alcohols of the formula ##STR99## where f, R 2 -R 5 , M, Z and W are as defined in Example 69 and R 8 is as defined in Example 8A.
EXAMPLE 73
Oxidation of the above secondary alcohols by the method of Example 24 similarly provides the corresponding ketones of the formula ##STR100## wherein f, R 2 -R 5 , R 8 , M, Z and W are as defined in Example 72.
EXAMPLE 74
The ketones provided above are reacted with molar excess of Grignard reagent by the procedure of Example 25 to provide tertiary alcohols of the formula ##STR101## where f, R 2 -R 5 , M, Z and W are as defined in Example 69 and R 8 and R 9 are the same and are defined in Example 25.
EXAMPLE 75
dl-4-(2-Hydroxyethyl)-5-hydroxy-1,2-dimethyl-7-(4-thiaoctyl)-1,2,3,4-tetrahydroquinoline
To a stirred solution of dl-4-(2-hydroxyethyl)-5-hydroxy-2-methyl-7-(4-thiaoctyl)-1,2,3,4-tetrahydroquinoline (337 mg, 1.0 mmole) in 5 ml acetonitrile cooled to 15° C. is added 0.5 ml aqueous formaldehyde and 100 mg sodium cyanoborohydride. Acetic acid is added to maintain a neutral pH unit the reaction is complete. The reaction mixture is partitioned between water and ethyl ether, the organic phase dried (MgSO 4 ) and evaporated to afford the title compound.
In like manner the corresponding compounds wherein R 6 is ethyl, n-butyl, isobutyl, isoamyl, n-hexyl, C 6 H 5 CH 2 , C 6 H 5 (CH 2 ) 2 , C 6 H 5 (CH 2 ) 3 and C 6 H 5 (CH 2 ) 4 are obtained when the formaldehyde employed in the above procedure is replaced by an equimolar amount of acetaldehyde, n-butyraldehyde, isobutyraldehyde, isoamylaldehyde, C 6 H 5 CHO, C 6 H 5 CH 2 CHO, C 6 H 5 (CH 2 ) 2 CHO or C 6 H 5 (CH 2 ) 3 CHO, respectively.
Similarly the compounds provided above wherein R 6 is hydrogen are converted to the corresponding compounds wherein R 6 is methyl, ethyl, n-butyl, isobutyl, isoamyl, n-hexyl, C 6 H 5 CH 2 , C 6 H 5 (CH 2 ) 2 , C 6 H 5 (CH 2 ) 3 or C 6 H 5 (CH 2 ) 4 by the same procedure.
EXAMPLE 76
Methyl dl-3-[5-acetoxy-1-benzoyl-2,2-dimethyl-7-(2-heptyloxy)-1,2,3,4-tetrahydroquinolin-3-yl]propionate
To a stirred solution of methyl dl-3-[5-acetoxy-2,2-dimethyl-7-(2-heptyloxy)-1,2,3,4-tetrahydroquinolin-3-yl]propionate (838 mg, 2 mmole) in 3 ml pyridine is added 0.42 g (3 mmole) benzoyl chloride in 5 ml chloroform. After stirring at reflux for one hour, the mixture is cooled, poured onto ice and extracted with ethyl ether. The combined ether extracts are washed with water, sodium bicarbonate, dried (MgSO 4 ) and evaporated to dryness to afford the desired product which is purified, if desired, by crystallization or column chromatography.
When the benzoyl chloride is replaced by an equimolar amount of acetyl chloride, propionyl chloride, isobutyryl chloride, valeryl chloride, 2-phenylacetyl bromide or 4-phenylbutyryl chloride, the corresponding compounds are obtained where R 6 is CH 3 CO, CH 3 CH 2 CO, (CH 3 ) 2 CHCO, CH 3 (CH 2 ) 3 CO, C 6 H 5 CH 2 CO or C 6 H 5 (CH 2 ) 3 CO, respectively.
In like manner the compounds provided above wherein R 6 is hydrogen are converted to the corresponding benzoyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, 2-phenylacetyl, 3-phenylpropionyl and 4-phenylbutyryl derivatives by reaction with the appropriate acyl chloride or acyl bromide. Use of carbobenzyloxy chloride affords the corresponding compounds wherein R 6 is COOCH 2 C 6 H 5 . Of course when the 2- or 3-substituent of the tetrahydroquinoline starting material contains a primary amino, secondary amino or hydroxy group, the corresponding bis-amides or acyloxy amides are also obtained.
EXAMPLE 77
dl-4-(3-Oxobutyl)-1,2-dimethyl-5-(4-morpholinobutyryloxy)-7-(5-phenyl-2-pentyloxy)-1,2,3,4-tetrahydroquinoline
To a solution of 614 mg (1.5 mmole) dl-4-(3-oxobutyl-5-hydroxy-2-methyl-7-(5-phenyl-2-pentyloxy)-1,2,3,4-tetrahydroquinoline in 40 ml of dry methylene chloride is added 315 mg (1.5 mmole) 4-morpholinobutyric acid hydrochloride, and the mixture is stirred at room temperature under a nitrogen atmosphere. To this is added dropwise 12.5 ml of 0.1 molar dicyclohexylcarbodiimide in methylene chloride and the resulting mixture is stirred for 24 hours. It is then cooled to 0° C., filtered, the filtrate extracted with 0.1N hydrochloric acid, the aqueous phase washed with ether, then made alkaline with sodium hydroxide solution and extracted with ether. The ether extracts are dried (MgSO 4 ) and evaporated to dryness to afford the title compound. The product is purified, if desired, by chromatography on silica gel.
Repetition of this procedure, but using an appropriate 5-hydroxy compound selected from those provided above and the appropriate alkanoic acid or acid of formula R 15 R 16 N(CH 2 ) p --COOH.HCl affords the corresponding 5-OR 1 substituted compounds wherein R 1 is as defined in Example 18.
EXAMPLE 78
dl-Butyl 3-[4-(2-hydroxyethyl)-5-hydroxy-1,2-dimethyl-1,2,3,4-tetrahydroquinolin-7-yl]propyl sulfoxide
Equimolar amounts of m-chloroperbenzoic acid and dl-4-(2-hydroxyethyl)-5-hydroxy-1,2-dimethyl-7-(4-thiaoctyl)-1,2,3,4-tetrahydroquinoline are added to a mixture of chloroform and acetic acid (2:1 v/v) and the mixture stirred at room temperature for one hour. The mixture is washed with water, the organic phase dried (MgSO 4 ) and evaporated to dryness at reduced pressure to afford the title compound.
In like manner the remaining thio ethers provided herein are oxidized to the corresponding sulfoxides.
EXAMPLE 79
dl-Butyl-3-[4-(2-hydroxyethyl)-5-hydroxy-1,2-dimethyl-1,2,3,4-tetrahydroquinolin-7-yl]propyl sulfone
The procedure of Example 78 is repeated but using 2 equivalents of m-chloroperbenzoic acid as oxidizing agent per mole of tio ether reactant to give the title sulfone.
Similarly the remaining thio ethers provided herein are oxidized to the corresponding sulfones.
EXAMPLE 80
General Hydrochloride Acid Addition Salt Formation
Into an ethereal solution of the appropriate free base of formula (I), where one or more of M, R 1 , and Q is a basic nitrogen containing group, is passed a molar excess of anhydrous hydrogen chloride and the resulting precipitate is separated and recrystallized from an appropriate solvent, e.g. methanol-ether.
Similarly, the free bases of formula (I) are converted to their corresponding hydrobromide, sulfate, nitrate, phosphate, acetate, butyrate, citrate, malonate, maleate, fumarate, malate, glycolate, gluconate, lactate, salicylate, sulfosalicylate, succinate, pamoate and tartarate salts.
EXAMPLE 81
dl-5-Hydroxy-4-(2-hydroxyethyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran, 100 mg, is intimately mixed and ground with 900 mg of starch. The mixture is then loaded into telescoping gelatin capsules such that each capsule contains 10 mg of drug and 90 mg of starch.
EXAMPLE 82
A tablet base is prepared by blending the ingredients listed below:
Sucrose: 80.3 parts
Tapioca starch: 13.2 parts
Magnesium stearate: 6.5 parts
Sufficient dl-5-acetoxy-4-(2-acetylaminoethyl)-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran is blended into this base to provide tablets containing 0.1, 0.5, 1, 5, 10 and 25 mg of drug.
EXAMPLE 83
Suspensions of dl-5-hydroxy-3-(3-hydroxypropyl)-2,2-dimethyl-7-(5-phenyl-2-pentyloxy)-3,4-dihydro-2H-benzopyran are prepared by adding sufficient amounts of drug to 0.5% methylcellulose to provide suspensions having 0.05, 0.1, 0.5, 1, 5 and 10 mg of drug per ml.
EXAMPLE 84
5-Benzyloxy-4-cyano-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A. A mixture of 5.0 g (12.3 mmole) 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-one and 20 ml benzene is stirred under nitrogen. To the resulting solution is added 2.04 ml trimethylsilylnitrile, 80 mg zinc iodide and stirring continued at room temperature for three hours. Pyridine, 16 ml, and phosphorus oxychloride, 9.4 g, are added and the mixture heated at reflux for 3.5 hours, cooled to room temperature, poured onto a mixture of ice and 35 ml concentrated hydrochloric acid. The resulting mixture is extracted with ethyl acetate, dried (MgSO 4 ) and the solvent evaporated in vacuo to provide 5.63 g residual oil which is purified by chromatography on silica gel, eluting with hexane/ethyl ether. Evaporation of solvent from the product fractions gives 3.93 g 5-benzyloxy-4-cyano-2,2-dimethyl-7-(1,1-dimethylheptyl)-2H-benzopyran. Repeating the above procedure on a 5-fold scale gives 24.5 g of crude material which is purified on silica gel to provide 19.06 g of product.
1 H-NMR(CDCl 3 )ppm(delta): 5.05 (s, 2H), 6.10 (s, 1H), 6.35 (s, 2H), 7.20 (m, 5H).
B. A mixture of 418 mg (1 mmole) of the unsaturated nitrile obtained in Part A, above, 485 mg magnesium turnings, 15 ml methanol and 5 ml tetrahydrofuran is stirred under nitrogen overnight at room temperature. The mixture is cooled in ice, water added to the flask to effect precipitation. The mixture is adjusted to pH 3.0 with hydrochloric acid and the clear solution extracted with ethyl acetate. The extracts are washed with water, brine and dried (MgSO 4 ). Evaporation of solvent at reduced pressure gives 422 mg crude material which is purified by chromatography on silica gel, eluting with hexane/ethyl ether. Evaporation of the combined product fractions yields 294 mg (70%) of the title compound.
1 H-NMR(CDCl 3 )ppm(delta): 4.00 (t, 1H), 5.10 (s, 2H), 6.40 (s, 2H), 7.30 (m, 5H).
EXAMPLE 85
5-Benzyloxy-4-carboxamido-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
To 3.4 g (8.2 mmole) 5-benzyloxy-4-cyano-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran is added a solution of 40 g potassium hydroxide in 160 g ethylene glycol and 10 ml water. The mixture is heated at 150° C. under an argon atmosphere for 24 hours, diluted with water (700 ml), acidified to pH 5 and extracted with ethyl acetate. The combined extracts are washed with water, brine, dried (MgSO 4 ) and solvent evaporated to give 8.5 g crude product. The crude is purified by chromatography on silica gel, eluting with ethyl ether/hexane (1:4, then 1:1). The combined product fractions are evaporated to give 2.0 g of the desired amide. Fractions containing starting material were combined, evaporated to dryness, hydrolyzed further under the above conditions for 48 hours and worked up as before to give 1.5 g crude material which is purified on a silica gel column to afford an additional 1.0 g of amide and 550 mg of the croresponding carboxylic acid.
The combined amide fractions were crystallized from methylene chloride/hexane to yield 2.55 g of product, m.p. 117°-120° C.
1 H-NMR(CDCl 3 )ppm(delta): 3.70 (t, 1H), 5.00 (s, 2H), 5.75 and 6.15 (broad singlets 1H+1H), 6.50 (s, 2H), 7.30 (m, 5H).
EXAMPLE 86
4-Carboxamido-5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A mixture of 1.6 g 5-benzyloxy-4-carboxamido-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran, 320 mg 10% palladium/carbon and 50 ml methanol is hydrogenated with shaking at 3 atmospheres pressure overnight. The catalyst is removed by filtration and the filtrate evaporated to afford 1.21 g solid which is crystallized from ethyl acetate to yield 520 mg product, m.p. 174.5°-175° C. An additional 220 mg of product is recovered from the mother liquors.
1 H-NMR(CDCl 3 )ppm(delta): 2.10 (d, 2H), 3.65 (t, 1H), 4.80 (broad s, 3H), 6.30 (dd, 2H).
EXAMPLE 87
4Cyano-5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
Hydrogenation of 5-benzyloxy-4-cyano-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran by the above procedure affords the title hydroxy nitrile, m.p. 142°-144° C.
1 H-NMR(CDCl 3 )ppm(delta): 2.20 (d, 2H), 4.05 (t, 1H), 6.40 (m, 2H).
EXAMPLE 88
5-Hydroxy-4-methoxycarbonyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A. 5-Benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylic acid
A mixture of 2.0 g 5-benzyloxy-4-cyano-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran, 20 g potassium hydroxide and 100 ml ethylene glycol are heated under nitrogen at reflux for 18 hours and cooled to ambient temperature. The mixture is acidified to pH 3 with concentrated hydrochloride acid, extracted with ethyl acetate and the extracts dried (MgSO 4 ). Evaporation of solvent gives an oil which is taken up in ethyl ether, washed with water, brine, dried (MgSO 4 ) and the solvent evaporated to give 2.09 g of crude solid. The crude was purified by chromatography on silica gel, eluting with ethyl ether/hexane. The combined product fractions are combined and solvent evaporated to afford 1.69 g of product, m.p. 137°-138° C.
B. Methyl 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylate
A solution of 550 mg of the above carboxylic acid dissolved in 20 ml dry ethyl ether is treated with a molar excess of diazomethane. The mixture is allowed to stand at room temperature for 15 minutes, washed with dilute sodium bicarbonate solution, dried (MgSO 4 ) and the ether evaporated to give 470 mg of methyl ester which was used to the next step without purification.
C. The product from Part B, above (470 mg), is mixed with 200 mg 10% palladium/carbon catalyst and 40 ml methanol. The mixture is hydrogenated with shaking at 3 atmospheres pressure for two hours. Removal of catalyst by filtration and evaporation of solvent gives 320 mg of crude product. This is purified by chromatography on silica gel, eluting with 1:1 hexane/ethyl ether to give 300 mg of the desired 5-hydroxy compound.
1 H-NMR(CDCl 3 )ppm(delta): 2.10 (dd, 2H), 3.75 (s, 3H), 3.80 (t, 1H), 6.40 (s, 2H), 6.50 (s, 1H).
EXAMPLE 89
4-N-Acetylcarboximido-5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
A. p-Nitrophenyl 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylate
A mixture of 3.3 g (7.53 mmole) 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylic acid, 5.0 g (21.3 mmole) p-nitrophenyl trifluoroacetate and 100 ml dry pyridine, under nitrogen, is stirred at room temperature for three hours. The pyridine is evaporated in vacuo, ethyl ether is added to the residue and this is washed with 1N sodium hydroxide, water, 10% hydrochloric acid, brine, dried (MgSO 4 ) and the solvent evaporated to obtain 4.5 g crude oil. This is taken up in pentane and cooled to obtain 3.38 g of crystals, m.p. 87°-87.5° C.
B. 4-N-Acetylcarboximido-5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
To 301 mg (5.1 mmole) acetamide is added 35 ml dry tetrahydrofuran and nitrogen passed through the solution while adding 103 mg sodium hydride (99%) (4.3 mmole). The resulting mixture is stirred overnight under nitrogen, 400 mg (0.716 mole) of the p-nitrophenyl ester provided in Part A is added and stirring is continued for one hour at room temperature. The mixture is poured onto ice/water, adjusted to pH 3.0 with 10% hydrochloric acid and extracted with ethyl acetate. The extracts are washed with brine, saturated sodium bicarbonate solution, brine again and dried (MgSO 4 ). Evaporation of solvent yields 416 mg crude solid. The crude is taken up in methylene chloride, washed with sodium bicarbonate solution, brine, dried (MgSO 4 ) and solvent evaporated to afford 331 mg foam. Upon addition of hexane, crystals are precipitated, 249 mg. Treatment of this with hot hexane gives 216 mg upon cooling and filtration, m.p. 157°-158° C.
1 H-NMR(CDCl 3 )ppm(delta): 2.20 (s, 3H), 3.80 (t, 1H), 5.0 (s, 2H), 6.50 (s, 2H), 7.30 (s, 5H), 8.10 (s, 1H).
C. The product from Part B, above, 216 mg, 45 mg 5% palladium/carbon and 25 ml ethyl acetate is shaken under hydrogen at atmospheric pressure for 2.5 hours. Filtration and evaporation of the filtrate affords 158 mg of product, m.p. 146°-147° C.
D. Repeating the procedure of Part B, above, with the appropriate amide of formula R 10 CONH 2 , sulfonamide of formula R 17 SO 2 NH 2 or urea in place of acetamide and hydrogenation of the resulting product by the method of Part C, above, affords the corresponding imido compounds of the formula below. ##STR102## where Q 3 is CONHCOR 19 , CONHSO 2 R 17 or CONHCONH 2 and R 7 and R 17 are as shown below.
______________________________________Q.sub.3 = CONHCOR.sub.19 :R.sub.19 Comment______________________________________CH(CH.sub.3).sub.2 M.P. 143-148° C.C(CH.sub.3).sub.3 Mass spectrum, m/e: M.sup.+ 431 base 360 .sup.1 H--NMR (CDCl.sub.3) ppm (delta): 4.05 (t, 1H), 6.50 (m, 2H), 7.1 (s, 1H)C.sub.6 H.sub.5 M.P. 172-173° C.C.sub.6 H.sub.5 CH(CH.sub.3) M.P. 141-146° C.(diastereomer A) Mass spectrum, m/e: M.sup.+ 479 .sup.1 H--NMR (DCCl.sub.3) ppm (delta): 3.85 (t, 1H), 4.3 (q, 1H), 6.2 (m, 2H), 7.2 (s, 5H)C.sub.6 H.sub.5 CH(CH.sub.3) M.P. 144-149° C.(diastereomer B) Mass spectrum, m/e: M.sup.+ 479 base 105 .sup.1 H--NMR (CDCl.sub.3) ppm (delta): 3.90 (t, 1H), 4.40 (q, lH), 6.35 (m, 2H), 7.25 (s, 5H)C.sub.6 H.sub.5 CH.sub.2 --n-C.sub.4 H.sub.9 --Q.sub.3 = CONHCONH.sub.2 M.P. 154-158° C. Mass spectrum, m/e: M.sup.+ 390 (M--NH.sub.3) 373______________________________________Q.sub.3 = CONHSO.sub.2 R.sub.17 :R.sub.17 Comment______________________________________CH.sub.3 M.P. 155-156° C. Mass spectrum, m/e: M.sup.+ 425 base 303C.sub.2 H.sub.5 --(CH.sub.3).sub.2 CH --CH.sub.3 (CH.sub.2).sub.4 --CH.sub.3 (CH.sub.2).sub.5 --(CH.sub.3).sub.2 CH(CH.sub.2).sub.3 --C.sub.6 H.sub.5 CH.sub.2 --4-CH.sub.3 C.sub.6 H.sub.4 --C.sub.6 H.sub.5 --2-ClC.sub.6 H.sub.4 --4-BrC.sub.6 H.sub.4 --3-FC.sub.6 H.sub.4 --4-NH.sub.2 C.sub.6 H.sub.4 --3-CH.sub.3 OC.sub.6 H.sub.4 --______________________________________
EXAMPLE 90
5-Hydroxy-4-(5-tetrazolyl)-2,2dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
Finely ground sodium azide (325 mg, 5 mmole) is added to a solution of 5-acetoxy-4-cyano-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran (1.855 g, 5 mmole) in 10 ml ethanol-free chloroform containing 271 mg (2 mmole) N-methylpiperidine hydrochloride and 5 drops of N-methylpiperidine. The mixture is heated at reflux for one hour, another 2 mmoles of N-methylpiperidine hydrochloride is added, refluxing is continued for one hour and the mixture is allowed to stand overnight at room temperature. The mixture is partitioned between chloroform and aqueous sodium carbonate solution, the aqueous phase is adjusted to pH 5 and extracted again with chloroform. The combined organic layers are washed with water, dried (MgSO 4 ) and the solvent evaporated in vacuo to afford the title compound.
In like manner any of the nitriles provided above are converted to the corresponding 5-tetrazolyl derivative by the above procedure.
EXAMPLE 91
5-Hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-hydroxamic acid
A. 5-Hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylic acid
A mixture of 5.0 g. 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylic acid (prepared by the method of Example 88, Part A), 500 mg. 5% palladium-on-carbon catalyst and 150 ml. ethyl acetate is hydrogenated for 18 hours by the procedure of Example 86. After removal of catalyst and evaporation of solvent 4.25 g. of foam is obtained. Purification by silica gel chromatography, eluting with 2:1 hexane/ethyl ether affords 1.84 g. of product, M.P. 147°-148° C.
B. p-Nitrophenyl-5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylate
A mixture of 4.25 g. (12.3 mmole) of the product of Part A, 8.67 g. (37 mmole) p-nitrophenyltrifluoroacetate and 50 ml. dry pyridine is stirred for 65 hours at room temperature. The mixture is evaporated to remove pyridine and the residue is worked up as described in Example 89, Part A, to obtain 5.085 g. (88%) of the desired ester; 1 H-NMR (CDCl 3 ) ppm (delta): 6.5 (m, 2H), 6.7 (s, OH), 7.0-7.3 (m, 2H), 8.0-8.3 (m, 2H).
C. A mixture of 43 mg. (1.066 mmole) powdered sodium hydroxide in 10 ml. pyridine under a nitrogen atmosphere is stirred and warmed to effect solution then cooled to 0° C. To this is added 111 mg. (1.6 mmole) hydroxylamine hydrochloride and the mixture stirred for 15 minutes. A solution of 250 mg. (0.533 mmole) of the product of Part B in 3.0 ml. pyridine is added, the mixture allowed to warm to room temperature and stirred overnight. The pyridine is evaporated, the residue taken up in water and extracted with ethyl acetate. The combined extracts are washed with water and saturated brine and dried (MgSO 4 ). Evaporation of solvent affords 260 mg. of crude product which is charged to a column of 30 g. silica gel. Elution with 1:1 hexane/ethyl ether for 10 fractions then with ethyl acetate to elute the desired product. Evaporation of solvent (fractions 18-20) gave 158 mg. title compound. Mass spectrum (M + 363); .sup. 1 H-NMR (CDCl 3 ) ppm (delta): 6.20 (4H, 2 aromatic, NH, OH), 10.0 (1H, exchanges with D 2 O).
EXAMPLE 92
N-2-Pyridyl 5-hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-carboxamide
A. N-2-Pyridyl 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyrancarboxamide
A mixture of 1.118 g. (2.0 mmole) 4-nitrophenyl 5-benzyloxy-2,2-dimethyl-7-(1,2-dimethylheptyl)-3,4-dihydro-2H-benzopyran-carboxylate, 376 mg. (4.0 mmole) 2-aminopyridine and 4 ml. pyridine is placed in a sealed tube and heated for 18 hours at 155°-157° C. After cooling the tube is opened, the mixture concentrated to dryness in vacuo, the residue dissolved in ethyl ether, washed with 1N hydrochloric acid (25 ml.), 1N sodium hydroxide (3×25 ml.), water (2×25 ml.) and brine (25 ml.). The washed ether solution is dried (MgSO 4 ) and solvent evaporated to afford 966 mg. of oil. The oil is purified by chromatography on a silica gel column, eluting with hexane/methylene chloride (1:4), then with 15% ethyl ether in methylene chloride. The product-containing fractions are combined and solvent evaporated in vacuo to yield 823 mg. (80%) of the desired amide.
B. A mixture of 691 mg. each of the above amide and 10% Pd/C catalyst, 1.08 g. 1,4-cyclohexadiene and 25 ml. dry ethanol is hydrogenated by the procedure of Example 86. After removal of solvent in vacuo 680 mg. of crude debenzylated product is obtained. This is purified by column chromatography on silica gel, eluting with methylene chloride, then methylene chloride containing 10% ethyl ether and finally with ethyl ether alone to obtain 515 mg. (90%) of debenzylated material which is crystallized from ethyl acetate/hexane to afford (398 mg. (70%) of product, M.P. 166°-167° C.; mass spectrum, m/e: 424 (molecular ion), 119 base.
C. By employing the appropriate amine, ArNH 2 , in place of 2-pyridylamine the following compounds are obtained by the above procedure.
______________________________________ ##STR103##Ar M.P. °C. Mass Spectra (m/e)______________________________________ ##STR104## 238.5-239 M.sup.+ 430 base 127 ##STR105## -- M.sup.+ 534 base 91 ##STR106## 208-209 M.sup.+ 444 base 141 ##STR107## -- M.sup.+ 425 base 96 ##STR108## -- --C.sub.6 H.sub.5 -- -- ##STR109## --______________________________________
EXAMPLE 93
5-Hydroxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-spiro[3,4-dihydro-2H-benzopyran-4,3'-pyrrolidin-2',5'-dione]
A. 5-Benzyloxy-4-ethoxycarbonylmethyl-4-methoxycarbonyl-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran
Under anhydrous conditions, under a nitrogen atmosphere 5.31 ml. of 1.6 molar n-butyllithium in hexane is charged to a flask containing 80 ml. dry tetrahydrofuran at -78° C. A solution of 1.2 ml. (848 mg., 8.4 mmole) freshly distilled diisopropylamine is added dropwise and the resulting mixture stirred at -78° C. for three hours. Then a solution of 3.1 g. (6.85 mmole) methyl 5-benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)-3,4-dihydro-2H-benzopyran-4-carboxylate (Example 88, Part B) in 10 ml. THF is added slowly and the resulting mixture stirred for three hours at -78° C. To this is added dropwise 1.40 g. (8.4 mmole) ethyl bromoacetate and the mixture stirred for 15 minutes. The reaction is quenched by addition of acetic acid and the mixture allowed to warm to ambient temperature. The product was isolated by the procedure described in Example 3, Part A, to obtain 2.89 g. (78%) of the desired diester, R f 0.29, hexane/ethyl ether, 3:1.
B. 5-Benzyloxy-2,2-dimethyl-7-(1,1-dimethylheptyl)spiro[3,4-dihydro-2H-benzopyran-4,3'-tetrahydrofuran-2',5'-dione]
A mixture of 2.355 g. (4.37 mmole) of the diester from Part A, above, 17.5 g. ethylene glycol, 1 ml. water and 8.74 g. potassium hydroxide is stirred under nitrogen at 150° C. for two hours then allowed to cool and stir overnight at room temperature. The mixture is poured into 350 ml. ice/water, acidified to pH 2-3 with 1N hydrochloric acid and extracted with ethyl acetate. The combined extracts are washed with water, brine and dried (MgSO 4 ). Upon evaporation of solvent in vacuo 2.0 g. of residual dicarboxylic acid is obtained. In a separate flask 50 ml. of acetic anhydride is stirred under a nitrogen atmosphere while heating to reflux (140° C.). To this is added dropwise over four minutes a solution of the dicarboxylic acid (2.0 g.) dissolved in 10 ml. ethyl acetate. The resulting mixture is stirred at 140° C. for ten minutes then allowed to cool to room temperature. The solvent is evaporated, the residue taken up in ethyl ether, washed with water, brine and dried (MgSO 4 ). Evaporation of solvent affords 1.9 g. of light brown solid. 1 H-NMR (CDCl 3 ) ppm (delta): 3.15 doublet, 5.1 singlet, 6.25 singlet and 7.3 singlet; infrared (CHCl 3 ): 1787 cm -1 (anhydride C═O).
C. A mixture of 100 mg. (0.209 mmole) of the product obtained in Part B and 125 mg. (2.08 mmole) urea is heated under nitrogen at 200° C. for 20 minutes and allowed to cool. The solidified reaction mixture is dissolved in ethyl ether, washed with water, brine and dried (MgSO 4 ). Evaporation of solvent yielded 67 mg. of the 5-benzyl ether of the title compound which is taken up in 15 ml. ethyl acetate and hydrogenated over 50 mg. of 10% palladium/carbon catalyst. The catalyst is removed by filtration, solvent evaporated and the residue taken up in ethanol (15 ml.) and hydrogenated again with fresh catalyst at 2.5 atmosphere pressure. Isolation of product by filtration and evaporation of solvent affords 54 mg. of the solid title compound, M.P. 105°-120° C. which upon crystallization gives crystals, M.P. 141°-143° C.; mass spectrum, molecular ion m/e 387; infrared (CHCl 3 ) 1715 cm -1 (C═O).
EXAMPLE 94
5-Benzyloxy-2,2-dimethyl-7-(2-methylpropyl)-3,4-dihydro-2H-benzopyran-4-one
A. 3,5-Dihydroxyisobutylbenzene
A mixture of 66.2 g. 1-hydroxy-1-(3,5-dimethoxyphenyl)-2-methylpropane (from reaction of 3,5-dimethoxybezaldehyde and isopropylmagnesium chloride in ethyl ether at 0°-5° C.) and 230 g. pyridine hydrochloride is heated under nitrogen at 190° C. for 3.5 hours. The resulting mixture is cooled to 30° C., poured into 500 ml. ice/water and the mixture acidified (pH 3.0) with 10% hydrochloric acid. The acid mixture is extracted three times with ethyl acetate, the extracts washed with water, brine, dried (MgSO 4 ) and the solvent evaporated in vacuo to provide 50.9 g. of residual oil. This is taken up in methylene chloride, filtered and the solvent evaporated to provide 43 g. of crude 3,5-dihydroxyisobutenylbenzene which is purified by chromatography on a silica gel column (1200 g.) eluting with mixtures of ethyl ether/methylene chloride to yield 31.9 g. of purified olefin. 1 H-NMR (CDCl 3 ) ppm (delta): 1.75 (d, 6H), 5.95 (s, 1 H), 6.05-6.35 (m, 3H), 6.50 (s, 2H).
To 16 g. of this olefin in 100 ml. ethyl acetate is added 1.6 g. 10% palladium/carbon and the mixture is hydrogenated at 3-4 atmosphere for 6 hours. Isolation of product in the usual manner affords 15.4 g. of material which is used in the next step.
1 H-NMR (CDCl 3 ) ppm (delta): 0.85 (d, 6H), 2.20 (d, 2H), 6.15 (s, 3H), 6.60 (s, 2H).
B. 5-Hydroxy-2,2-dimethyl-7-(2-methylpropyl)-3,4-dihydro-2H-benzopyran-4-one
A mixture of 20.3 ml. methanesulfonic acid and 1.0 g. phosphorus pentoxide under nitrogen is heated to 70° C. and 2.1 g. (12.7 mmole) of the product of Part A in 5 ml. ethyl ether is added. To this is added 1.27 g. (12.7 mmole) 3,3-dimethylacrylic acid and the mixture is maintained at 70° C. for 15 minutes then poured into ice/water and extracted with ethyl acetate. After washing of the extracts with water and brine, the extracts are dried (MgSO 4 ) and evaporated to provide a residual oil. Purification on a silica gel column, eluting with methylene chloride affords 1.04 g. of the desired product, R f 0.75, CH 2 Cl 2 ; 1 H-NMR (CDCl 3 ) ppm (delta): 2.30 (d, 2H), 2.65 (s, 2H), 6.10-6.25 (m, 2H), 11.6 (s, 7H).
C. A mixture of 2.0 g. of the product of Part B, above, 50 ml. acetone and 5.55 g. powdered potassium carbonate is stirred for five minutes and 1.38 g. of benzyl bromide is added. The mixture is stirred at reflux for 16 hours, cooled, filtered and the filtrate evaporated to provide an oil which gives crystals from cold hexane, M.P. 77.5°-78° C., 1.49 g. 1 H-NMR (CDCl 3 ) ppm (delta): 2.30 (d, 2H), 2.60 (s, 2H), 5.04 (s, 2H), 6.25 (s, 2H), 7.05-7.60 (m, 5H).
EXAMPLE 95
5-Benzyloxy-4-cyano-2,2-dimethyl-7-(2-methoxypropyl)-3,4-dihydro-2H-benzopyran
A. By the procedure of Example 84, Part A a mixture of 1.49 g. (4.43 mmole) 5-benzyloxy-2,2-dimethyl-7-(2-methylpropyl)-3,4-dihydro-2H-benzopyran-4-one, 10 ml. benzene, 0.8 ml. trimethylsilylnitrile, 30 mg. zinc iodide, 6 ml. pyridine and 3.5 g. phosphorus oxychloride are converted to 5-benzyloxy-4-cyano-2,2-dimethyl-7-(2-methylpropyl)-2H-benzopyran, 2.2 g. 1 H-NMR (CDCl 3 ) ppm (delta): 2.25 (d, 2H), 5.05 (s, 2H), 6.15 (s, 1H), 6.23 (s, 2H), 7.05-7.60 (m, 5H).
B. Hydrogenation of the above olefin by the method of Example 84, Part B, employing 1.94 g. magnesium turnings and 100 ml. methanol gives 12.3 g. of crude dihydro nitrile which is purified by silica gel chromatography, eluting with ethyl acetate/methylene chloride, 1:4. The product fractions yield 7.8 g. of the title compound. 1 H-NMR (CDCl 3 ) ppm (delta): 3.85 (t, 1H), 5.04 (s, 2H), 6.20 (s, 2H), 7.05-7.60 (m, 5H).
EXAMPLE 96
4-Nitrophenyl 5-benzyloxy-2,2-dimethyl-7-(2-methylpropyl)-3,4-dihydro-2H-benzopyran-4-carboxylate
A. 5-Benzyloxy-2,2-dimethyl-7-(2-methylpropyl)-3,4-dihydrobenzopyran-4-carboxylic acid
A mixture of 7.8 g. (22.2 mmole) of the product of the preceding Example, 12.5 g. KOH pellets and 200 ml. ethylene glycol are reacted by the procedure of Example 88, Part A to provide 8.25 g. of crude acid which is purified by silica gel chromatography, eluting with ethyl ether/methylene chloride, 1:4, ether alone and finally methanol/ethyl ether, 1:9 affords 6.13 g. which gave crystals from methylene chloride/hexane, M.P. 152°-153° C.
B. A mixture of 3.0 g. (8.15 mmole) of the acid obtained in Part A, 2.87 g. (12.2 mmole) p-nitrophenyl trifluoroacetate and 40 ml. dry pyridine is stirred at room temperature for 60 hours. The pyridine is evaporated in vacuo, the residue washed with 1N hydrochloric acid (3×25 ml.), 1N sodium hydroxide (4×25 ml.), water, brine and dried (MgSO 4 ). Evaporation of solent provides 4.0 g. of crude product as a foam which is crystallized from methylene chloride/hexane to give 3.67 g. of title compound, M.P. 125°-126° C.
EXAMPLE 97
5-Hydroxy-2,2-dimethyl-7-(2-methylpropyl)-3,4-dihydro-2H-benzopyran-4-carboxylic acid
The title compound, M.P. 185°-187° C. is obtained by catalytic hydrogenolysis of the corresponding 5-benzyl ether provided in Example 96, Part A, employing methods described above.
EXAMPLE 98
A. Employing the methods of Examples 89 and 92, but starting with the p-nitrophenyl ester provided in Example 96 and the appropriate amide or urea, the following compounds are obtained in like manner.
______________________________________ ##STR110##Q.sub.3 M.P. °C.______________________________________CONHCOCH.sub.3 156-157CONHCOCH(CH.sub.3).sub.2 117-120CONH.sub.2 206-207CONHCOC.sub.6 H.sub.5 --CONHtetrazol-5-yl -- ##STR111## --CONHCOC(CH.sub.3).sub.3 --CONHCOCH.sub.2 (CH.sub.3).sub.2 --CONHSO.sub.2 CH(CH.sub.3).sub.2 --CONHSO.sub.2 C.sub.6 H.sub.5 --______________________________________
EXAMPLE 99
A. Employing 3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-8-benzyloxy-1-tetralone (provided in U.S. Pat. No. 4,188,495) as starting material in the procedure of Example 84, Part A affords a quantitative yield of the corresponding unsaturated nitrile, 8-benzyloxy-1-cyano-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-3,4-dihydronaphthalene as an orange oil.
B. The oil from Part A above is hydrogenated by the procedure of Example 84, Part B to provide the corresponding tetralin, 8-benzyloxy-1-cyano-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin, in 89% yield as an orange oil.
C. The tetralin nitrile provided above is hydrolyzed in ethylene glycol with potassium hydroxide by the procedure of Example 88, Part A, to provide the corresponding acid, 8-benzyloxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-tetralin-1-carboxylic acid as a white foam in 39% yield.
D. A mixture of 1.6 g. of the product of Part C, above, 20 ml. methanol and 320 mg. 5% Pd/C catalyst is hydrogenated at three atmospheres pressure for three hours and the product isolated by filtration and evaporation of the filtrate to give 1.2 g. of colorless solid foam which is 92.5% pure mixture of diastereomers by HPLC analysis on a Zobax Sil (registered Trademark of E. I. duPont de Nemours and Co., Inc., Wilmington Del.) column, 2% isopropyl alcohol in hexane at 1 ml./minute. 1 H-NMR (CDCl 3 ) ppm (delta): 0.8 (s, 3H), 1.0 (s, 3H), 1.2 (d, 4H), 1.74 (m, 6H), 2.5 (m, 4H), 3.7 (m, 1H), 4.16 (m, 1H), 6.1 (s, 2H), 7.1 (s, 5H), 8.1 (broad s, 1H) which is in agreement with the structure for 8-hydroxy-3,3-dimethyl-6-(5-phenyl-2 -pentyloxy)tetralin-1-carboxylic acid.
E. Reaction of the above acid (3.14 mmole) with p-nitrophenyl trifluoroacetate (3.45 mmole) in pyridine (15 ml.) by the method of Example 91, Part B gives 1.1 g. (69%) of p-nitrophenyl 8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylate as a yellow oil.
F. Use of the benzyl ether provided in Part C, above, in the procedure of Part E, above, affords p-nitrophenyl-8-benzyloxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylate as an oil in 90% yield; TLC: R f 0.68 with hexane/ethyl acetate, 2:1 solvent.
EXAMPLE 100
8-Hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxamide
A. Reaction of 2.3 g. (3.9 mmole) p-nitrophenyl-8-benzyloxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylate in an excess of liquid ammonia at -70° C. for 30 minutes and evaporation of excess ammonia gives a yellow paste which upon silica gel chromatography eluting with 1:1 ethyl acetate/hexane yields 730 mg. of amide, R f 0.15 on TLC with 2:1 ethyl acetate/hexane solvent system. Starting material (1.15 g.) is also recovered.
B. Hydrogenations of the product of Part A in 50 ml. methanol with 400 mg. 5% Pd/C catalyst at 3 atmospheres pressure for 4.5 hours and work-up in the usual manner affords a crude product which is purified on a silica gel column using 2:1 ethyl acetate/hexane as solvent to give 130 mg. of title compound, as a white solid, M.P. 155°-157° C. 1 H-NMR (CDCl 3 ) ppm (delta): 0.8 (s, 3H), 1.0 (s, 3H), 1.16 (d, 3H), 1.7 (m, 6H), 2.47 (m, 4H), 3.57 (m, 1H), 4.16 (m, 1H), 6.1 (d, 3H), 7.2 (s, 5H).
C. Reaction of 0.55 g. (1.1 mmole) p-nitrophenyl 8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylate in 10 ml. tetrahydrofuran with an excess of methylamine (gas) at room temperature, pouring the resulting mixture into 10% hydrochloric acid, extracting with ethyl acetate and work-up in the usual manner affords 0.50 g, of the N-methyl amide: N-methyl 8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxamide as a foam.
1 H-NMR (CDCl 3 ) ppm (delta): 0.8 (s, 3H), 1.0 (s, 3H), 1.2 (d, 4H), 1.7 (m, 6H), 2.53 (m, 6H), 3.6 (m, 1H), 4.23 (m, NH), 6.2 (d, 2H), 7.13 (s, 5H).
EXAMPLE 101
8-Hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-tetralin-1-carbonyl urea
By reacting 1.2 g. (2 mmole) p-nitrophenyl 8-benzyloxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylate, 0.3 g. (5 mmole) urea and 0.248 g. (10 mmole) sodium hydride in 12 ml. dimethylsulfoxide at room temperature for one hour and isolation of product by the method of Example 89, Part B and removal of benzyl group by hydrogenolysis by the procedure of Example 89, Part C affords the pure title compound in 36% overall yield. 1 H-NMR (CDCl 3 ) ppm (delta): 0.77 (s, 3H), 1.1 (m, 8H), 1.7 (m, 4H), 2.5 (m, 4H), 3.6 (m, 1H), 4.16 (m, 1H), 5.7 (s, 1H), 6.1 (s, 2H), 7.1 (s, 5H), 8.2 (s, 2H).
EXAMPLE 102
Reacting 1.1 g. (1.9 mmole) p-nitrophenyl 8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylate, 1.0 g. (17 mmole) acetamide, 361 mg. (15 mmole) sodium hydride in 70 ml. tetrahydrofuran by the method of Example 89, Parts B and C, likewise provides 8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)-1-N-acetylcarboximide in 55% yield as a foam; 1 H-NMR (CDCl 3 ) ppm (delta): 0.7 (s, 3H), 1.0 (s, 3H), 1.16 (d, 3H), 1.6 (m, 6H), 2.3 (s, 3H), 2.5 (m, 4H), 3.73 (m, 1H), 4.13 (m, 1H), 6.1 (s, 2H), 7.1 (s, 5H), 8.5 (NH).
EXAMPLE 103
Ethyl 3-[8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-yl]-3-oxopropionate
A solution of 0.50 g. (1 mmole) 8-benzyloxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylic acid in 5 ml. ethyl ether is cooled to 0° C. and 0.25 g. (1.2 mmole) phosphorus pentachloride is added. The mixture is stirred at 0° C. for 30 minutes then at room temperature for 30 minutes. Evaporation of ether in vacuo affords the acid chloride as a brown oil.
In a separate flask 0.5 ml. (3.4 mmole) diisopropylamine in 6 ml. tetrahydrofuran is cooled to -78° C. and 1.4 ml. of 2.1M n-butyllithium is added and the mixture allowed to warm to 0° C. and stirred at 0° C. for 30 minutes. The mixture is then cooled to -78° C. and 0.30 ml. (3.1 mmole) ethyl acetate (dry, distilled) is added and the mixture is stirred at -78° C. for 2.5 hours. To this is added the above acid chloride in 2 ml. tetrahydrofuran and the mixture is stirred at -78° C. for two hours. The reaction is quenched with water, warmed to room temperature, poured into 10% hydrochloric acid and the mixture extracted with ethyl ether. The extracts are washed with water, brine and dried (MgSO 4 ). Evaporation of solvent affords 0.55 g. of yellow oil which is purified by chromatography on silica gel with 3:1 hexane ethyl ether as solvent to afford 0.13 g. (24%) of the benzyl ether of the title compound which is hydrogenated by the method of Example 89, Part C, to yield 110 mg. of colorless oil which is further purified by silica gel chromatography: 61 mg. (56%). 1 H-NMR (CDCl 3 ) ppm (delta): 0.8 (s, 3H), 1.07 (s, 3H), 1.2 (m, 7H), 1.7 (m, 5H), 2.53 (m, 4H), 3.5 (s, 2H), 3.8 (m, 2H), 4.13 (m, 2H), 6.13 (s, 2H), 6.5 (s, 1H), 7.13 (s, 5H). Mass spectrum (m/e): M + 452.
EXAMPLE 104
3-[8-Hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-yl]-3-oxopropionitrile
To a solution of 2.4 ml. of 2.1M n-butyllithium in 3.7 ml. tetrahydrofuran at -78° C. is added a solution of 0.26 ml. (5 mmole) acetonitrile in 3.7 ml. THF and the mixture is stirred for one hour at -78° C. A solution of 1.1 g. (2.0 mmole) p-nitrophenyl 8-benyzloxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-carboxylate in 3.7 ml. THF is added and stirring continued at -78° C. for 30 minutes. The reaction mixture is warmed to room temperature, quenched with 7 ml. 10% hydrochloric acid and extracted with ethyl ether. Isolation of product as in the preceding Example affords 1.13 g. of crude benzyl ether which gives 500 mg. of purified intermediate by silica gel chromatography: mass spectrum--molecular ion, 495.
Removal of the benzyl group by hydrogenolysis by the method of Example 89, Part C gives the pure title compound. 1 H-NMR (CDCl 3 ) ppm (delta): 0.8 (s, 3H), 1.06 (s, 3H), 1.2 (m, 5H), 1.7 (m, 4H), 2.5 (m, 4H), 3.5 (s, 2H), 4.0 (m, 2H), 6.1 (s, 2H), 7.1 s, 5H).
EXAMPLE 105
8-Hydroxy-1-trifluoroacetylaminomethyl-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin
To a suspension of 114 mg. (3 mmole) lithium aluminum hydride in 10 ml. ethyl ether at room temperature is added a solution of 1.36 g. (3.0 mmole) 8-benzyloxy-1-cyano-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin in 10 ml. tetrahydrofuran and the mixture is heated at reflux for two hours. After cooling to 0° C. 30 ml. ether is added and the reaction is quenched by addition of 150 ml. water, 150 ml. sodium hydroxide. Another 450 ml. water is added, the mixture is stirred for 15 minutes, filtered washing with ether and the separated organic layer is dried (MgSO 4 ) and concentrated to about 50 ml. volume. To this solution of crude amine 0.70 ml. triethylamine and 565 microliters (4.0 mmole) trifluoroacetic anhydride is added over a 15 minute period at room temperature. The mixture is then diluted with 50 ml. ether and washed with 10% hydrochloric acid (25 ml.), water (25 ml.), saturated sodium bicarbonate solution, brine and dried (MgSO 4 ). Evaporation of solvent and column chromatography of the residue on silica gel eluting with methanol/methylene chloride 1:9 gives 500 mg. of the benzyl ether of the title compound which is debenzylated by the method of Example 89, Part C, to afford 250 mg. of oil. Mass spectrum (m/e): 367, 337, 191, 91, 69.
1 H-NMR (CDCl 3 ) ppm (delta): 0.7 (s, 3H), 0.8 (s, 3H), 1.1 (d, 3H), 1.2-2.0 (m, 6H), 2.0-3.0 (m, 7H), 4.0 (m, 1H), 5.8-6.0 (m, 2H), 6.1 (NH), 7.0 (s, 5H).
EXAMPLE 106
Employing the procedures of Examples 84-105 the following compounds are obtained in similar manner ##STR112## where M, R 1 , R 4 , R 5 , Z and W are as previously defined and Q 3 is:
______________________________________ Q.sub.3______________________________________ 5-tetrazolyl COOCH.sub.2 C.sub.6 H.sub.5 COOC.sub.2 H.sub.5 COOCH(CH.sub.3).sub.2 COO(CH.sub.2).sub.3 CH.sub.3 CONHOH CONHCONH.sub.2 CONH.sub.2 CONHCH.sub.3 CONHCH.sub.2 CH(CH.sub.3).sub.2 CONH(CH.sub.2).sub.5 CH.sub.3 CONHCH(CH.sub.3).sub.2 CONHCH(CH.sub.3)(CH.sub.2).sub.3 CH(CH.sub.3).sub.2 CONHC.sub.6 H.sub.5 CONHCH.sub.2 C.sub.6 H.sub.5 ##STR113## ##STR114## ##STR115## ##STR116## ##STR117## CONHCOCH.sub.3 CONHCOC.sub.2 H.sub.5 CONHCO(CH.sub.2).sub.2 CH.sub.3 CONHCOCH(CH.sub.3).sub.2 CONHCOCH.sub.2 CH(CH.sub.3).sub.2 CONHCOCH(CH.sub.3)CH.sub.2 CH.sub.3 CONHCOC(CH.sub.3).sub.2 CONHCOC.sub.6 H.sub.5 CONHCOCH.sub.2 C.sub.6 H.sub.5 CONHCOCH.sub.2 CH.sub.2 C.sub.6 H.sub.5 CONHSO.sub.2 CH.sub.3 CONHSO.sub.2 CH(CH.sub.3).sub.2 CONHSO.sub.2 CH(CH.sub.3)(CH.sub.2).sub.3 CH.sub.3 CONHSO.sub.2 CH(CH.sub.3)CH.sub.2 CH.sub.3 CONHSO.sub.2 CH.sub.2 C.sub.6 H.sub.5 CONHSO.sub.2 C.sub.6 H.sub.5 CONHSO.sub.2 (4-CH.sub.3 C.sub.6 H.sub.4) CONHSO.sub.2 (3-NH.sub.2 C.sub.6 H.sub.4) CONHSO.sub.2 (4-FC.sub.6 H.sub.4) CONHSO.sub.2 (2-ClC.sub.6 H.sub.4) CONHSO.sub.2 (3-CH.sub.3 OC.sub.6 H.sub.4) ##STR118## COCH.sub.2 CN COCH.sub.2 COOH COCH.sub.2 CO.sub.2 C.sub.2 H.sub.5 ##STR119## ##STR120## ##STR121## ##STR122## ##STR123## ##STR124## ##STR125## ##STR126## ##STR127## ##STR128## ##STR129##______________________________________
EXAMPLE 107
2-[8-Acetoxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-yl]acetic acid
To a solution of sodium methoxide prepared from 0.2 g. sodium metal and 32 ml. methanol is added a solution of 0.20 g. (0.53 mmole) of the lactone of 2-[8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-yl]acetic acid and the mixture is stirred for 30 minutes. The methanol is evaporated in vacuo, the residue is cooled in ice and a cold solution of 6.4 ml. acetyl chloride in 12.8 ml. ethyl acetate is added and the resulting mixture stirred 15 minutes. The mixture is concentrated to dryness in vacuo, the residue taken up in fresh ethyl acetate, washed with water, brine and dried (MgSO 4 ) to yield 0.30 g. yellow oil. the oil is purified on a silica gel column using mixtures of methylene chloride and methanol as eluant to afford 110 mg. (47%) of title compound. 1 H-NMR (CDCl 3 ) ppm (delta): 0.8 (s, 3H), 1.03 (s, 3H), 1.23 (d, 4H), 1.7 (m, 6H), 2.3 (s, 3H), 2.5 (m, 4H), 2.9 (m, 1H), 3.13 (m, 1H), 4.2 (m, 1H), 6.4 (s, 2H), 7.13 (s, 5H).
EXAMPLE 108
2-[8-Hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-yl]acetamide
A solution of 0.76 g. (2 mmole) 2-[8-hydroxy-3,3-dimethyl-6-(5-phenyl-2-pentyloxy)tetralin-1-yl]acetic acid lactone in 10 ml. ethyl ether is added to an excess of liquid ammonia at -30° C. and the mixture stirred while warming to room temperature over two hours. Evaporation of solvent affords a solid white residue which is taken up in ethyl acetate, washed with water, brine and dried (MgSO 4 ). Evaporation of solvent yields 800 mg. (100%) of title compound, M.P. 67°-72° C. 1 H-NMR (CDCl 3 ) ppm (delta): 0.86 (s, 3H), 1.06 (s, 3H), 1.26 (d, 5H), 1.7 (m, 6H), 2.6 (m, 6H), 3.4 (m, 1H), 4.26 (m, 1H), 5.6 (m, 2H, NH 2 ), 6.2 (m, 2H), 7.2 (s, 5H). | Bicyclic fused benzenoid compounds of the formula ##STR1## and pharmaceutically acceptable cationic and acid addition salts thereof, where M is O, CH 2 or NR 6 ; R 6 is hydrogen, formyl, carbobenzyloxy or certain carboalkoxyalkyl, alkanoyl, alkyl, aralkyl or aralkylcarbonyl groups;
A' is:
(1) A where one of A and B is hydrogen such that when A is hydrogen, B is C(R 2 R 3 )(CH 2 ) f Q and f is 1 or 2; when B is hydrogen, A is C(R 2 R 3 )(CH 2 ) f Q and f is 0 or 1, when taken together A and OR 1 form a lactone or certain derivatives thereof;
(2) A' is ##STR2## (3) A' is Q 3 ; Q is CO 2 R 7 , COR 8 , C(OH)R 8 R 9 , CN, CONR 12 R 13 , CH 2 NR 12 R 13 , CH 2 NHCOR 14 , CH 2 NHSO 2 R 17 or 5-tetrazoyl;
Q 3 is ##STR3## 5-tetrazolyl, CH 2 CONHCOR 7 , COOH or certain ester, amide, carboximido or sulfonimido derivatives thereof, CONHOH, CONHCONH 2 , or COCH 2 Q 4 where Q 4 is CN or COOH or certain esters thereof;
R 1 is hydrogen, benzyl or certain acyl groups; R 4 is hydrogen, certain alkyl or certain aralkyl groups; R 5 is hydrogen or certain alkyl groups; Z is (C 1 -C 9 )alkylene, optionally interrupted by O, S, SO or SO 2 ; and W is hydrogen, methyl, certain aryl or cycloalkyl groups; useful in mammals as analgesics, tranquilizers, anteimetic agents, diuretics, anticonvulsants, antidiarrheals, antitussives, in treatment of glaucoma, and intermediates therefore. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 09/741,524, filed Dec. 20, 2000, now U.S. Pat. No. 6,375,435, and claims priority to U.S. Provisional Patent Application No. 60/236,293, filed Sep. 28, 2000, both of which are herein incorporated by reference in their entirety to the extent they are not inconsistent with this disclosure.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The subject invention relates to fuel pumps for gas turbine engines, and more particularly, to vane pumps which are used in applications that require high operational reliability and a predicted failure mode.
2. Background of the Related Art
Vane pumps are being developed within the aerospace industry as an alternative to traditional gear pumps. An example of a variable displacement vane pump is disclosed in U.S. Pat. No. 5,545,014 to Sundberg et al., the disclosure of which is herein incorporated by reference in its entirety to the extent that it does not conflict with the present disclosure.
Vane pumps traditionally include, among other things, a housing, a cam member and a rotor supported within the housing by axially opposed journal bearings. The housing defines an interior chamber, a fluid inlet and a fluid outlet and the cam member and rotor are disposed within the interior chamber. The cam member has a central bore which defines the circumferential boundary of the internal pumping chamber. Mounted for rotational movement within the central bore of the cam member, is a rotor supported by axial opposed journal bearings. The rotor element has circumferentially spaced apart slots machined therein which support corresponding radially movable vane elements.
Variable displacement vane pumps differ from other vane pumps, such as fixed displacement vane pumps, in that the cam member pivots about a fulcrum aligned with the vertical centerline of the pump, thereby adjusting its position with respect to the rotor. This adjustment allows the relative volumes of the inlet and discharge buckets to be changed and thereby vary the displacement capacity of the pump.
In a single rotation, the vanes of the rotor element of the pump traverse at least four distinct arcuate regions which make up the 360 degree revolution. The first region is the inlet arc segment in which fluid is received into the pumping chamber and over this region the bucket volume increases. The second region is the discharge arc segment in which pressurized fluid is discharged from the pumping chamber and over this region the bucket volume decrease. Lastly, seal arc segments separate the inlet and discharge arc segments and represent the regions through which the bucket volume remains substantially constant.
In operation, fluid at a first pressure is fed into the pumping chamber through the housing inlet, and into the space defined between adjacent vane elements, known as the bucket. In positive displacement vane pumps, as the vane elements rotate within the pumping chamber from the inlet region to the outlet region, the configuration of the cam member causes the vanes to retract within the corresponding slots. This causes the volume defined by the bucket to decrease. Since the amount of fluid received into an inlet bucket is greater than that contained within the corresponding discharge bucket, a fluid volume equivalent in size to the volumetric difference is discharged or displaced through the outlet port at a pressure equal to the downstream pressure which must be overcome.
Typically, pumping pressures and velocities are so high within the pump housing that the use of heavy, high wear resistant materials for the cam member and the vane elements becomes necessary to handle the wear which is caused by these high levels of pressure and velocity.
Prior variable displacement vane pumps are illustrated in U.S. Pat. No. 5,545,014 to Sundberg et al. and U.S. Pat. No. 5,833,438 to Sundberg. U.S. Pat. No. 5,545,014 discloses a durable, single action, variable displacement vane pump capable of undervane pumping and a pressure balancing method. U.S. Pat. No. 5,833,438 to Sundberg teaches a variable displacement vane pump having a durable rotor member with journal ends at each side of a large diameter central vane section and a mechanism for confining the high pressure within the cam member and thereby preventing axial pressure leakage along the length of the rotor member. The disclosure contained within these patent is hereby incorporated by reference in their entirety to the extent it does not conflict with the present disclosure.
The advantages of variable displacement pumps over conventional pumps, namely gear pumps, is that they solve the problem where excess heat generation becomes a crucial impediment to pump performance. Also, a variable displacement vane pump can be used to eliminate certain fuel flow metering components by utilizing the pump as the metering device.
One of the disadvantages associated with vane pump technology is the failure mode. As a result, there is a reluctance to implement this technology in applications, such as high performance aircraft, that require high operational reliability and a predicted failure mode. With a conventional gear pump, the failure mechanism is well known. Typically as the pump degrades, the performance drops off far enough so that eventually one cannot start the engine, thus a safe failure occurs. With a vane pump, however, as the vanes wear away due to contact with the cam surface, the cantilevered load that the pressure puts on each vane can become so high that a catastrophic failure of a vane can occur during pump operation and effectively destroys the whole pumping system without warning. In an applications such as helicopter fuel systems, this type of failure can cause damage to the control system and engine. In order to prevent such an occurrence, the vane pump must be inspected and maintained frequently.
In view of the foregoing, a need exists for an improved vane pump which resembles the failure mode of a gear pump by “tracking” wear of the vanes, and disabling the engine from starting after a certain level of wear is attained.
SUMMARY OF THE INVENTION
The subject application is directed to vane pumps for use with gas turbine engines which include a mechanism for altering the failure mode of the pump thereby preventing an operational failure. In a preferred embodiment, the vane pump includes a pump housing, a cam member, a rotor member and a mechanism for communicating a high pressure fluid from the discharge arc region to the inlet arc region so as to prevent pump start-up when a predetermined wear state has been reached.
The pump housing typically includes a cylindrical interior chamber which defines a central axis through which a vertical centerline and a horizontal centerline extend. The cam member is mounted for pivotable movement within the interior chamber of the pump housing about a fulcrum aligned with the vertical centerline of the interior chamber. The cam member has a bore extending therethrough which defines a circumferential surface of a pumping cavity. The circumferential surface of the pumping cavity includes a discharge arc segment, an inlet arc segment and seal arc segments separating the inlet arc segment and the discharge arc segments from one another.
The cylindrical rotor member is mounted for rotational movement within the bore of the cam member about the central axis of the interior chamber. The rotor member has a central body portion with first and second axially opposed end surfaces and a plurality of circumferentially spaced apart radially extending vane slots formed therein. Each vane slot supports a corresponding vane element mounted for radial movement therein. Each of the vane elements have a radially outer tip surface which is adapted for slideably engaging the circumferential surface of the pumping cavity and a radially inner undervane portion which is positioned within each vane slot.
The mechanism for communicating a high pressure fluid from the discharge arc region to the inlet arc region so as to prevent pump start-up activates when the tip surface of each vane element has worn a predetermined amounted with respect to the undervane portion of each vane element.
In a preferred embodiment, the mechanism for communicating a high pressure fluid from the discharge arc region to the inlet arc region when the tip surface of each vane element has worn a predetermined amount includes arcuate channels formed in the first end surface of the body portion of the rotor member. The arcuate channels each extend between each vane slot. It is envisioned that the arcuate channels are spaced from the central axis by a radial distance and the radial distance defines the predetermined amount of wear.
In an alternate embodiment, the means for communicating a high pressure fluid from the discharge arc region to the inlet arc region when the tip surface of each vane element has worn a predetermined amount includes arcuate channels formed in the second end surface of the body portion of the rotor member
It is presently preferred that the predetermined amount of wear is reached when the undervane portion of each vane element at a point in the pumping cavity is positioned radially outward of the arcuate channels formed in the body portion of the rotor. As a result of this relative positioning, fluid is allowed to communicate from the discharge arc segment to the inlet arc segment of the pumping cavity.
The circumferential surface of the pump cavity includes a discharge arc segment of about 150 degrees, a first seal arc segment of about 30 degrees, an inlet arc segment of about 150 degrees and a second seal arc segment of about 30 degrees.
It is further envisioned that first and second axially spaced apart end plates are disposed within the interior chamber of the pump housing. Each end plate has a first surface which is adjacent to the rotor member and forms an axial end portion of the pumping cavity. Each end plate is spaced from the rotor member so as to allow frictionless rotation of the rotor member within the pumping cavity. Preferably the end plates include a mechanism associated with the first surface of each end plate for communicating fluid from the discharge arc segment of the pumping cavity to the undervane portion of each vane element when each vane element passes through the discharge and seal arc segments. Additionally, the first surface of each end plate includes a mechanism for communicating fluid from the inlet arc region of the pumping cavity to the undervane portion of each vane element when each vane element passes through the inlet arc segment as the rotor member rotates about the central axis.
It is presently envisioned that the rotor member further includes a plurality of substantially axial fluid passages formed in the central body portion of the rotor. Each passage is positioned between the plurality of circumferentially spaced apart radial vane slots and provides a path through the rotor body portion for fluid to communicate axially from the pumping cavity to the first and second end plate.
The subject application is also directed to a vane pump which includes, among other things, a pump housing a cam member, a rotor member. The rotor member being substantially cylindrical and mounted for rotational movement within the bore of the cam member about the central axis of the interior chamber. The rotor member includes a central body portion with first and second axially opposed end surfaces and a plurality of circumferentially spaced apart radially extending vane slots formed therein.
It is envisioned that each vane slot supports a corresponding vane element mounted for radial movement therein. Each vane element has a radially outer tip surface adapted for slideably engaging the circumferential surface of the pumping cavity and a radially inner undervane portion within each vane slot. Preferably, the first end surface of the body portion has arcuate channels formed therein which extend between each vane slot. The arcuate channels providing a path for high pressure fluid to leak from the discharge arc segment to the inlet arc segment of the pumping cavity when each vane tip surface has worn such that the undervane portion is positioned radially outward of the arcuate channels.
In a preferred embodiment, the arcuate channels are spaced from the central axis by a radial distance whereby the radial distance defines an amount of allowable vane tip surface wear which can occur before high pressure fluid can leak from the discharge arc segment to the inlet arc segment of the pumping cavity.
The present application is also directed to a vane pump which includes a pump housing, a cam member, a rotor member, a leak path, first and second axially spaced apart end plates. The leak path communicates fluid from the discharge arc region to the inlet arc region when the cam member is in a start-up position and each undervane portion is positioned radially outward of the leak path. It is envisioned that the leak path includes arcuate channels formed in the first end surface of the body portion of the rotor member which extend between each vane slot.
Those skilled in the art will readily appreciate that the inventive aspects of this disclosure can be applied to any type of vane pump, such as fixed or variable displacement vane pumps.
BRIEF DESCRIPTION OF THE DRAWINGS
So that those having ordinary skill in the art to which the present application appertains will more readily understand how to make and use the same, reference may be had to the drawings wherein:
FIG. 1 is a cross-sectional view of a variable displacement vane pump constructed in accordance with a preferred embodiment of the present application which includes a pump housing, a pivotal cam member, and a rotor member with associated vane elements;
FIG. 2 is a side elevational view in cross-section of the vane pump of FIG. 1 illustrating the manner in which fluid is received into and discharged from the pumping chamber;
FIG. 3 is a side elevational view of the face of the end plate of the pump of FIG. 1 illustrating a series of channels and recesses formed therein;
FIG. 4 is a cross-sectional view of the rotor of FIG. 2, the rotor having arcuate recesses or channels cut in each end of the body portion between adjacent vane slots;
FIG. 5 is a side elevational view taken in cross-section of the rotor member of the vane pump of FIG. 1 illustrating arcuate channels formed in an end of the rotor for allowing high pressure fuel to communicate with the low pressure side of the sealing arc when a pre-established vane wear state has been reached; and
FIG. 6 is an enlarged localized cross-sectional view of a variable displacement vane pump in the worn state wherein fuel communicates from the high pressure side of the pumping chamber to the low pressure side of the sealing arc.
These and other features of the vane pump of the present application will become more readily apparent to those having ordinary skill in the art form the following detailed description of the preferred embodiments.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
Referring now to the drawings wherein like reference numerals identify similar structural aspects of the subject invention, there is illustrated in FIG. 1 a variable displacement vane pump constructed in accordance with a preferred embodiment of the subject application and designated generally by reference numeral 10 . Vane pump 10 includes a pump housing 12 defining an interior chamber which supports a cam member 14 and a rotor member 16 . Rotor member 16 includes a plurality of radially extending slots 17 . Each slot is configured to support a corresponding vane element 18 . Cam member 14 is mounted for pivotal movement within pump housing 12 about a pivot pin 20 that defines a fulcrum, so as to vary the displacement of vane pump 10 . Cam member 14 includes a one-piece body that defines a bore 22 forming a cam chamber. The circular bore 22 defines a smooth continuous circumferential surface 24 of the pumping cavity, making continuous contact with the outer tip surfaces 21 of each vane element 18 . A lever 25 extends from the body of cam member 14 and is pivotably connected to actuation piston assembly 15 , for varying the position of the cam member 14 relative to the rotor member 16 .
As illustrated in FIG. 1, each vane element 18 fits snugly within a corresponding slot 17 and functions like a piston as it is depressed radially inwardly during movement of the rotor member 16 through the high pressure discharge arc region 62 (FIG. 3) of the pumping chamber. Each slot 17 has a radially inner undervane cavity 19 defining an area that is open to low inlet pressure when the vane element 18 is in the inlet arc region 60 ( FIG. 3) of the pumping chamber, and to high discharge pressure when the vane element 18 is in the discharge arc region 62 of the pumping chamber and the seal arc regions 64 a and 64 b (FIG. 3) of the pumping chamber. The manner in which pressurized fluid is communicated to the undervane cavity will be described in more detail herein below with respect to FIG. 3 .
Referring to FIG. 2, vane pump 10 further includes an inlet region 50 for admitting low pressure fluid into the pumping chamber and a discharge region 52 for discharging high pressure fluid from the pumping chamber. A main drive shaft 32 extends through the interior chamber of pump housing 12 along the longitudinal axis thereof for driving a central shaft member 34 . Shaft member 34 is supported for rotation by opposed journal bearings 36 a and 36 b, and is keyed to rotor member 16 for imparting rotational motion thereto.
Opposed sideplates 40 and 42 , which are disposed within the interior chamber, form a sealed cavity between cam member 14 and rotor member 16 , and provide inlet and discharge ports for the cavity. Axial spacer 30 is supported within the housing 12 , between sideplates 40 and 42 , and has a thickness that is slightly greater than the thickness of cam member 14 . This allows the sideplates 40 and 42 to be tightly clamped against the spacer 30 by a plurality of threaded fasteners (not shown) while allowing small gaps to remain between the cam member 14 and the sideplates to reduce or eliminate friction therebetween.
Referring now to FIG. 3, surface 44 of side plate 40 is disposed adjacent rotor member 16 . The 360 degree pumping chamber includes an inlet arc region 60 , a discharge arc region 62 and sealing arc regions 64 a and 64 b positioned between the inlet and discharge arc regions 60 and 62 . The inlet arc region 60 represents the portion of the pumping chamber in which the volume contained between adjacent vane elements (i.e., within the buckets) increases and low pressure fluid is received into the pumping chamber. The discharge arc region 62 is the portion of the pumping chamber in which the volume contained between adjacent vane elements decreases. In the seal arc regions 64 a and 64 b, the volume remains substantially constant.
When the rotor 16 rotates within the pumping chamber, the centrifugal force created thereby imparts a radially outward force on each vane elements 18 . In addition, the pressurized fluid contained within adjacent buckets imparts a radially inward force on each adjacent vane element 18 . Often, the opposed forces which are applied to each vane element 18 are not balanced. As a result, the vane tip 21 of each vane 18 is either subjected to excessive wear due to a net radially outward force or fluid leaks from within the bucket due to a net radially inward force. This reduces pumping efficiency. An ideal pump operating condition occurs when the pressure applied to the vane elements is balanced and the vane elements “float” within the slots defined in the rotor. This condition results in minimum wear to the vane tips and minimizes the pressure losses caused by the lack of contact between the vane tips and the cam member.
Pump 10 is adapted and configured to correct the unbalanced vane condition by applying pressure to the undervane portion 23 of each vane element 18 . More specifically, low pressure from within each bucket traversing the inlet region 60 is supplied to the undervane portion 23 of vane elements 18 within the inlet arc region 60 . Similarly, the undervane portion 23 of the vanes traversing the discharge arc region 62 and the seal arc regions 64 a and 64 b are supplied with high pressure from the buckets located in the discharge arc region 62 . The pressure, in the form of pressurized fluid, is supplied from the inlet arc region 60 and discharge arc region 62 to the undervane portion 23 of each vane element 18 by way of flow ports machined in the rotor body portion and by providing end plates which have flow channels formed therein.
Referring to FIGS. 4 and 5, the body portion 19 of rotor 16 includes a plurality of flow ports 84 formed therein. Each flow port 84 is positioned between the plurality of circumferentially spaced apart radial vane slots 17 and provides a path for fluid to flow from the pumping cavity to channels 66 i and 66 d ( see FIG. 3) formed in end plate 40 , or in both end plate 40 and 42 . Each flow port 84 is substantially T-shaped and includes a radial conduit 85 and an axial conduit 86 .
This feature is advantageous because fluid must travel radially inward from the bucket into each flow port 84 , against the centrifugal force created by the rotation, so that the fluid is effectively filtered prior to entering each flow port 84 . Moreover, particulate contained within the fluid in the pumping chamber is forced radially outward by the centrifugal motion, leaving particulate free fluid on the radially inner portion of the bucket.
Referring now to FIG. 3, arcuate outer channels 66 i and 66 d are formed in face 44 of endplate 40 and are in fluid communication with the inlet and discharge arc regions, 60 and 62 , respectively by way of flow ports 84 of rotor member 16 . Low pressure fluid from the inlet arc region 60 is received into arcuate outer channel 66 i and then flows radially inward through passages 68 a-e to arcuate inner channel 69 i. The passages 68 a-e and the inner channel 69 i are also formed in face 44 of side plate 40 . Inner channel 69 i communicates with the undervane portion of each vane element 18 positioned within the inlet arc region 60 .
In a similar manner, on the discharge side of the pumping chamber, high pressure fluid from within the discharge arc region 62 is received by arcuate outer channel 66 d. The fluid then flows radially inward through passages 67 a-d to arcuate inner channel 69 d. As before, the passages 67 a-d and the inner channel 69 d are each machined into face 44 of side plate 40 . Arcuate inner channel 69 d communicates with the undervane portion of each vane element 18 positioned within the discharge arc region 62 and the sealing arc regions 64 a and 64 b. One skilled in the art would readily appreciate that the quantity of channels and passages can be varied depending on the configuration of the pump and the associated operating pressures.
The communication of pressurized fluid through the above described series of ports and channels to the undervane portion of each vane element functions to balance the forces imparted on the vanes or at least to ensure that a net force directed radially outward is applied thereto.
As mentioned above, one of the disadvantages associated with vane pump technology is the failure mode. Unlike conventional gear pumps, which will not start up when the pumping elements have experienced a pre-determined amount of wear, traditional vane pumps fail without warning and often catastrophically during pump operation.
Fuel pump 10 is adapted and configured to change the failure mode normally associated with vane pump technology to one which is substantially similar to that of gear pumps. As illustrated in FIGS. 3 and 4, a series of leak paths 87 a and 87 b are formed in ends 92 a and 92 b of body portion 19 of rotor member 16 . These leak paths 92 a and 92 b allow high pressure which is contained with arcuate outer channel 66 d, arcuate inner channel 69 d and passages 67 a-d to flow into the low pressure inlet arc region 60 when the vane elements 18 have worn such that the undervane portion 23 is positioned radially outward of leak paths 87 a and 87 b.
More specifically, in a variable displacement vane pump, maximum vane protrusion from within the corresponding slot occurs when cam member 14 is disposed in the position corresponding to pump start-up, as illustrated in FIG. 1 . As depicted, in the pump start-up position, the vane elements 18 located in sealing arc region 64 a are subjected to the maximum protrusion from within the vane slots 17 . When vane pump 10 is new and not worn, the undervane portion 23 of each vane element 18 prevents fluid from flowing into leak paths 87 a and 87 b. However, as the vane tips 21 wear due to their contact with the circumferential surface 24 of the pumping cavity, the radial position of the undervane portion 23 of each vane element 18 with respect to leak paths 87 a and 87 b is altered. Eventually, the vane elements 18 wear to the extent that the undervane portion 23 is positioned radially outward of the leak paths 87 a and 87 b, and can no longer prevent fuel from leak paths 87 a and 87 b. Consequently, the leak paths 87 a and 87 b formed in rotor 16 begin to slowly communicate high pressure fuel to the low pressure inlet side of the sealing arc 64 a.
Referring now to FIG. 6, vane elements 18 of vane pump 10 are shown in a worn condition. As the vane elements 18 wear, it is through the channels or recesses formed in the end plates, that the high pressure communicates to the low pressure side of the pump. As wear continues further, this communication becomes more pronounced and substantial. Eventually, a certain level of leakage through this path is achieved such that the ability of the pump to provide sufficient flow to start the engine becomes diminished and start-up cannot occur. Thus, it will be necessary to remove the pump for overhaul prior to attaining a point where failure due to an overloaded vane is imminent and a major failure can be avoided.
The failure mode only affects the engine's ability to start. Higher leakage during operation is not critical to the survival of a mission and therefore there is no danger that the additional leakage will interfere with engine operation. This operational scenario is identical to that of a gear pump.
The radial position of the leak paths 87 a and 87 b are established based on the configuration and size of the pumping components and the material properties of the vane elements. The leak path location is selected so that the above-described failure mode is ensured and catastrophic operational failures are avoided.
It is envisioned that the porting connections of the pump can be achieved through a variety of methods. Pump configurations can use various cuts in cams, sideplates and rotors to communicate different pressures for different reasons including, but not limited to, bearing lubrication, pressure balancing and the like. The preferred embodiment of the invention utilizes porting cuts in the rotor to provide for a controlled failure mode thus providing the vane pump with operational reliability similar to that of a gear pump.
While the invention has been described with respect to preferred embodiments, those skilled in the art will readily appreciate that various changes and/or modifications can be made to the invention without departing from the spirit or scope of the invention as defined by the appended claims. | A vane pump is disclosed for use with gas turbine engines adapted and configured to provide a failure mode similar to that of a traditional gear pump. The vane pump includes a pump housing, a cam member, a cylindrical rotor member and a mechanism for communicating a high pressure fluid from the discharge arc region to the inlet arc region when the tip surface of each vane element has experienced a predetermined amounted of wear so as to prevent pump startup. The wearing of the tip surface of each vane element resulting from the slideable engagement with the circumferential surface of the pumping cavity. | 5 |
This is a division, of application Ser. No. 227,984 filed Jan. 23, 1981 now abandoned.
BACKGROUND OF THE INVENTION
In laser reaction systems a target of selected material, usually in a vacuum chamber, is exposed to one or more high power laser beams for the purpose of inducing a reaction such as thermonuclear fusion. Whether or not such a reaction occurs the radiation power involved (15 to 30 joules per square centimeter) causes the target to eject debris of macroscopic size as well as in sub-molecular size and electromagnetic wave form. Similarly bombardment of targets with other high energy beams such as accelerated particles produces such reaction debris. Escape of such debris from the reaction chamber is undesirable for several reasons including the risk of contamination of very expensive laser optical components between the chamber and the laser.
Plain sheet or film epoxy resin has been sold and has experimentally been found effective as a non-distorting window for high power laser beams and as a shield of laser fusion debris. However, a satisfactory way of mounting thin epoxy films as debris shields has not previously been found, and it is one object of the present invention to provide a way of mounting an epoxy film in a laser or other high energy reaction debris shield. A further object is to provide optically active laser reaction debris shields.
STATEMENT OF INVENTION
According to the invention a method of making a high energy reaction debris shield comprises applying to the opposable faces of two supports a release coat; applying a liquid, transparent epoxy compound on the coat of one support and pressing the two supports face to face to shape an epoxy shield between the faces, and allowing the epoxy to cure; removing at least one support at the release coat and attaching a holder at the periphery of the shield; and removing the protective coat from the shield to form a window optically transparent and physically resistant to the high energy to and physically obstructive of reaction debris.
Further according to the invention a high energy reaction debris shield comprises a window of clear epoxy resin compound optically transparent to the high energy and physically obstructive of laser reaction debris, and having at least one optically active, non-planar face such as a converging lens or other lenticular element.
Still further the invention relates to the shield itself with a frame attached to its periphery, particularly a ring attached to a circular epoxy shield.
DRAWING
FIG. 1 is a schematic view of a laser fusion system with a shield;
FIGS. 2 to 5 are side elevations showing the steps of making a shield;
FIG. 6 is a plan view of the shield; and
FIG. 7 is a sectional elevation of an alternative form of shield in the process of manufacture corresponding to FIG. 3.
DESCRIPTION
The laser fusion system shown in FIG. 1 comprises a laser A transmitting a coherent beam B of light radiation at 1.06 microns, for example. Other high energy sources such as accelerated particles may be used. The beam is directed into a reaction chamber C, usually evacuated, through an entrance E enclosing a focussing lens L and a shield S which is the subject of this invention, to target T of fusible material, for example. The target T, under the intense power of the laser beam ejects macroscopic fragments D in all directions, the directions indicated by the arrows back toward the entrance E being of concern. The shield S serves to obstruct ejection of this debris out the entrance E as well as admitting the laser beam to the target while maintaining the optical quality of the beam with minimum distortion of the transmitted wavefront.
FIGS. 2 to 6 illustrate the method of making one new form of laser fusion debris shield. Two circular glassy or metal blank supports 1 and 2 have polished, optically flat faces 3 and 4 which are to be opposed. First each face is coated with a layer of release or parting agent 6, typically by vapor deposition, although other techniques, such as spinning, may be used to provide the very uniform film that is required. Then a thin protective film 7 of aluminum, for example, is applied by vapor deposition over the release coat 6 if needed. A thin film of gold may serve as a release and a second film omitted. On the coat 6, 7 of one support 2 is poured a bead 8 of liquid, transparent epoxy compound. A suitable compound is a 10 to 1 viscous mixture of an epoxy resin with terminal epoxide groups and a liquid polyamine curing agent. The prepared face 3 of the other support 1 is then pressed down by its own weight or otherwise, face to face, over the epoxy compound, spreading the epoxy so as to shape a shield disc layer 8* (FIGS. 3 to 6) uniformly a few thousandths of an inch thick (e.g. 0.001 to 0.005). The epoxy shield is then allowed to cure.
When the epoxy shield is cured the upper blank support 1 is lifted off the shield parting at the upper release layer 6, leaving a film 7 of aluminum over the epoxy shield 8* (FIG. 4). Preferably an annular area around the periphery of the circular shield is cleaned of its exposed aluminum film by abrasion or by a solution of sodium hydroxide and water in the proportion of one cup to five gallons of water. A frame or holder comprising a ring 9 of at least the peripheral dimension (diameter) of the shield is then adhered with epoxy cement to the cleaned peripheral area of the epoxy shield (FIG. 4), preferably while it is still on the lower blank support 2. The ring may be aluminum or other material with a coefficient of thermal expansion close to that of epoxy. When the cement is cured the shield disc 8* and its attached holder 9 are parted from the lower support 2. The remaining protective aluminum film is then removed from the two sides of the epoxy disc leaving the completed shield S. (FIGS. 5 and 6)
A debris shield so made has a high optical quality, passing 1.06 micron laser radiation with a transmitted wave front of one tenth to one half wavelength irregularity. It is of sufficient optical quality and structure to resist damage from the high power density of the laser beam. And with the peripheral support described it is particularly effective to protect the optical elements such as the lens L, the mirrors M and the laser A itself from the fusion debris. The framing ring 9 also facilitates mounting the shield in an optical barrel such as the reaction chamber entrance E.
As shown in FIGS. 7 and 8, instead of being the passive plano-plano element of FIGS. 5 and 6, the debris shield may be optically active in the sense of focussing, refracting, collimating, diffracting or similarly controlling an incident light beam. In FIG. 7 the blank supports 1A and 2A, instead of having the optically flat faces 3 and 4 as in FIG. 2, have opposed concave faces 3A and 4A forming a double convex cavity between them. Either of these faces might be planar or concave. Each face has a release layer 6 and a protective layer 7 conforming to the planar or non-planar face of its support. A double convex lenticular epoxy shield 8A formed therein according to the previously described method serves not only as a laser beam window and reaction debris shield but also as a focussing lens, replacing the function of the lens L as well as the shield S in FIG. 1. Such a lenticular shield may be mounted on a ring or otherwise shaped holder as previously described and assembled in an optical barrel like the entrance E to the vacuum chamber of FIG. 1.
It should be understood that the present disclosure is for the purpose of illustration only and that this invention includes all modifications and equivalents which fall within the scope of the appended claims. | A shield for admitting laser beams to a target in a reaction chamber while obstructing exit of target ejected debris from the chamber is formed by coating the opposable faces of two supports with a layer of release agent and a coating protecting the release layer. A bead of transparent epoxy compound is then pressed between the two supports to form an epoxy shield. While the shield is on one support a framing holder is epoxied to the shield. | 6 |
TECHNICAL FIELD
[0001] The present invention relates to a method for sizing paperboard to provide resistance to hot penetrants. This method can he used for aseptic packaging board to provide resistance to both the hot hydrogen peroxide solution that is used to sterilize the package as well as the liquid that is to be packaged in the container.
BACKGROUND OF INVENTION
[0002] For some time liquid products, and in particular liquid dairy products such as milk and cream, have been packaged in containers made of coated paperboard. This board, known in the industry as liquid packaging board, is typically coated on both sides with polyethylene.
[0003] To be functional in this application, the board must be resistant to the effects of the liquid. For liquid dairy products, the most aggressive component of the liquid is generally lactic acid. The most vulnerable portion of the board is usually the cut edge. It is known that board sized with AKD (alkyl ketene dimer) has good resistance to edge penetration by lactic acid-containing liquids.
[0004] In recent years there has been a trend toward aseptic packaging of consumable liquids. Aseptic containers are formed from a composite structure consisting of coated or uncoated paperboard, polyethylene and aluminum foil. The board is sterilized before filling by passing through a hydrogen peroxide solution at elevated temperature.
[0005] Therefore this board must resist not only the liquid that will ultimately be packaged in the container, but the hot hydrogen peroxide solution used to sterilize the container as well. The AKD based sizing agents that are known to provide superior resistance to edge penetration by lactic acid containing liquids were found to be only moderately effective against hot hydrogen peroxide solutions (see for example U.S. Pat. No. 4,927,496, U.S. Pat. No. 5,308,441, U.S. Pat. No. 5,456,800, U.S. Pat. No. 5,626,719). Rosin based sizing agents have been demonstrated to provide the needed resistance to hot hydrogen peroxide solutions, but are not as effective against the acidic materials packaged in these containers (see for example U.S. Pat. No. 4,927,496, U.S. Pat. No. 5,308,441, U.S. Pat. No. 5,456,800, U.S. Pat. No. 5,626,719)).
[0006] As a consequence, a dual sizing system is used for aseptic packaging grades. Both AKD and rosin are used to provide sizing in aseptic packaging, either with both sizing agents added internally (U.S. Pat. No. 4,927,496) or with one used internally and the other added on the surface (U.S. Pat. No. 5,308,441). Unfortunately the optimum pH for rosin sizing efficiency, about pH 5, is lower than the optimum pH for AKD sizing efficiency, about pH 7.5. Therefore, the system is run at a compromise pH for both sizing agents, about 6.5, resulting in less than optimal performance (U.S. Pat. No. 7,291,246). Additionally, the system is cumbersome since typically two sizing agents must be inventoried and metered into the papermaking system.
[0007] Previous attempts to address these shortcomings include the use of a combination of cellulose reactive and non-reactive sizing agents with thermosetting resins (U.S. Pat. No. 5,456,800, U.S. Pat. No. 5,626,719) and the use of catalase or manganese ore to decompose the hydrogen peroxide to form oxygen gas that forms a protective gas layer which prevents penetration of the paperboard (U.S. Pat. No. 7,291,246).
[0008] U.S. Pat. Nos. 4,859,244 and 3,311,532 disclose paper sizing agents composed of blends of fatty acid anhydrides and alkyl ketene dimers that provide improved sizing. However, neither discusses the problem caused by sterilization by hot hydrogen peroxide, nor is there any indication that the sizing agents disclosed would have any effect on resistance to edge penetration by hot hydrogen peroxide or other hot penetrants. Additionally, U.S. Pat. No. 4,859,244 teaches that “the sizing quality is substantially unaffected by the presence of alum”, providing data that demonstrates equal performance with and without alum in the system.
BRIEF SUMMARY OF THE INVENTION
[0009] The present invention addresses the shortcomings of the use of a dual sizing system to achieve the sizing requirements of aseptic packaging board, resistance to hot hydrogen peroxide and resistance to lactic acid. It has been discovered that use of fatty acid anhydride alone or in combination with AKD, both reactive sizing agents, along with an insolubilizing agent provides resistance to both lactic acid containing liquids and hot hydrogen peroxide solutions superior to either ketene dimer alone or the dual sizing system of ketene dimer and rosin. A reactive sizing agent is one that chemically reacts with cellulose.
[0010] The present invention provides a process to increase the resistance of paper board to penetration by hot penetrants, the process comprises a) adding i) an aqueous emulsion, comprising a reactive sizing agent and ii) an insolubilizing agent, either separately or in blended form to an aqueous pulp slurry, wherein the reactive sizing agent comprises at least 30% by weight fatty acid anhydride and b) forming the slurry into paper or paperboard.
DETAILED DESCRIPTION OF THE INVENTION
[0011] It has been found that if fatty acid anhydride or a blend of fatty acid anhydride and ketene dimer are added, together with an insolubilizing agent to a pulp slurry at a near neutral pH (for example, pH 6.0 to 7.5, preferably 6.5 to 7.5, or preferably 6.7 to 7.3) and the pulp is then formed into board, the board has good resistance to edge penetration by both hot hydrogen peroxide and lactic acid solutions.
[0012] Moreover, it has been found that the resistance of the board to hot hydrogen peroxide is unexpectedly better when a blend of fatty acid anhydride and ketene dimer are used than would be predicted by adding together the effects of the two sizes when used alone.
[0013] The reactive sizing agents useful in this invention can be emulsified separately and added separately to the pulp slurry, emulsified separately then mixed together at the addition point before addition to the pulp slurry or blended before emulsification.
[0014] Any of the ketene dimers known in the art may he used in the process of the present invention. Ketene dimers used as sizing agents are dimers having the formula:
[0000]
[0000] wherein R1 and R2 are alkyl radicals, which may be saturated or unsaturated, having from 6 to 24 carbon atoms, preferably more than 10 carbon atoms and most preferably from 14 to 16 carbon atoms. R1 and R2 can be the same or different. These ketene dimers are well known, for example from U.S. Pat. No. 2,785,067, the disclosure of which is incorporated herein by reference.
[0015] Suitable ketene dimers include decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl ketene dimers, as well as ketene dimers prepared from palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, myristoleic acid and eleostearic acid. The ketene dimer may be a single species or may contain a mixture of species. The most preferred ketene dimers are alkyl ketene dimers prepared from C14-C22 linear saturated fatty acids.
[0016] Acid anhydrides used as sizing agents can be characterized by the general formula:
[0000]
[0000] wherein R3 and R4 are alkyl radicals, which may be saturated or unsaturated, having from 6 to 24 carbon atoms, preferably more than 10 carbon atoms and most preferably from 14 to 16 carbon atoms. R3 and R4 can be the same or different. The most preferred acid anhydrides are acid anhydrides prepared from C14-C22 linear saturated fatty acids.
[0017] Any of the methods known for the preparation of dispersions of ketene dimer can be used to emulsify the acid anhydride and the ketene dimer. Frequently, the AKD is combined with dispersant systems which include cationic starch and sodium lignosulfonate. Examples of such dispersions can be found in U.S. Pat. No. 4,861,376 to Edwards, and U.S. Pat. No. 3,223,544 to Savina, the disclosures of which are hereby incorporated for reference. Alternatively, the acid anhydride and ketene dimer can be emulsified in-mill using any of the known methods.
[0018] These emulsions may include other additives common to size emulsions, for example, promoter resins for ketene dimers, biocides, antifoams, etc. The solids in the emulsions may vary from about 2 to about 50% by weight, preferably from about 4 to 40% and most preferably from about 5 to 35%.
[0019] The ketene dimer and fatty acid anhydride can be emulsified separately and added separately to the papermaking system, or the emulsions may be mixed together before addition. Alternatively the acid anhydride and ketene dimer can be blended before emulsification. The fatty acid anhydride and ketene dimer can be manufactured as a blend or they can be manufactured separately.
[0020] Fatty acid anhydrides react with cellulose to form an ester and a molecule of free fatty acid. The free fatty acid can react with the insolubilizing agent to form an insoluble salt. It is this insoluble salt that is believed to provide the enhanced resistance to hot penetrants.
[0021] The insolubilizing agent may be any one of those known in the art, such as papermaker's alum (aluminum sulfate), polyaluminum chloride (PAC) or other polyaluminum compounds, and is preferably alum. The amount of alum to be used is determined based on the type of pulp, the amount of sizing agent being applied, and other factors well known to those skilled in the art (e.g., system alkalinity, level of anionic “trash”, etc.). Generally, the amount of insolubilizing agent will be from about 5 to 15 lb/T (0.25 to 0.75% based on dry weight of fiber).
[0022] The insolubilizing agent may be added at the same addition point as the sizing agent, or the feed may be split so that some is added early in the system to neutralize anionic materials with the rest being added with the sizing agent.
[0023] Fatty acid anhydride can be used alone or in combination with alkyl ketene dimer. If used in combination with alkyl ketene dimer, the blend must contain at least 30% fatty acid anhydride. In the preferred blend, 40-70% of the reactive sizing material is fatty acid anhydride.
[0024] The sizing agents of this invention can be applied as internal sizing agents or surface sizing agents. Internal sizing involves adding the size to the paper pulp slurry before sheet formation, while surface sizing involves immersion of the paper in a solution containing the sizing agent, followed by drying at elevated temperatures in accordance with known drying techniques. Internal sizing is preferred.
[0025] The present invention is useful in sizing paper materials such as, for example, aseptic packaging board. The amount used is based on the desired sizing requirements of the customer, depending upon the required degree of sizing, the grade of paper, the type of pulp furnish used to make the paper, and other factors well known and easily determined empirically by those skilled in the art. In general, the least amount of sizing agent is used to obtain the desired sizing specifications. Typically, the amount of sizing agent will be from 4 to 10 lb/T (0.2 to 0.5% based on dry weight of fiber).
[0026] The pulp slurry may be processed in any conventional manner, for instance into board for aseptic packaging use, and any other conventional additives, such as retention aids, strength additives, pigments or fillers, may be added as desired.
[0027] The present invention also includes products, such as boards, made from pulp treated by the process of the present invention.
[0028] In addition to providing good resistance to hot hydrogen peroxide the compositions of this invention provide good resistance to other hot penetrants (i.e., penetrants above about 40° C.) commonly encountered in the industry, for example boiling water, hot coffee and hot coffee with cream, tests commonly used for testing cupstock (i.e., paperboard used in the production of drink cups).
EXAMPLES
[0029] The following examples are given for the purpose of illustrating the present invention. All parts and percentages are by weight unless otherwise indicated.
[0030] In the following examples, evaluations were made using a pilot scale papermachine designed to simulate a commercial Fourdrinier, including stock preparation, refining and storage. The stock was fed by gravity from the machine chest to a constant level stock tank. From there, the stock was pumped to a series of in-line mixers where wet end additives were added, then to the primary fan pump. The stock was diluted with white water at the fan pump to about 0.2% solids. Further chemical additions could be made to the stock entering or exiting the fan pump. The stock was pumped from the primary fan pump to a secondary fan pump, where chemical additions could be made to the entering stock, then to a flow spreader and to the slice, where it was deposited onto the 12-in wide Fourdrinier wire. Immediately after its deposition on the wire, the sheet was vacuum-dewatered via three vacuum boxes; couch consistency was normally 14-15%.
[0031] The wet sheet was transferred from the couch to a motor-driven wet pick-up felt. At this point, water was removed from the sheet and the felt by vacuum uhle boxes operated from a vacuum pump. The sheet was further dewatered in a single-felted press and left the press section at 38-40% solids.
[0032] In the following examples, evaluations were made using a blend of bleached hardwood kraft (70%) and bleached softwood kraft (30%) with a Canadian standard freeness of 350-400 cc. The water for dilutions was adjusted to contain 50 ppm hardness and 120 ppm alkalinity. Addition levels for all additives are given in percent based on dry weight of fiber. The addition of 0.95% quaternary-amine substituted cationic starch (Sta-Lok® 400, A.E. Staley, Decatur, Ill.) was split between the stock pump and the fan pump outlet. Alum and size were added in the amounts indicated in the examples at the fan pump inlet. PerForm® PM9025, an inorganic microparticle retention aid (Hercules Incorporated, Wilmington, Del.) was added at 0.038% at the secondary FP. Stock temperature was maintained at 55° C. The headbox pH was controlled to 6.8 unless otherwise indicated.
[0033] A 244 g/sq m (150 lb/3000 ft2 ream) sheet was formed and dried on seven dryer cans to 5% moisture (dryer can surface temperatures increased from 65 to 110° C.) and passed through a single nip of a 5-nip, 6 roll calendar stack at 28 pli. Edgewick resistance was measured on board naturally aged in a CT room (50% RH, 25° C.).
[0034] Edgewick tests are standard tests in the liquid packaging industry for measuring the degree of sizing. For this test, samples of board are laminated on both sides using a self-adhesive tape. Coupons of a given size are cut from the laminated board, weighed, and then immersed in the test solution at the designated temperature. After the specified time the samples are removed from the test solution, dried by blotting and reweighed. The results are reported as kg of solution absorbed per sq meter of exposed edge (kg/sq m). Low edgewick values are better than high values. The amount of sizing desired depends upon the grade of board being made.
[0035] The test solutions used were:
Hot hydrogen peroxide: 35% hydrogen peroxide at 70° C.; 10 min soak Lactic Acid: 20% lactic acid at 25° C.; 30 min soak
Example 1
Superior Resistance to Hot Hydrogen Peroxide
[0038] Emulsions of Aquapel® 364 alkyl ketene dimer (Hercules Incorporated, Wilmington, Del.) and stearic anhydride (99% Aldrich), stabilized with cationic starch were prepared by known methods (see, for example, U.S. Pat. No. 3,223,544, U.S. Pat. No. 4,861,376) and evaluated on the pilot papermachine as described above. The control was a binary sizing system comprised of Hi-pHase® 35 cationic dispersed rosin size (Hercules Incorporated, Wilmington, Del.) and the emulsion of Aquapel® 364.
[0039] In this evaluation 0.375% alum was used as the insolubilizing agent. The SA/AKD blend was made by adding the stearic anhydride emulsion and the AKD emulsion through a mixing T at a 60/40 ratio (based on actives) to reach the target level of sizing agent (e.g., for 0.10% sizing agent, 0.06% stearic anhydride and 0.04% AKD emulsions (based on actives) were added).
[0000]
TABLE 1
Hot Hydrogen Peroxide Wicks, kg/sq m
Control:
AKD
Stearic
Size Addition
Rosin/AKD
0.05%
Anhydride
SA/AKD
Levels
0.375% alum
alum
0.375% alum
0.375% alum
Control: 0.21%
0.9
Rosin/0.12%
AKD
0.10%
4.31
2.64
2.34
0.20%
1.47
0.89
0.74
0.30%
0.65
0.63
[0040] This example demonstrates that stearic anhydride provides better resistance to hot hydrogen peroxide than the binary sizing system (control) at similar addition levels (pick up of only 0.65 kg/sq m at 0.3% hydrophobe with SA vs. 0.9 with 0.33% hydrophobe with the binary system). Alternatively, stearic anhydride provided similar resistance to hot hydrogen peroxide as the binary sizing system (control) at reduced levels of hydrophobe (only 0.2% of the stearic anhydride was needed to achieve a hot hydrogen peroxide wick of 0.89 kg/sq m vs. 0.33% hydrophobe required to achieve that level of resistance for the binary system).
[0041] Surprisingly the blend of stearic anhydride and AKD provided better resistance to hot hydrogen peroxide than either sizing agent alone, at equal levels of hydrophobe: 0.2% SA/AKD (i.e., 0.12% of the SA and 0.08% of the AKD emulsions) resulted in a hot hydrogen peroxide wick of 0.74 kg/sq m whereas 0.2% SA gave 0.89 and 0.2% AKD gave 1.47.
Example 2
Superior Resistance to Lactic Acid
[0042] The board produced in Example 1 was also evaluated for resistance to lactic acid. Though not as effective as AKD, the blend of stearic anhydride and AKD also provides superior resistance to lactic acid compared to the binary control sizing system:
[0000]
TABLE 2
20% Lactic Acid Wicks, kg/sq m
Control:
AKD
Stearic
Rosin/AKD
0.05%
Anhydride
SA/AKD
Size Addition Level
0.375% alum
alum
0.375% alum
0.375% alum
Control: 0.21%
0.54
rosin/0.12% AKD
0.10%
1.12
21.66
12.59
0.20%
0.39
1.14
0.42
0.30%
0.48
0.21
[0043] To work as an effective system for an aseptic packaging application both lactic acid resistance and hot hydrogen peroxide resistance is needed.
Example 3
Effect of pH
[0044] Board was prepared as described in Example 1, varying the headbox pH from 6.5 to 7.5 , and using 0.375 wt. percent alum as the insolubilizing agent. The ratio of SA to AKD was 60:40. A near neutral, slightly acidic pH gave the best resistance to hot hydrogen peroxide:
[0000]
TABLE 3
Hot Hydrogen Peroxide Wicks, kg/sq m
pH
0.1% SA/AKD
0.2% SA/AKD
0.3% SA/AKD
6.5
1.84
0.76
0.46
7
2.99
0.79
0.48
7.5
5.65
1.17
0.57
[0000]
TABLE 4
20% Lactic Acid Wicks, kg/sq m
pH
0.1% SA/AKD
0.2% SA/AKD
0.3% SA/AKD
6.5
13.90
0.43
0.31
7
13.76
0.36
0.32
7.5
15.03
0.40
0.22
Example 4
Resistance to Other Hot Penetrants
[0045] Board was prepared as described in Example 1. The ratio of SA to AKD was 60:40. Board was tested for resistance to boiling water (boiling boat test: time for boiling water to penetrate through the z-direction of the board), Dixie Cobb (standard Cobb test run with hot water) and hot coffee and hot coffee with creamer Cobbs (see Tappi Test Method T 441om-04 for a description of the Cobb test).
[0000]
TABLE 5
Dixie Cobb (82 C. (180 F.) water, 2 min soak), g/sq m
Control: 0.21%
Stearic
rosin/0.12% AKD
AKD
Anhydride
SA/AKD
0.5% alum
0.05% alum
0.5% alum
0.5% alum
0.21% rosin/
32
0.12% AKD
0.20%
38
34
35
0.30%
35
32
34
[0000]
TABLE 6
Coffee Cobb (82 C. (180 F.) Maxwell house coffee,
2 min soak)
Control: 0.21%
Stearic
rosin/0.12% AKD
AKD
Anhydride
SA/AKD
0.5% alum
0.05% alum
0.5% alum
0.5% alum
0.21% rosin/
44
0.12% AKD
0.20%
41
55
0.30%
46
38
44
[0000]
TABLE 7
Coffee with creamer
(82 C. (180 F.) Maxwell House coffee with
Domino creamer, 2 min soak)
Control: 0.21%
Stearic
rosin/0.12% AKD
AKD
Anhydride
SA/AKD
0.5% alum
0.05% alum
0.5% alum
0.5% alum
0.21% rosin/
50
0.12% AKD
0.20%
51
46
50
0.30%
48
43
45
[0046] The boiling boat results for all of the above samples were 2000+ seconds.
[0047] The results showed that the inventive process provides resistance to other hot penetrants.
Example 5
Increasing Alum Addition Level
[0048] Board was prepared as described in Example 1, varying the alum addition level from 0.0 to 0.75%, maintaining headbox pH at 6.5. Clearly, resistance to hot hydrogen peroxide improved as the level of insolubilizing agent was increased
[0000]
TABLE 8
Hot Hydrogen Peroxide
Wicks, kg/sq m
0.1%
0.2%
0.3%
Alum level
SA/AKD
SA/AKD
SA/AKD
0
7.27
2.42
1.02
0.375
1.84
0.76
0.43
0.75
1.76
0.66
0.38
[0049] For reference, the control system with 0.21% rosin, 0.12% AKD and 0.375% alum had a hot hydrogen peroxide wick of 0.50 kg/sq m.
Example 6
Varying the Fatty Acid Anhydride to Alkyl Ketene Dimer Ratio
[0050] Board was prepared as described in Example 1 except the ratio of stearic anhydride to Aquapel 364 was varied. There was a general trend toward improved resistance to hot hydrogen peroxide with increased levels of stearic anhydride in the blend.
[0000]
TABLE 9
Hot Hydrogen Peroxide Wicks, kg/sq m
40 SA/60
50 SA/50
60 SA/40
Size Addn Level, %
Control
AKD
AKD
AKD
0.21% rosin +
1.88
0.12% AKD
0.2
2.08
2.06
1.60
0.3
1.30
0.89
1.03 | A process to increase the resistance of paper board to hot penetrants using a sizing agent containing fatty acid anhydride, and an insolubilizing agent is disclosed. Additionally a composition useful to impart hot penetrant resistance is disclosed | 3 |
BACKGROUND OF THE INVENTION
In order to recover solvents from waste gases or else in order to purify waste gases, condenser coolers or recuperative cold reservoirs are used, through which the solvent flows, a process during which the solvents condense out and freeze out. As soon as sufficient solvent has been separated, the flow of waste gas is guided through another group of condenser coolers. The first group is warmed up, and the solvent can be removed as a liquid product. A device of this type is disclosed, for instance, in German preliminary published application no. DE-OS 34 14 246.
Even though the processes according to the state of the art function satisfactorily, they require elaborate equipment since a double-installation is necessary to freeze out and to thaw the solvents. Furthermore, the mode of alternating operations calls for high energy consumption.
SUMMARY OF THE INVENTION
Therefore, the invention is based on the task of creating a process to recover solvents from waste gases or else to purify waste gases, which can be carried out continuously, that is to say, without alternating operations.
Accordingly, the inventive idea consists of continuously passing cooled shaped objects, for example, steel spheres, through a shaped-object reservoir. The gas to be purified flows in a countercurrent through the shaped-object reservoir. In this process, the waste gas cools off to such an extent on the shaped objects that the solvent or other vapors to be removed are then separated. The solvent separated in the solid state reaches the lower section of the shaped-object reservoir together with the shaped objects and then it melts due the presence of higher temperatures there. The melted ice drips down together with the resulting condensate and is then carried off to the outside. The warmed up shaped objects are removed from the shaped-object reservoir through a transfer lock and conveyed back to the inlet of the shaped-object reservoir. In this process, they are cooled off in a heat exchanger which can be operated, for example, with liquid nitrogen as the coolant. In a preferred embodiment, prior to cooling off in the heat exchanger, the shaped objects pass through an additional packing in which a flow of cold, purified waste gas passes through these objects and pre-cools them. This packing can also be cooled by means of evaporated nitrogen from the heat exchanger. In another preferred embodiment, the shaped objects removed from the shaped-object reservoir are passed through a dryer before they move to the conveying device.
Commonly employed recovery processes entail the disadvantage that, when the solvent is frozen out, the pressure drop in the devices increases steadily, thus giving rise to a non-stationary mode of operation. After a short period of time, the pressure loss is so great that it becomes necessary to switch the waste-gas flow over to a second device while the first one is warmed up and thawed. The cold losses associated with this, the heating energy additionally needed, the complicated equipment and the switching-over all are avoided with the process according to the invention, since freezing up cannot occur as a result of the continuous transportation of the shaped objects from the cold end to the warm end of the shaped-object reservoir. All of the process steps take place simultaneously and continuously, so that devices corresponding to the process according to the invention can be operated in a stationary manner.
THE DRAWINGS
FIG. 1 shows a device for carrying out the process in schematic form; and
FIG. 2 shows a variant of the device according to FIG. 1, having an additional packing.
DETAILED DESCRIPTION
The device shown in FIG. 1 consists of a shaped-object reservoir 1 whose lower section has a connection 2 for the feeding of the waste gases and whose upper section has a connection 3 for the removal of the waste gases. The middle section of the shaped-object reservoir 1 is filled with shaped objects 4 which are steel spheres. The shaped objects 4 lie on a funnel-like perforated plate 5 which ends in a transfer lock 6 which serves for the removal of the shaped objects. Connected to this transfer lock 6, there is a removal tube 7 which leads to a conveying device 8 for the shaped objects. In a corresponding manner, a charging tube 9 leads from the conveying device 8 back to the upper section of the shaped-object reservoir 1. The charging tube 9 is interrupted by a heat exchanger 10. The heat exchanger 10 has a connection 11 which serves to supply liquid nitrogen as the coolant and a connection 12 which serves to remove the gaseous nitrogen which has evaporated. Moreover, in the heat exchanger 10, there is a cooling surface 13 which is linked to the connection 3 and from which a connection 14 leads out of the heat exchanger 10. There is a drain 15 on the bottom of the shaped-object reservoir 1. The arrows (which do not have any position numbers) indicate the direction of flow of the materials.
Below, the process for recovering solvents from waste gas is described with reference to the device shown in FIG. 1.
Shaped objects 4 leave the conveying device 8 through the charging tube 9 and move to the shaped-object reservoir 1, in which they form a packing which lies on the perforated plate 5. The charging tube 9 is interrupted by a heat exchanger 10 in which the shaped objects 4 are cooled off. The cooling off is done by means of liquid nitrogen which is fed into the heat exchanger 10 through the connection 11 and which is then removed in gaseous form through the connection 12. There is an additional cooling of the shaped objects 4 on the cooling surface 13 which is exposed to cold, purified waste gas from the shaped-object reservoir 1. By means of the transfer lock 6, the shaped objects 4 are fed back to the conveying device 8 through the removal tube 7. The amount of shaped objects 4 removed is regulated by the operation of the transfer lock 6. Therefore, the shaped objects 4 continuously move from the top to the bottom through the shaped-object reservoir 1.
The waste gas loaded with solvents passes through the connection 2 into the lower section of the shaped-object reservoir 1. Then the waste-gas flows in a countercurrent with respect to the shaped objects 4 through the shaped-object reservoir 1 towards the top and then leaves this unit through connection 3. In this process, the waste gas cools off on the shaped objects 4 to such an extent that the solvents freeze out. The solvent ice reaches the lower section of the shaped-object reservoir 1 together with the shaped objects and melts, since the temperatures are higher there. The melted ice drips down together with the condensate which has formed in the lower section of the device and is then carried off to the outside through the drain 15. The shaped objects 4 warmed up by the waste-gas flow pass through the transfer lock 6 and through the removal tube 7 and move back to the conveying device 8, while the cold, purified waste gas passes through the connection 3, the cooling surface 13 and the connection 14 on its way out of the device. Naturally, the cold, purified waste gas can also be directly removed through the connection 3 without utilizing its coldness in the heat exchanger 10.
FIG. 2 shows a variant of FIG. 1 in which the same reference numbers are employed for the same parts of the installation. The main difference lies in the fact that there is an additional packing 16 of shaped objects 4 which likewise lie on a perforated plate 17 and which can be circulated by means of a transfer lock 18. The packing 16 is integrated into the shaped-object reservoir 1, although it can also be arranged separately. From the packing 16, the shaped objects 4 move through the transfer lock 18 and the removal tube 19 to the heat exchanger 10. Then they pass through the charging tube 20- which corresponds to the charging tube 9 of FIG. 1- and return to the shaped-object reservoir 1. The heat exchanger 10 is likewise exposed to liquid nitrogen which, however, still serves to pre-cool the packing 16 by means of the cooling surface 21 after the nitrogen has been removed through the connection 12 in the gaseous state from the heat exchanger 10. Furthermore, the cold, purified waste gas also passes through the packing 16 before it is removed from the installation through the connection 3. A difference from the embodiment according to FIG. 1 is that the shaped objects removed through the transfer lock 6 and the removal tube 7 also pass through a dryer 22. Purified waste gas or nitrogen can be used for purposes of drying. The drying medium is likewise removed from the dryer 22 through line 23 and fed into the shaped-object reservoir 1, thus making it possible to remove the condensate and solvent components absorbed in the dryer 22. These condensate and solvent components can also be removed separately in an additional condenser.
The shaped objects can consist, for instance, of ceramic or glass. They can also be hollow and contain a filling which stores coldness or they can be coated. | The recovery of solvents from waste gases takes place according to the state of the art by condensation, freezing out or desublimation of the solvent in recuperative cold reservoirs which can be switched over. In order to reduce the amount of equipment and the cold losses, the condensation and freezing-out operations are run continuously in a shaped-object reservoir through which cooled shaped objects move in a countercurrent to the waste gas. | 1 |
FIELD OF THE INVENTION
This invention relates to pressure gauges for use in a well bore and more particularly to a system for monitoring one or more pressure gauges in a permanent installation in a high temperature production well.
BACKGROUND OF THE INVENTION
In a production well in a well bore, the amount of production from the well can be optimized if the downhole pressure at or near the producing formations is known. To obtain downhole pressure measurements in a production well, it has been heretofore a practice to dispose a production string of tubing in a well bore with an attached pressure gauge at the lower end of the production string of tubing. The pressure gauge has access to the bore of the production tubing for sensing pressure in the tubing and an exterior conductor cable couples the pressure sensing device to the earth's surface for a determination and monitoring of the pressure in the bore of the string of tubing. With the knowledge of pressure in the downhole string of tubing, the operator can optimize the flow of production and adjust the production rate to the downhole pressures for optimum production conditions.
In permanent installations where a pressure gauge is installed, the production of the well may occur over an extended period of time, which may be months into years before the production tubing is removed, if removed at all. Thus, it is necessary that a pressure gauge for use in a permanent installation have a long life and reliability because it is often times impractical and too expensive to remove a production string to replace a failed pressure gauge.
In deep well bores particularly, the downhole temperature increases as a function of depth and the temperatures typically are greater than 100° C. Temperatures above 100° C. introduce special problems for pressure gauges typically employed for measurement of downhole pressure. This is because a high temperature adversely affects the electronics in the components in a pressure gauge and will accelerate failure and wear out of the electrical components. Obviously, the likelihood of a system failure increases as a function of the number of electronic components in the tool as well as the ambient temperature.
In an effort to solve the problem of gauge failure, it has been proposed to use redundant downhole pressure systems. That is, two completely separate pressure gauge systems are used to increase the reliability factor. However, the use of redundant downhole pressure systems creates a degree of difficulty and expense of installing two separate cables to the earth's surface which can be prohibitive and in some cases impossible to obtain. Two pressure gauge systems could be connected to a single cable if the transmission of pressure measurements is alternated. With alternate transmission, only one pressure sensor gauge system would communicate at a time with the cable and there would be no interference from one pressure sensor gauge system to another. This approach, however, would require synchronization of the electronics in the pressure gauge system and require interconnection which limits the pressure gauge system to a common housing.
In the present invention the reliability of a downhole pressure system for high temperature wells is increased by reducing the number of electronic components which are exposed to the environment. Additionally, the present invention contemplates reducing power dissipation in the downhole tool to minimum since power dissipation in downhole components only increases the operating temperature above ambient and aggravates the temperature exposure problem of electronic components. Multiple independent pressure gauge systems can be used with a single wire cable.
SUMMARY OF THE PRESENT INVENTION
The present invention involves a system for monitoring the downhole pressure in a high temperature well bore over an extended period of time using multiple pressure sensing tools in the well bore which are respectively connected to a common single conductor cable. In the downhole well tool, the functions are kept to an absolute minimum and no microprocessor system is used. Instead a dedicated logic integrated circuit is employed with a line driver, a voltage discriminator, a crystal clock, an Eprom memory, and a power regulator which couple to a sensor system which develops a digital output signal representative of a pressure measurement.
In operation, a pressure measurement from one of a number of tools is obtained by transmitting a digital polling signal from the earth's surface which is unique to one of the pressure sensing tools to initiate operation of the sensing tool. The sensing tool is activated by the recognition of the polling signal and converts from a low power state to an operational state where it can transmit pressure measurements. The downhole system of the polled sensing tool utilizes low power programmed circuits to sample and transmit pressure measurements to the earth's surface.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of the environment for the present invention;
FIG. 2 is a schematic illustration of the configuration of the present invention;
FIG. 3 is a schematic illustration of a Prior Art configuration for permanent pressure gauge installations;
FIG. 4 is a flow chart of Prior Art operations for a permanent pressure gauge installation; and
FIG. 5 is a flow chart of the operation for the present invention.
DESCRIPTION OF THE INVENTION
Referring now to FIG. 1, the present invention involves installation in a well bore 10 as illustrated where the well bore 10 traverses earth formations and is lined with a casing which is cemented in place. Disposed in the well bore 10 is a production packer 12 and a production tubing 14 which extends to the surface of the earth. Attached to the production tubing 14 are three pressure gauge sensing assemblies 15, 16, 17 which are respectively connected to a single wire cable 18 (sometimes called monocable) to the earth's surface and which have their pressure sensors open to the interior bore of the production tubing 14. A single wire cable is, of course, a single wire with a ground return which is commonly referred to as a single conductor cable. When the earth formations 20 produce fluids through the perforations 21 into the well bore 10, the fluids are transmitted via the production tubing 14 to the earth's surface. It is desired in the production of fluids to measure the downhole pressure of the produced fluids over a long period of time and under high temperatures.
A prior art pressure gauge system for permanent well installations is illustrated schematically in FIG. 3. As shown in FIG. 3, a pressure gauge unit 24 is connected to a single wire conductor cable 26, with only one wire being shown. The pressure gauge unit 24 has a voltage regulator 28 which receives a D.C. power input from the two wipe cable conductor 26 and supplies power to the downhole pressure unit.
The downhole pressure unit 24 includes a RAM memory 30, a sensor unit CPU 32, a non-volatile memory 33, a clock 34, a sensor unit 35 for pressure and a sensor unit 36 for temperature. A voltage/current modulator system is utilized to transmit and receive data. In this system, the pressure and temperature measurements are digitized and transmitted according to programmed instructions in the CPU 32 to the earth's surface via a current signal generator 38.
With reference to FIG. 4, the CPU 32 in the downhole unit is preprogrammed prior to being installed in the well bore with instructions for obtaining pressure and temperature measurements usually for selected time periods. The downhole unit is attached to a production tubing in a well bore and connected by a cable to the earth's surface. After the system is installed in a well bore and a measurement is desired, a surface generated start up signal at the surface powers up the downhole CPU 32 and the instructions 45 are loaded into the CPU 32 (see FIG. 4). The clock 34 times the instructions to sample temperature and pressure measurements. When the first instruction 47 is located, the programming checks the recording instruction and operates the system to sample the pressure and temperature measurements in a sequence which are transmitted in digital form to the surface where the measurements are read out and recorded in a memory of the surface CPU 48. Further details and description of this type of transmission and components of the system are found in U.S. Pat. No. 4,763,259 issued Aug. 8, 1988 and in U.S. Ser. No. 08/020,393 filed Feb. 22, 1993.
When a system such as illustrated in FIG. 3 is employed in permanent well installations for high temperature wells above 100° C., the higher ambient temperature accelerates failure of the system.
Reliability in a permanent installation type of well application is a very important consideration since it can be prohibitively expensive to recover a failed gauge. In the past, this has tended to make permanent gauge installations increasingly impractical as operating ambient temperatures went above 100° C.
One way that reliability can be increased for a high temperature application is to reduce the electrical component count exposed to this environment. This means that, in the case of the permanent gauge, the system complexity should be concentrated in functions performed at the earth's surface as opposed to downhole.
Another important factor for enhancing reliability in a high ambient temperature environment is to keep power dissipation in the downhole unit to a minimum. Obviously, any power dissipation in the downhole components will only increase their operating temperature above the ambient and aggregate the temperature exposure problem.
Also, if two completely redundant systems can be used the reliability is increased by a factor of four, assuming there are no common wearout or failure mechanisms. This is the same principle that applies to reducing the number of components in each system. This is the direct result of the increased likelihood of installing a component with an undetected failure mechanism as the number of system components increases.
However, use of redundant downhole gauge systems is complicated due to the degree of difficulty and expense of installing two separate cables to the surface which can be prohibitive. It is desirable to have two independent systems which have the capability to be powered and to communicate with a common cable. The systems should also be such that a failure in one does not result in disabling the other.
The most direct method of having two pressure gauges share the same cable for communication is to alternate their transmissions. Since only one gauge would be communicating with the cable at a time then there can be no crosstalk or interference from one gauge to another. The direct approach for doing this, however, requires synchronization of the gauge electronics and interconnection. This limits or requires the gauges to be within the same housing.
The approach of polling the gauges from the surface for selective retrieval of the downhole data is a more universal solution. This would allow each gauge to be independently connected to the cable and also would provide the added versatility of allowing each gauge to be used for a redundant or separate physical measurement. The drawback to this approach, however, is that conventional techniques for achieving this result involve relatively complex, power hungry downhole systems. This occurs because a microprocessor system is required which is complex and therefore also requires more power.
It would seem that recent, single-chip microprocessors would also meet the above requirements. To some extent this is true (the component count will still likely be higher) but there is also another serious limitation that enters the picture. All microprocessors must rely on a high density program memory to perform their function and experience has shown that these memory systems are not reliable at high temperature.
Some background on memory for high temperature applications may be in order. Random access memory (RAM) normally operates well under elevated temperature conditions since this memory is simply composed of transistors arranged to hold an entered logic state. Of course, this type of memory will not hold its information if power is removed and therefore is unsuitable as a program memory.
Another type of memory that is suitable to be a program memory is Eprom or EEprom. Both of these will hold their information with the removal of power but both can give problems at high temperature. These memory types rely on a stored electrical charge as a means of storing information and high temperature aggravates conditions which can cause this to be lost.
A type of memory that can be reliable at high temperature and which is also suitable as a program memory is the mask programmable type. The big disadvantage to this type of memory is that it is very expensive unless large volumes of memory devices are involved. This is because the custom pattern must be installed at the chip level and therefore it is not economical for small runs.
In the present invention it is possible to achieve the low power, low electrical component count goals, however, by keeping the downhole system functions to an absolute minimum and by not using a microprocessor system. In a present invention, all functions are performed by dedicated logic elements and the component count is minimized by the use of a programmable logic device.
Even though the programmable logic device requires a memory for configuration, this memory is read only once on start up. This is in contrast to a CPU where an instruction must be read from the program memory prior to each operation. Also, a much smaller memory is required for the programmable logic device than for a CPU and the high temperature performance capability of an EPROM type memory drops as the density increases.
A programmable logic device is ideal with simple functions and it is practical with low density one time programmable Eproms (since power is only applied to the memory during start up) but fusible link memories can be used. Fusible link memory is practical because the required memory capacity is low.
Referring now to FIG. 2, a pressure gauge unit 60, which is structurally identical to another pressure gauge unit 85 shown above it, is connected to a single wire conductor cable 62 where D.C. power is applied to a voltage regulator 64 in the unit 60. The conductor cable 62 also connects to a voltage discriminator 68 which can receive and input digital bits in a voltage format to a programmable logic device 70. The logic device 70 is configured by a serial EPROM 71 at start up time. The EPROM 71 is operated at the start up by applied power through an on/off switch 72 which also disconnects power from the EPROM 71 after the logic device 70 is configured by the EPROM 71. The temperature and pressure sensors 76 (and switching circuits) as well as a clock 78 are connected to the logic device 70 and include electronics to produce frequency signals as a function of pressure and a function of temperature. The electronics for the sensors 76 are activated by a switch 80 where the switch 80 is controlled by the logic device.
The programmable logic device 70 is also sometimes referred to as a programmable gate array. This device is available from XILINX which is located at San Jose, Calif. In particular, a XILINX array XC3042A is suitable and this device provides a group of high density, high performance, digitally integrated circuits. In the array, the user logic functions and interconnections are stored in internal static memory cells. The EPROM 71, such as a XILINX chip XC1736, provides a permanent storage of a configuration program for the array and is a low density memory chip. The EPROM 71 is activated when power is applied and provides an automatic loading of the configuration program to the logic device 70 for providing digital data representative of pressure and temperature from the sensors. When the configuration program is loaded into the logic device 70, the EPROM 71 is turned off by an instruction to the switch 92 from the logic device 70. Switch 92 is reset when power is first applied from the regulator 64.
A significant advantage of the logic device 70 over a CPU is that the logic device 70 reads the configuration program in the non-volatile memory (EPROM) 71 only once on start up and then operates in a low power state until activated by an address signal. In contrast, a CPU requires a high density memory which is read for each program step. Thus, the memory 71 can be a low density type which is more reliable at high temperatures than a high density memory. Moreover, the read-write cycles in a high density memory required with a CPU reduces the life of a memory device.
In operation, the pressure gauge unit 60 is in an idle, low power mode and a power switch 80 to the sensors 76 removes power from the electronics for the sensors. The clock 78 is controlled as to its on and off state by the logic device 70. The logic device 70 is in a low level state of operation until it is activated by a unique digital address. When a unique digital bit stream containing the address is transmitted from the earth's surface via the cable 62 it is received and recognized or not recognized by the logic device 70. If the address is recognized, the logic device 70 connects up power to the various shut down circuits. The digital bit stream containing the address is generated by the surface unit which has a CPU 77, a power source 79, a current sensor 81 for detecting a current signal from downhole and a voltage regulator 82 controlled by the CPU 77 for communicating with the downhole unit with a bit signal. A unique digital address as dictated by the CPU 77 is transmitted by voltage regulator 82 in digital bit form to the downhole voltage discriminator 68. The voltage discriminator 68 provides the digital bit stream containing the address to the programmable logic device 70. If the address is for the pressure gauge unit 60, the programmable logic device 70 recognizes the address and actuates the switch 80 which turns on the electronics for the sensors 76 and the clock 78 is started by the logic device 70. The digital address is followed by digital bit instructions which dictate the number of readings or measurements to be sent back. The number of measurements to be sent back is controlled by digital bit instructions to the programmable logic device 70 from the CPU 77 at the earth's surface.
In the idle mode of the gauge downhole, much of the electronics is powered down by use of the switch 80 and the switch 92 which prolongs the high temperature life of the electronics. The logic device 70 is configured to receive program bit instructions from the CPU at the earth's surface so that the pressure measurements are output by current signal modulation means in the voltage regulator 64 to the cable conductor 62 according to the bit instructions. The current modulation does not affect the power regulation to the system. Other pressure and temperature gauges such as gauge 85 are connected in parallel on the same downhole cable conductor.
All addressing and sequencing of the device 70 is under software control of the CPU 77 at the surface. The power-down feature is used when gauges are not required to transmit data often or sequence at a high speed, which is normally the case. This feature not only extends the life of a powered down component, but also greatly reduces the power required by multiple gauges on a common line.
The number of readings from each gauge is totally flexible and easily changed at the surface. Any gauge can be addressed to digitally transmit one or more readings and this can be followed by any other gauge or no readings for a period.
All readings from the current modulation means and addresses to the voltage discriminator 68 are transmitted and received as a string of tones which have no D.C. component and can be A.C. coupled. For example, with a 600 H z signal, by changing the cycles per bit, digital signals are created, i.e., a "011" address could be one cycle at 600 H z , two cycles at 1200 H z and two cycles at 600 H z . The change in frequency is used to distinguish between two adjacent bits. This allows transmission over the long downhole cable and capacitor coupling to the electronics with no problem. Transmission from the gauges is accomplished by current modulation of the current drawn by the unit. Address transmission to the downhole gauges is accomplished by voltage modulation of the line voltage supplied at the surface.
It will be apparent to those skilled in the art that various changes may be made in the invention without departing from the spirit and scope thereof and therefore the invention is not limited by that which is disclosed in the drawings and specifications but only as indicated in the appended claims. | A pressure and temperature system for monitoring pressure and temperature conditions in a permanent installation in a high temperature production well traversing earth formations where the system in a pressure tool incorporates a programmable logic array device and a low density memory device. Each of a number of independent pressure tools is programmed to respond to a distinct digital polling signal for selecting a particular tool so that a single wire conductor can be used for data and control signal communication between the pressure tools placed downhole and a computer system situated at the earth surface. The system in a tool is powered up and down for each selected operation to conserve individual component useful life and the number of downhole components subject to high temperature is minimized. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application Ser. No. 61/551,772 filed Oct. 26, 2011, which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to novel amide derivatives of N-urea substituted amino acids, processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals as modulators of the N-formyl peptide receptor like-1 (FPRL-1) receptor. The invention relates specifically to the use of these compounds and their pharmaceutical compositions to treat disorders associated with the N-formyl peptide receptor like-1 (FPRL-1) receptor modulation.
BACKGROUND OF THE INVENTION
The N-formyl peptide receptor like-1 (FPRL-1) receptor is a G protein-coupled receptor that is expressed on inflammatory cells such as monocytes and neutrophils, as well as T cells and has been shown to play a critical role in leukocyte trafficking during inflammation and human pathology. FPRL-1 is an exceptionally promiscuous receptor that responds to a large array of exogenous and endogenous ligands, including Serum amyloid A (SAA), chemokine variant sCKβ8-1, the neuroprotective peptide human, anti-inflammatory eicosanoid lipoxin A4 (LXA4) and glucocorticoid-modulated protein annexin A1. FPRL-1 transduces anti-inflammatory effects of LXA4 in many systems, but it also can mediate the pro-inflammatory signaling cascade of peptides such as SAA. The ability of the receptor to mediate two opposite effects is proposed to be a result of different receptor domains used by different agonists (Parmentier, Marc et al. Cytokine & Growth Factor Reviews 17 (2006) 501-519).
Activation of FPRL-1 by LXA4 or its analogs and by Annexin I protein has been shown to result in anti-inflammatory activity by promoting active resolution of inflammation which involves inhibition of polymorphonuclear neutrophil (PMN) and eosinophil migration and also stimulate monocyte migration enabling clearance of apoptotic cells from the site of inflammation in a nonphlogistic manner. In addition, FPRL-1 has been shown to inhibit natural killer (NK) cell cytotoxicity and promote activation of T cells which further contributes to down regulation of tissue damaging inflammatory signals. FPRL-1/LXA4 interaction has been shown to be beneficial in experimental models of ischemia reperfusion, angiogenesis, dermal inflammation, chemotherapy-induced alopecia, ocular inflammation such as endotoxin-induced uveitis, corneal wound healing, re-epithelialization etc. FPRL-1 thus represents an important novel pro-resolutionary molecular target for the development of new therapeutic agents in diseases with excessive inflammatory responses.
JP 06172288 discloses the preparation of phenylalanine derivatives of general formula:
as inhibitors of acyl-coenzyme A:cholesterol acyltransferase derivatives useful for the treatment of arteriosclerosis-related various diseases such as angina pectoris, cardiac infarction, temporary ischemic spasm, peripheral thrombosis or obstruction.
Journal of Combinatorial Chemistry (2007), 9(3), 370-385 teaches a thymidinyl dipeptide urea library with structural similarity to the nucleoside peptide class of antibiotics:
WO 9965932 discloses tetrapeptides or analogs or peptidomimetics that selectively bind mammalian opioid receptors:
Helvetica Chimica Acta (1998), 81(7), 1254-1263 teaches the synthesis and spectroscopic characterization of 4-chlorophenyl isocyanate (1-chloro-4-isocyanatobenzene) adducts with amino acids as potential dosimeters for the biomonitoring of isocyanate exposure:
EP 457195 discloses the preparation of peptides having endothelin antagonist activity and pharmaceutical compositions comprising them:
Yingyong Huaxue (1991), 7(1), 1-9 teaches the structure-activity relations of di- and tripeptide sweeteners and of L-phenyl analine derivatives:
FR 2533210 discloses L-phenyl analine derivatives as synthetic sweeteners:
WO2005047899 discloses compounds which selectively activate the FPRL-1 receptor represented by the following scaffolds:
SUMMARY OF THE INVENTION
A group of amide derivatives of N-urea substituted amino acids, which are potent and selective FPRL-1 modulators, has been discovered. As such, the compounds described herein are useful in treating a wide variety of disorders associated with modulation of FPRL-1 receptor. The term “modulator” as used herein, includes but is not limited to: receptor agonist, antagonist, inverse agonist, inverse antagonist, partial agonist, and partial antagonist.
This invention describes compounds of Formula I, which have FPRL-1 receptor biological activity. The compounds in accordance with the present invention are thus of use in medicine, for example in the treatment of humans with diseases and conditions that are alleviated by FPRL-1 modulation.
In one aspect, the invention provides a compound represented by Formula I or the individual geometrical isomers, individual enantiomers, individual diastereoisomers, individual tautomers, individual zwitterions or a pharmaceutically acceptable salt thereof:
wherein:
a is 0 or 1;
b is 0, 1, 2, 3 or 4;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NH 2 , —OH, —O(C 1-8 alkyl),
R 2 is optionally substituted C 1-8 alkyl, optionally substituted C 6-10 aryl,
R 3 is H, optionally substituted C 1-8 alkyl, halogen, —COOH, —OH, —NH 2 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl;
R 4 is H, optionally substituted C 1-8 alkyl, halogen, —COOH, —OH, —NH 2 , —NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl;
R 5 is optionally substituted C 1-8 alkyl, halogen, —COOH, —OH, —NH 2 , —NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl;
R 6 is H, optionally substituted C 1-8 alkyl, halogen, —COOH, —OH, —NH 2 , —NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl;
R 7 is H, optionally substituted C 1-8 alkyl, halogen, —COOH, —OH, —NH 2 , —NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl;
and compounds:
In another aspect, the invention provides a compound represented by Formula II or the geometrical isomers, enantiomers, diastereoisomers, tautomers, zwitterions, hydrates, cryslat forms, solvates or a pharmaceutically acceptable salt thereof:
wherein:
a is 1 and b is 0;
a is 0 and b is 1;
a is 1 and b is 1;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted
C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen, CF 3 or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl;
with the provisos:
a). when a=1 and b=0 then:
R 9 is not optionally substituted benzyl; and
R 11 is not:
and
the compound of Formula II is not of structures:
and
b). when a=0 and b=1 then:
R 1 is OR 13 ; and
the compound of Formula II is not of structure:
and
c). when a=1 and b=1 then:
R 11 is not:
In another aspect, the invention provides a compound represented by Formula II, wherein:
a is 1 and b is 0;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen, CF 3 or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl;
with the provisos:
R 9 is not optionally substituted benzyl; and
R 11 is not:
and
the compound of Formula II is not of structures:
In another aspect, the invention provides a compound represented by Formula II, wherein:
a is 1 and b is 0;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NR 11 R 12 or —OR13;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen, CF 3 or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl;
with the provisos:
R 9 is not optionally substituted benzyl; and
R 11 is not:
and
the compound of Formula II is not of structures:
In another aspect, the invention provides a compound represented by Formula II, wherein:
a is 1 and b is 0;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is —CF 3 ;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl;
with the provisos:
R 9 is not optionally substituted benzyl; and
R 11 is not:
and
the compound of Formula II is not of structures:
In another aspect, the invention provides a compound represented by Formula II, wherein:
a is 1 and b is 0;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is halogen;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl;
with the provisos:
R 9 is not optionally substituted benzyl;
and the compound of Formula II is not of structures:
and
R 11 is not:
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 1 and b is 0;
R 1 is optionally substituted C 1-8 alkyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 ;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 ;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 ;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 ;
R 8 is hydrogen or optionally substituted C 1-8 alkyl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen or optionally substituted C 1-8 ;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl;
with the provisos:
R 9 is not optionally substituted benzyl;
and the compound of Formula II is not of structures:
and
R 11 is not:
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 1 and b is 0;
R 1 is optionally substituted C 1-8 alkyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl;
R 3 is hydrogen or halogen;
R 4 is hydrogen;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen;
R 7 is hydrogen;
R 8 is hydrogen, optionally substituted C 1-8 alkyl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen or optionally substituted C 1-8 alkyl;
with the provisos:
R 9 is not optionally substituted benzyl;
and the compound of Formula II is not of structures:
and
R 11 is not:
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 0 and b is 1;
R 1 is —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen, CF 3 or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl; and
the compound of Formula II is not of structure:
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 0 and b is 1;
R 1 is —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is halogen;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl; and
the compound of Formula II is not of structure:
In another aspect, the invention provides a compound represented by Formula II, wherein:
a is 0 and b is 1;
R 1 is —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 8 is hydrogen;
R 9 is hydrogen;
R 10 is hydrogen, optionally substituted C 1-8 alkyl;
R 9a is hydrogen, optionally substituted C 1-8 alkyl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl; and
R 14 is hydrogen, CF 3 or optionally substituted C 1-8 alkyl; and
the compound of Formula II is not of structure:
In another aspect, the invention provides a compound represented by Formula II, wherein:
a is 0 and b is 1;
R 1 is —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl;
R 3 is hydrogen or halogen;
R 4 is hydrogen;
R 5 is halogen;
R 6 is hydrogen;
R 7 is hydrogen;
R 8 is hydrogen;
R 9 is hydrogen;
R 10 is hydrogen or optionally substituted C 1-8 alkyl;
R 9a is hydrogen or optionally substituted C 1-8 alkyl;
R 10a is hydrogen or optionally substituted C 1-8 alkyl; and
R 13 is hydrogen; and
the compound of Formula II is not of structure:
In another aspect, the invention provides a compound represented by Formula II, wherein:
a is 0 and b is 1;
R 1 is —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl;
R 3 is hydrogen or halogen;
R 4 is hydrogen;
R 5 is halogen;
R 6 is hydrogen;
R 7 is hydrogen;
R 8 is hydrogen;
R 9 is hydrogen;
R 10 is hydrogen or optionally substituted C 1-8 alkyl;
R 9a is optionally substituted C 1-8 alkyl;
R 10a is optionally substituted C 1-8 alkyl; and
R 13 is hydrogen.
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 1 and b is 1;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen or optionally substituted C 1-8 alkyl; and
R 15 is hydrogen or optionally substituted C 1-8 alkyl; and
with the proviso:
that R 11 is not:
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 1 and b is 1;
R 1 is optionally substituted C 1-8 alkyl, optionally substituted C 3-8 cycloalkyl, optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl, optionally substituted C 3-8 cycloalkenyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 5 is halogen;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen, —COOR 15 , —OR 13 , —NR 11 R 12 , NO 2 , optionally substituted heterocycle, optionally substituted C 3-8 cycloalkyl, optionally substituted C 6-10 aryl or optionally substituted C 3-8 cycloalkenyl;
R 8 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 9a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 15 is hydrogen or optionally substituted C 1-8 alkyl; and
with the proviso:
that R 11 is not:
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 1 and b is 1;
R 1 is optionally substituted C 1-8 alkyl, —NR 11 R 12 or —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 4 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 5 is halogen, —CF 3 or —S(O) n R 14 ;
n is 0, 1 or 2;
R 6 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 7 is hydrogen, optionally substituted C 1-8 alkyl, halogen;
R 8 is hydrogen;
R 9 is hydrogen, optionally substituted C 1-8 alkyl;
R 10 is hydrogen, optionally substituted C 1-8 alkyl;
R 9a is hydrogen, optionally substituted C 1-8 alkyl;
R 10a is hydrogen, optionally substituted C 1-8 alkyl;
R 11 is hydrogen or optionally substituted C 1-8 alkyl;
R 12 is hydrogen or optionally substituted C 1-8 alkyl;
R 13 is hydrogen or optionally substituted C 1-8 alkyl;
R 14 is hydrogen or optionally substituted C 1-8 alkyl; and
R 15 is hydrogen or optionally substituted C 1-8 alkyl;
with the proviso:
that R 11 is not:
In another aspect, the invention provides a compound represented by Formula II, wherein
a is 1 and b is 1;
R 1 is —OR 13 ;
R 2 is optionally substituted C 1-8 alkyl or optionally substituted C 6-10 aryl;
R 3 is hydrogen;
R 4 is hydrogen;
R 5 is halogen;
R 6 is hydrogen;
R 7 is hydrogen;
R 8 is hydrogen;
R 9 is hydrogen;
R 10 is hydrogen;
R 9a is hydrogen;
R 10a is hydrogen; and
R 13 is hydrogen or optionally substituted C 1-8 alkyl; and
with the proviso:
that R 11 is not:
The term “alkyl”, as used herein, refers to saturated, monovalent or divalent hydrocarbon moieties having linear or branched moieties or combinations thereof and containing 1 to 8 carbon atoms. One methylene (—CH 2 —) group, of the alkyl group can be replaced by oxygen, sulfur, sulfoxide, nitrogen, carbonyl, carboxyl, sulfonyl, sulfate, sulfonate, amide, sulfonamide, by a divalent C 3-8 cycloalkyl, by a divalent heterocycle, or by a divalent aryl group. Alkyl groups can have one or more chiral centers. Alkyl groups can be independently substituted by halogen atoms, hydroxyl groups, cycloalkyl groups, amino groups, heterocyclic groups, aryl groups, carboxylic acid groups, phosphonic acid groups, sulphonic acid groups, phosphoric acid groups, nitro groups, amide groups, sulfonamide groups.
The term “cycloalkyl”, as used herein, refers to a monovalent or divalent group of 3 to 8 carbon atoms derived from a saturated cyclic hydrocarbon. Cycloalkyl groups can be monocyclic or polycyclic. Cycloalkyl can be independently substituted by halogen atoms, sulfonyl C 1-8 alkyl groups, sulfoxide C 1-8 alkyl groups, sulfonamide groups, nitro groups, cyano groups, —OC 1-8 alkyl groups, —SC 1-8 alkyl groups, —C 1-8 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups.
The term “cycloalkenyl”, as used herein, refers to a monovalent or divalent group of 3 to 8 carbon atoms derived from a saturated cycloalkyl having at least one double bond. Cycloalkenyl groups can be monocyclic or polycyclic. Cycloalkenyl groups can be independently substituted by halogen atoms, sulfonyl groups, sulfoxide groups, nitro groups, cyano groups, —OC 1-6 alkyl groups, —SC 1-6 alkyl groups, —C 1-6 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups.
The term “halogen”, as used herein, refers to an atom of chlorine, bromine, fluorine, iodine.
The term “alkenyl”, as used herein, refers to a monovalent or divalent hydrocarbon radical having 2 to 6 carbon atoms, derived from a saturated alkyl, having at least one double bond. One methylene (—CH 2 —) group, of the alkenyl can be replaced by oxygen, sulfur, sulfoxide, nitrogen, carbonyl, carboxyl, sulfonyl, sulfate, sulfonate, amide, sulfonamide, by a divalent C 3-8 cycloalkyl, by a divalent heterocycle, or by a divalent aryl group. C 2-6 alkenyl can be in the E or Z configuration. Alkenyl groups can be substituted by alkyl groups, as defined above or by halogen atoms.
The term “alkynyl”, as used herein, refers to a monovalent or divalent hydrocarbon radical having 2 to 6 carbon atoms, derived from a saturated alkyl, having at least one triple bond. One methylene (—CH 2 —) group, of the alkynyl can be replaced by oxygen, sulfur, sulfoxide, nitrogen, carbonyl, carboxyl, sulfonyl, sulfate, sulfonate, amide, sulfonamide, by a divalent C 3-8 cycloalkyl, by a divalent heterocycle, or by a divalent aryl group. Alkynyl groups can be substituted by alkyl groups, as defined above, or by halogen atoms.
The term “heterocycle” as used herein, refers to a 3 to 10 membered ring, which can be aromatic or non-aromatic, saturated or unsaturated, containing at least one heteroatom selected form oxygen, nitrogen, sulfur, or combinations of at least two thereof, interrupting the carbocyclic ring structure. The heterocyclic ring can be interrupted by a C═O; the S and N heteroatoms can be oxidized. Heterocycles can be monocyclic or polycyclic. Heterocyclic ring moieties can be substituted by halogen atoms, sulfonyl groups, sulfoxide groups, nitro groups, cyano groups, —OC 1-6 alkyl groups, —SC 1-6 alkyl groups, —C 1-8 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups.
The term “aryl” as used herein, refers to an organic moiety derived from an aromatic hydrocarbon consisting of a ring containing 6 to 10 carbon atoms, by removal of one hydrogen atom. Aryl can be substituted by halogen atoms, sulfonyl C 1-6 alkyl groups, sulfoxide C 1-6 alkyl groups, sulfonamide groups, carboxcyclic acid groups, C 1-6 alkyl carboxylates (ester) groups, amide groups, nitro groups, cyano groups, —OC 1-6 alkyl groups, —SC 1-6 alkyl groups, —C 1-6 alkyl groups, —C 2-6 alkenyl groups, —C 2-6 alkynyl groups, ketone groups, aldehydes, alkylamino groups, amino groups, aryl groups, C 3-8 cycloalkyl groups or hydroxyl groups. Aryls can be monocyclic or polycyclic.
The term “hydroxyl” as used herein, represents a group of formula “—OH”.
The term “carbonyl” as used herein, represents a group of formula “—C(O)—”.
The term “ketone” as used herein, represents an organic compound having a carbonyl group linked to a carbon atom such as —(CO)R x wherein R x can be alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
The term “amine” as used herein, represents a group of formula “—NR x R y ”, wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
The term “carboxyl” as used herein, represents a group of formula “—C(O)O—”.
The term “sulfonyl” as used herein, represents a group of formula “—SO 2 − ”.
The term “sulfate” as used herein, represents a group of formula “—O—S(O) 2 —O—”.
The term “sulfonate” as used herein, represents a group of the formula “—S(O) 2 —O—”.
The term “carboxylic acid” as used herein, represents a group of formula “—C(O)ON”.
The term “nitro” as used herein, represents a group of formula “—NO 2 ”.
The term “cyano” as used herein, represents a group of formula “—CN”.
The term “amide” as used herein, represents a group of formula “—C(O)NR x R y ,” wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
The term “sulfonamide” as used herein, represents a group of formula “—S(O) 2 NR x R y ” wherein R x and R y can be the same or independently H, alkyl, aryl, cycloalkyl, cycloalkenyl, heterocycle as defined above.
The term “sulfoxide” as used herein, represents a group of formula “—S(O)—”.
The term “phosphonic acid” as used herein, represents a group of formula “—P(O)(OH) 2 ”.
The term “phosphoric acid” as used herein, represents a group of formula “—OP(O)(OH) 2 ”.
The term “sulphonic acid” as used herein, represents a group of formula “—S(O) 2 OH”.
The formula “H”, as used herein, represents a hydrogen atom.
The formula “O”, as used herein, represents an oxygen atom.
The formula “N”, as used herein, represents a nitrogen atom.
The formula “S”, as used herein, represents a sulfur atom.
The invention discloses compounds
{[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-indol-3-yl)propanoyl]amino}acetic acid; tert-butyl {[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-indol-3-yl)propanoyl]amino}acetate; [(4-amino-2-{[(4-bromophenyl)carbamoyl]amino}-4-oxobutanoyl)amino]acetic acid; tert-butyl [(4-amino-2-{[(4-bromophenyl)carbamoyl]amino}-4-oxobutanoyl)amino]acetate; 2-{[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoic acid; tert-butyl 2-{[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoate; {[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-imidazol-4-yl)propanoyl]amino}acetic acid; tert-butyl {[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-imidazol-4-yl)propanoyl]amino}acetate; {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfonyl)butanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfonyl)butanoyl]amino}acetate; {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfanyl)butanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfanyl)butanoyl]amino}acetate; 2-methyl-2-{[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}propanoic acid; tert-butyl 2-methyl-2-{[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}propanoate; {[(2S)-4-methyl-2-({[4-(methylsulfonyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl {[(2S)-4-methyl-2-({[4-(methylsulfonyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; {[(2S)-4-methyl-2-({[4-(methylsulfinyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl{[(2S)-4-methyl-2-({[4-(methylsulfinyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; 2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoic acid; tert-butyl 2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoate; ({(2S)-4-methyl-2-[({4-[(trifluoromethyl)sulfanyl]phenyl}carbamoyl)amino]pentanoyl}amino)acetic acid; tert-butyl ({(2S)-4-methyl-2-[({4-[(trifluoromethyl)sulfanyl]phenyl}carbamoyl)amino]pentanoyl}amino)acetate; {[(2S)-4-methyl-2-({[4-(methylsulfanyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl {[(2S)-4-methyl-2-({[4-(methylsulfanyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; {[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetic acid; tert-butyl {[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetate; {[(2R,3R)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetic acid tert-butyl {[(2R,3R)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetate; {[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl {[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; {[(2R)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetic acid; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-[2-(dimethylamino)-2-oxoethyl]-4-methylpentanamide; [(2-{[(4-bromophenyl)carbamoyl]amino}-2-methylpropanoyl)amino]acetic acid; tert-butyl [(2-{[(4-bromophenyl)carbamoyl]amino}-2-methylpropanoyl)amino]acetate; [(2-{[(4-bromophenyl)carbamoyl]amino}-2-ethylbutanoyl)amino]acetic acid; tert-butyl [(2-{[(4-bromophenyl)carbamoyl]amino}-2-ethylbutanoyl)amino]acetate; [(2-{[(4-bromophenyl)carbamoyl]amino}-2,4-dimethylpentanoyl)amino]acetic acid; tert-butyl [(2-{[(4-bromophenyl)carbamoyl]amino}-2,4-dimethylpentanoyl)amino]acetate; (2S)—N-[(1S)-2-amino-2-oxo-1-phenylethyl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}(phenyl)ethanoic acid; tert-butyl (2S)-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}(phenyl)ethanoate; (2S)—N-[(2S)-1-amino-1-oxopentan-2-yl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}pentanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}pentanoate; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-[(2R)-1-hydroxypropan-2-yl]-4-methylpentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2,3-dihydroxypropyl)-4-methylpentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(1,3-dihydroxypropan-2-yl)-4-methylpentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-hydroxy-2-methylpropyl)-4-methylpentanamide; (2S)—N-[(2S)-1-amino-3-methyl-1-oxobutan-2-yl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-3-methylbutanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-3-methylbutanoate; (2S)—N-[(2S)-1-amino-1-oxopropan-2-yl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoate; (2S)—N-[(2S)-1-amino-1-oxopropan-2-yl]-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoate; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)-4-methylpentanamide; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methyl-N-(2-oxopropyl)pentanamide; (2S)—N-(2-amino-2-oxoethyl)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanamide; {[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetate; (2S)—N-(2-amino-2-oxoethyl)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}pentanamide; (2S)—N-(2-amino-2-oxoethyl)-2-{[(4-bromophenyl)carbamoyl]amino}pentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methyl-N-(2-oxopropyl)pentanamide; (2S)—N-(2-amino-2-oxoethyl)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetic acid; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)-4-methylpentanamide; tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetate; {[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}pentanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}pentanoyl]amino}acetate; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-N-(2-oxopropyl)pentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-oxopropyl)pentanamide; propan-2-yl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}pentanoyl]amino}acetate; ethyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}pentanoyl]amino}acetate; methyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}pentanoyl]amino}acetate; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)pentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)pentanamide; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)-3-phenylpropanamide; {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}pentanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}pentanoyl]amino}acetate; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-N-(2-oxopropyl)-3-phenylpropanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-oxopropyl)-3-phenylpropanamide; (2S,3S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)-3-methylpentanamide; (2S,3S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)-3-methylpentanamide; (2S,3S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-3-methyl-N-(2-oxopropyl)pentanamide; (2S,3S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methyl-N-(2-oxopropyl)pentanamide; (2S,3S)—N-(2-amino-2-oxoethyl)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-3-methylpentanamide; (2S,3S)—N-(2-amino-2-oxoe;thyl)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanamide {[(2S,3S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetic acid; tert-butyl {[(2S,3S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetate; {[(2S,3S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetic acid; tert-butyl {[(2S,3S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetate; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)-3-phenylpropanamide; 3-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-phenylpropanoyl]amino}propanoic acid; tert-butyl 3-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-phenylpropanoyl]amino}propanoate; {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-phenylpropanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-phenylpropanoyl]amino}acetate.
In another aspect the invention discloses compounds:
{[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-imidazol-4-yl)propanoyl]amino}acetic acid; tert-butyl {[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-imidazol-4-yl)propanoyl]amino}acetate; {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfonyl)butanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfonyl)butanoyl]amino}acetate; {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfanyl)butanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-(methylsulfanyl)butanoyl]amino}acetate; 2-methyl-2-{[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}propanoic acid; tert-butyl 2-methyl-2-{[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}propanoate; {[(2S)-4-methyl-2-({[4-(methylsulfonyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl {[(2S)-4-methyl-2-({[4-(methylsulfonyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; {[(2S)-4-methyl-2-({[4-(methylsulfinyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl {[(2S)-4-methyl-2-({[4-(methylsulfinyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; 2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoic acid; tert-butyl 2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoate; ({(2S)-4-methyl-2[({4-[(trifluoromethyl)sulfanyl]phenyl}carbamoyl)amino]pentanoyl}amino)acetic acid; tert-butyl ({(2S)-4-methyl-2-[({4-[(trifluoromethyl)sulfanyl]phenyl}carbamoyl)amino]pentanoyl}amino)acetate; {[(2S)-4-methyl-2-({[4-(methylsulfanyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl {[(2S)-4-methyl-2-({[4-(methylsulfanyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; {[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetic acid; tert-butyl {[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetate; {[(2R,3R)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetic acid; tert-butyl {[(2R,3R)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanoyl]amino}acetate; {[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetic acid; tert-butyl {[(2S)-4-methyl-2-({[4-(trifluoromethyl)phenyl]carbamoyl}amino)pentanoyl]amino}acetate; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-[2-(dimethylamino)-2-oxoethyl]-4-methylpentanamide; [(2-{[(4-bromophenyl)carbamoyl]amino}-2-methylpropanoyl)amino]acetic acid; tert-butyl [(2-{[(4-bromophenyl)carbamoyl]amino}-2-methylpropanoyl)amino]acetate; [(2-{[(4-bromophenyl)carbamoyl]amino}-2-ethylbutanoyl)amino]acetic acid; tert-butyl [(2-{[(4-bromophenyl)carbamoyl]amino}-2-ethylbutanoyl)amino]acetate; [(2-{[(4-bromophenyl)carbamoyl]amino}-2,4-dimethylpentanoyl)amino]acetic acid; tert-butyl [(2-{[(4-bromophenyl)carbamoyl]amino}-2,4-dimethylpentanoyl)amino]acetate; (2S)—N-[(1S)-2-amino-2-oxo-1-phenylethyl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}(phenyl)ethanoic acid; tert-butyl (2S)-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}(phenyl)ethanoate; (2S)—N-[(2S)-1-amino-1-oxopentan-2-yl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}pentanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}pentanoate; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-[(2R)-1-hydroxypropan-2-yl]-4-methylpentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2,3-dihydroxypropyl)-4-methylpentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(1,3-dihydroxypropan-2-yl)-4-methylpentanamide; (2S)-2-{[(4-bromophenyl)carbamoyl]amino}-N-(2-hydroxy-2-methylpropyl)-4-methylpentanamide; (2S)—N-[(2S)-1-amino-3-methyl-1-oxobutan-2-yl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-3-methylbutanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-3-methylbutanoate; (2S)—N-[(2S)-1-amino-1-oxopropan-2-yl]-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoate; (2S)—N-[(2S)-1-amino-1-oxopropan-2-yl]-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanamide; (2S)-2-{[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoic acid; tert-butyl (2S)-2-{[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}propanoate; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-N-(2-hydroxyethyl)-4-methylpentanamide; (2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methyl-N-(2-oxopropyl)pentanamide; (2S)—N-(2-amino-2-oxoethyl)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanamide; {[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetic acid; tert-butyl {[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}acetate; tert-butyl 2-{[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoate; 2-{[(2R)-2-{[(4-bromophenyl)carbamoyl]amino}-4-methylpentanoyl]amino}-2-methylpropanoic acid; tert-butyl [(4-amino-2-{[(4-bromophenyl)carbamoyl]amino}-4-oxobutanoyl)amino]acetate; [(4-amino-2-{[(4-bromophenyl)carbamoyl]amino}-4-oxobutanoyl)amino]acetic acid; tert-butyl {[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-indol-3-yl)propanoyl]amino}acetate; {[2-{[(4-bromophenyl)carbamoyl]amino}-3-(1H-indol-3-yl)propanoyl]amino}acetic acid.
Some compounds of Formula I and of Formula II and some of their intermediates have at least one asymmetric center in their structure. This asymmetric center may be present in an R or S configuration, said R and S notation is used in correspondence with the rules described in Pure Appli. Chem. (1976), 45, 11-13.
The term “pharmaceutically acceptable salts” refers to salts or complexes that retain the desired biological activity of the above identified compounds and exhibit minimal or no undesired toxicological effects. The “pharmaceutically acceptable salts” according to the invention include therapeutically active, non-toxic base or acid salt forms, which the compounds of Formula I and of Formula II are able to form.
The acid addition salt form of a compound of Formula I and of Formula II that occurs in its free form as a base can be obtained by treating the free base with an appropriate acid such as an inorganic acid, for example, hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid and the like; or an organic acid such as for example, acetic acid, hydroxyacetic acid, propanoic acid, lactic acid, pyruvic acid, malonic acid, fumaric acid, maleic acid, oxalic acid, tartaric acid, succinic acid, malic acid, ascorbic acid, benzoic acid, tannic acid, pamoic acid, citric acid, methylsulfonic acid, ethanesulfonic acid, benzenesulfonic acid, formic and the like (Handbook of Pharmaceutical Salts, P. Heinrich Stahal & Camille G. Wermuth (Eds), Verlag Helvetica Chemica Acta-Zürich, 2002, 329-345).
The base addition salt form of a compound of Formula I and of Formula II that occurs in its acid form can be obtained by treating the acid with an appropriate base such as an inorganic base, for example, sodium hydroxide, magnesium hydroxide, potassium hydroxide, Calcium hydroxide, ammonia and the like; or an organic base such as for example, L-Arginine, ethanolamine, betaine, benzathine, morpholine and the like. (Handbook of Pharmaceutical Salts, P. Heinrich Stahal & Camille G. Wermuth (Eds), Verlag Helvetica Chemica Acta-Zürich, 2002, 329-345).
Compounds of Formula I and of Formula II and their salts can be in the form of a solvate, which is included within the scope of the present invention. Such solvates include for example hydrates, alcoholates and the like.
With respect to the present invention reference to a compound or compounds, is intended to encompass that compound in each of its possible isomeric forms and mixtures thereof unless the particular isomeric form is referred to specifically.
Compounds according to the present invention may exist in different polymorphic forms. Although not explicitly indicated in the above formula, such forms are intended to be included within the scope of the present invention.
The compounds of the invention are indicated for use in treating or preventing conditions in which there is likely to be a component involving the N-formyl peptide receptor like-1 receptor.
In another embodiment, there are provided pharmaceutical compositions including at least one compound of the invention in a pharmaceutically acceptable carrier.
In a further embodiment of the invention, there are provided methods for treating disorders associated with modulation of the N-formyl peptide receptor like-1-receptor.
Such methods can be performed, for example, by administering to a subject in need thereof a pharmaceutical composition containing a therapeutically effective amount of at least one compound of the invention.
Therapeutic utilities of the N-formyl peptide receptor like-1 receptor modulators are ocular inflammatory diseases including, but not limited to, wet and dry age-related macular degeneration (ARMD), uveitis, dry eye, Keratitis, allergic eye disease and conditions affecting the posterior part of the eye, such as maculopathies and retinal degeneration including non-exudative age related macular degeneration, exudative age related macular degeneration, choroidal neovascularization, diabetic retinopathy (proliferative), retinopathy of prematurity (ROP), acute macular neuroretinopathy, central serous chorioretinopathy, cystoid macular edema, and diabetic macular edema; infectious keratitis, uveitis, herpetic keratitis, corneal angiogenesis, lymphangiogenesis, uveitis, retinitis, and choroiditis such as acute multifocal placoid pigment epitheliopathy, Behcet's disease, birdshot retinochoroidopathy, infectious (syphilis, lyme, tuberculosis, toxoplasmosis), intermediate uveitis (pars planitis), multifocal choroiditis, multiple evanescent white dot syndrome (mewds), ocular sarcoidosis, posterior scleritis, serpiginous choroiditis, subretinal fibrosis and uveitis syndrome, Vogt-Koyanagi- and Harada syndrome; vasuclar diseases/exudative diseases such as retinal arterial occlusive disease, central retinal vein occlusion, cystoids macular edema, disseminated intravascular coagulopathy, branch retinal vein occlusion, hypertensive fundus changes, ocular ischemic syndrome, retinal arterial microaneurysms, Coat's disease, parafoveal telangiectasis, hemi-retinal vein occlusion, papillophlebitis, central retinal artery occlusion, branch retinal artery occlusion, carotid artery disease (CAD), frosted branch angiitis, sickle cell retinopathy and other hemoglobinopathies, angioid streaks, familial exudative vitreoretinopathy, and Eales disease; traumatic/surgical conditions such as sympathetic ophthalmia, uveitic retinal disease, retinal detachment, trauma, post surgical corneal wound healing, conditions caused by laser, conditions caused by photodynamic therapy, photocoagulation, hypoperfusion during surgery, radiation retinopathy, and bone marrow transplant retinopathy; proliferative disorders such as proliferative vitreal retinopathy and epiretinal membranes, and proliferative diabetic retinopathy; infectious disorders such as ocular histoplasmosis, ocular toxocariasis, presumed ocular histoplasmosis syndrome (PONS), endophthalmitis, toxoplasmosis, retinal diseases associated with HIV infection, choroidal disease associate with HIV infection, uveitic disease associate with HIV infection, viral retinitis, acute retinal necrosis, progressive outer retinal necrosis, fungal retinal diseases, ocular syphilis, ocular tuberculosis, diffuse unilateral subacute neuroretinitis, and myiasis; genetic disorders such as retinitis pigmentosa, systemic disorders with associated retinal dystrophies, congenital stationary night blindness, cone dystrophies, Stargardt's disease and fundus flavimaculatus, Best's disease, pattern dystrophy of the retinal pigmented epithelium, X-linked retinoschisis, Sorsby's fundus dystrophy, benign concentric maculopathy, Bietti's crystalline dystrophy, and pseudoxanthoma elasticum; retinal tears/holes such as retinal detachment, macular hole, and giant retinal tear; tumors such as retinal disease associated with tumors, congenital hypertrophy of the retinal pigmented epithelium, posterior uveal melanoma, choroidal hemangioma, choroidal osteoma, choroidal metastasis, combined hamartoma of the retina and retinal pigmented epithelium, retinoblastoma, vasoproliferative tumors of the ocular fundus, retinal astrocytoma, and intraocular lymphoid tumors; and miscellaneous other diseases affecting the posterior part of the eye such as punctate inner choroidopathy, acute posterior multifocal placoid pigment epitheliopathy, myopic retinal degeneration, and acute retinal pigment epitheliitis, systemic inflammatory diseases such as stroke, coronary artery disease, obstructive airway diseases, HIV-mediated retroviral infections, cardiovascular disorders including coronary artery disease, neuroinflammation, neurological disorders, pain and immunological disorders, asthma, allergic disorders, inflammation, systemic lupus erythematosus, psoriasis, CNS disorders such as Alzheimer's disease, arthritis, sepsis, inflammatory bowel disease, cachexia, angina pectoris, post-surgical corneal inflammation, blepharitis, MGD, dermal wound healing, burns, rosacea, atopic dermatitis, acne, psoriasis, seborrheic dermatitis, actinic keratoses, viral warts, photoaging rheumatoid arthritis and related inflammatory disorders, alopecia, glaucoma, branch vein occlusion, Best's vitelliform macular degenartion, retinitis pigmentosa, proliferative vitreoretinopathy (PVR), and any other degenerative disease of either the photoreceptors or the RPE (Perretti, Mauro et al. Pharmacology & Therapeutics 127 (2010) 175-188.)
These compounds are useful for the treatment of mammals, including humans, with a range of conditions and diseases that are alleviated by the N-formyl peptide receptor like-1 receptor modulation: including, but not limited to the treatment of wet and dry age-related macular degeneration (ARMD), diabetic retinopathy (proliferative), retinopathy of prematurity (ROP), diabetic macular edema, uveitis, retinal vein occlusion, cystoids macular edema, glaucoma, branch vein occlusion, Best's vitelliform macular degenartion, retinitis pigmentosa, proliferative vitreoretinopathy (PVR), and any other degenerative disease of either the photoreceptors or the RPE.
In still another embodiment of the invention, there are provided methods for treating disorders associated with modulation of the FPRL-1 receptor. Such methods can be performed, for example, by administering to a subject in need thereof a therapeutically effective amount of at least one compound of the invention, or any combination thereof, or pharmaceutically acceptable salts, hydrates, solvates, crystal forms and individual isomers, enantiomers, and diastereomers thereof.
The present invention concerns the use of a compound of Formula I and of Formula II or a pharmaceutically acceptable salt thereof, for the manufacture of a medicament for the treatment of ocular inflammatory diseases including, but not limited to, wet and dry age-related macular degeneration (ARMD), uveitis, dry eye, Keratitis, allergic eye disease and conditions affecting the posterior part of the eye, such as maculopathies and retinal degeneration including non-exudative age related macular degeneration, exudative age related macular degeneration, choroidal neovascularization, diabetic retinopathy (proliferative), retinopathy of prematurity (ROP), acute macular neuroretinopathy, central serous chorioretinopathy, cystoid macular edema, and diabetic macular edema; infectious keratitis, uveitis, herpetic keratitis, corneal angiogenesis, lymphangiogenesis, uveitis, retinitis, and choroiditis such as acute multifocal placoid pigment epitheliopathy, Behcet's disease, birdshot retinochoroidopathy, infectious (syphilis, lyme, tuberculosis, toxoplasmosis), intermediate uveitis (pars planitis), multifocal choroiditis, multiple evanescent white dot syndrome (mewds), ocular sarcoidosis, posterior scleritis, serpiginous choroiditis, subretinal fibrosis and uveitis syndrome, Vogt-Koyanagi- and Harada syndrome; vasuclar diseases/exudative diseases such as retinal arterial occlusive disease, central retinal vein occlusion, cystoids macular edema, disseminated intravascular coagulopathy, branch retinal vein occlusion, hypertensive fundus changes, ocular ischemic syndrome, retinal arterial microaneurysms, Coat's disease, parafoveal telangiectasis, hemi-retinal vein occlusion, papillophlebitis, central retinal artery occlusion, branch retinal artery occlusion, carotid artery disease (CAD), frosted branch angiitis, sickle cell retinopathy and other hemoglobinopathies, angioid streaks, familial exudative vitreoretinopathy, and Eales disease; traumatic/surgical conditions such as sympathetic ophthalmia, uveitic retinal disease, retinal detachment, trauma, post surgical corneal wound healing, conditions caused by laser, conditions caused by photodynamic therapy, photocoagulation, hypoperfusion during surgery, radiation retinopathy, and bone marrow transplant retinopathy; proliferative disorders such as proliferative vitreal retinopathy and epiretinal membranes, and proliferative diabetic retinopathy; infectious disorders such as ocular histoplasmosis, ocular toxocariasis, presumed ocular histoplasmosis syndrome (PONS), endophthalmitis, toxoplasmosis, retinal diseases associated with HIV infection, choroidal disease associate with HIV infection, uveitic disease associate with HIV infection, viral retinitis, acute retinal necrosis, progressive outer retinal necrosis, fungal retinal diseases, ocular syphilis, ocular tuberculosis, diffuse unilateral subacute neuroretinitis, and myiasis; genetic disorders such as retinitis pigmentosa, systemic disorders with associated retinal dystrophies, congenital stationary night blindness, cone dystrophies, Stargardt's disease and fundus flavimaculatus, Best's disease, pattern dystrophy of the retinal pigmented epithelium, X-linked retinoschisis, Sorsby's fundus dystrophy, benign concentric maculopathy, Bietti's crystalline dystrophy, and pseudoxanthoma elasticum; retinal tears/holes such as retinal detachment, macular hole, and giant retinal tear; tumors such as retinal disease associated with tumors, congenital hypertrophy of the retinal pigmented epithelium, posterior uveal melanoma, choroidal hemangioma, choroidal osteoma, choroidal metastasis, combined hamartoma of the retina and retinal pigmented epithelium, retinoblastoma, vasoproliferative tumors of the ocular fundus, retinal astrocytoma, and intraocular lymphoid tumors; and miscellaneous other diseases affecting the posterior part of the eye such as punctate inner choroidopathy, acute posterior multifocal placoid pigment epitheliopathy, myopic retinal degeneration, and acute retinal pigment epitheliitis, systemic inflammatory diseases such as stroke, coronary artery disease, obstructive airway diseases, HIV-mediated retroviral infections, cardiovascular disorders including coronary artery disease, neuroinflammation, neurological disorders, pain and immunological disorders, asthma, allergic disorders, inflammation, systemic lupus erythematosus, psoriasis, CNS disorders such as Alzheimer's disease, arthritis, sepsis, inflammatory bowel disease, cachexia, angina pectoris, post-surgical corneal inflammation, blepharitis, MGD, dermal wound healing, burns, rosacea, atopic dermatitis, acne, psoriasis, seborrheic dermatitis, actinic keratoses, viral warts, photoaging rheumatoid arthritis and related inflammatory disorders, alopecia, glaucoma, branch vein occlusion, Best's vitelliform macular degenartion, retinitis pigmentosa, proliferative vitreoretinopathy (PVR), and any other degenerative disease of either the photoreceptors or the RPE.
The actual amount of the compound to be administered in any given case will be determined by a physician taking into account the relevant circumstances, such as the severity of the condition, the age and weight of the patient, the patient's general physical condition, the cause of the condition, and the route of administration.
The patient will be administered the compound orally in any acceptable form, such as a tablet, liquid, capsule, powder and the like, or other routes may be desirable or necessary, particularly if the patient suffers from nausea. Such other routes may include, without exception, transdermal, parenteral, subcutaneous, intranasal, via an implant stent, intrathecal, intravitreal, topical to the eye, back to the eye, intramuscular, intravenous, and intrarectal modes of delivery. Additionally, the formulations may be designed to delay release of the active compound over a given period of time, or to carefully control the amount of drug released at a given time during the course of therapy.
In another embodiment of the invention, there are provided pharmaceutical compositions including at least one compound of the invention in a pharmaceutically acceptable carrier thereof. The phrase “pharmaceutically acceptable” means the carrier, diluent or excipient must be compatible with the other ingredients of the formulation and not deleterious to the recipient thereof.
Pharmaceutical compositions of the present invention can be used in the form of a solid, a solution, an emulsion, a dispersion, a patch, a micelle, a liposome, and the like, wherein the resulting composition contains one or more compounds of the present invention, as an active ingredient, in admixture with an organic or inorganic carrier or excipient suitable for enteral or parenteral applications. Invention compounds may be combined, for example, with the usual non-toxic, pharmaceutically acceptable carriers for tablets, pellets, capsules, suppositories, solutions, emulsions, suspensions, and any other form suitable for use. The carriers which can be used include glucose, lactose, gum acacia, gelatin, mannitol, starch paste, magnesium trisilicate, talc, corn starch, keratin, colloidal silica, potato starch, urea, medium chain length triglycerides, dextrans, and other carriers suitable for use in manufacturing preparations, in solid, semisolid, or liquid form. In addition auxiliary, stabilizing, thickening and coloring agents and perfumes may be used. Invention compounds are included in the pharmaceutical composition in an amount sufficient to produce the desired effect upon the process or disease condition.
Pharmaceutical compositions containing invention compounds may be in a form suitable for oral use, for example, as tablets, troches, lozenges, aqueous or oily suspensions, dispersible powders or granules, emulsions, hard or soft capsules, or syrups or elixirs. Compositions intended for oral use may be prepared according to any method known in the art for the manufacture of pharmaceutical compositions and such compositions may contain one or more agents selected from the group consisting of a sweetening agent such as sucrose, lactose, or saccharin, flavoring agents such as peppermint, oil of wintergreen or cherry, coloring agents and preserving agents in order to provide pharmaceutically elegant and palatable preparations. Tablets containing invention compounds in admixture with non-toxic pharmaceutically acceptable excipients may also be manufactured by known methods. The excipients used may be, for example, (1) inert diluents such as calcium carbonate, lactose, calcium phosphate or sodium phosphate; (2) granulating and disintegrating agents such as corn starch, potato starch or alginic acid; (3) binding agents such as gum tragacanth, corn starch, gelatin or acacia, and (4) lubricating agents such as magnesium stearate, stearic acid or talc. The tablets may be uncoated or they may be coated by known techniques to delay disintegration and absorption in the gastrointestinal tract and thereby provide a sustained action over a longer period. For example, a time delay material such as glyceryl monostearate or glyceryl distearate may be employed.
In some cases, formulations for oral use may be in the form of hard gelatin capsules wherein the invention compounds are mixed with an inert solid diluent, for example, calcium carbonate, calcium phosphate or kaolin. They may also be in the form of soft gelatin capsules wherein the invention compounds are mixed with water or an oil medium, for example, peanut oil, liquid paraffin or olive oil.
The pharmaceutical compositions may be in the form of a sterile injectable suspension. This suspension may be formulated according to known methods using suitable dispersing or wetting agents and suspending agents. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose any bland fixed oil may be employed including synthetic mono- or diglycerides, fatty acids (including oleic acid), naturally occurring vegetable oils like sesame oil, coconut oil, peanut oil, cottonseed oil, etc., or synthetic fatty vehicles like ethyl oleate or the like. Buffers, preservatives, antioxidants, and the like can be incorporated as required.
The compounds of the invention may also be administered in the form of suppositories for rectal administration of the drug. These compositions may be prepared by mixing the invention compounds with a suitable non-irritating excipient, such as cocoa butter, synthetic glyceride esters of polyethylene glycols, which are solid at ordinary temperatures, but liquefy and/or dissolve in the rectal cavity to release the drug.
Since individual subjects may present a wide variation in severity of symptoms and each drug has its unique therapeutic characteristics, the precise mode of administration and dosage employed for each subject is left to the discretion of the practitioner.
The compounds and pharmaceutical compositions described herein are useful as medicaments in mammals, including humans, for treatment of diseases and/or alleviations of conditions which are responsive to treatment by agonists or functional antagonists of the N-formyl peptide receptor like-1 (FPRL-1) receptor. Thus, in further embodiments of the invention, there are provided methods for treating a disorder associated with modulation of the N-formyl peptide receptor like-1 (FPRL-1) receptor. Such methods can be performed, for example, by administering to a subject in need thereof a pharmaceutical composition containing a therapeutically effective amount of at least one invention compound. As used herein, the term “therapeutically effective amount” means the amount of the pharmaceutical composition that will elicit the biological or medical response of a subject in need thereof that is being sought by the researcher, veterinarian, medical doctor or other clinician. In some embodiments, the subject in need thereof is a mammal. In some embodiments, the mammal is human.
The present invention concerns also processes for preparing the compounds of Formula I. The compounds of formula I according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry. Synthetic Scheme 1 set forth below, illustrates how the compounds according to the invention can be made.
Compounds of Formula I were prepared as depicted in Scheme 1. Compounds of Formula II were prepared as depicted in Scheme 2. In general, a t-butyl ester derivative of an amino acid is reacted with a substituted phenylisocyanate to produce a phenylurea derivative. The t-butyl ester protecting group is then removed under acidic conditions to give the amino acid urea. The carboxylic acid group is then converted to an amide by treating the compound with activating reagents, such as 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDCI) and Hydroxybenzotriazole (HOBt) in the presence of an amine, or by other methods known to those skilled in the art. At this stage, those skilled in the art will appreciate that many additional compounds that fall under the scope of the invention may be prepared by performing various common chemical reactions. Details of certain specific chemical transformations are provided in the examples.
Those skilled in the art will be able to routinely modify and/or adapt the following scheme to synthesize any compounds of the invention covered by Formula I or Formula II.
DETAILED DESCRIPTION OF THE INVENTION
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention claimed. As used herein, the use of the singular includes the plural unless specifically stated otherwise.
It will be readily apparent to those skilled in the art that some of the compounds of the invention may contain one or more asymmetric centers, such that the compounds may exist in enantiomeric as well as in diastereomeric forms. Unless it is specifically noted otherwise, the scope of the present invention includes all enantiomers, diastereomers and racemic mixtures. Some of the compounds of the invention may form salts with pharmaceutically acceptable acids or bases, and such pharmaceutically acceptable salts of the compounds described herein are also within the scope of the invention.
The present invention includes all pharmaceutically acceptable isotopically enriched compounds. Any compound of the invention may contain one or more isotopic atoms enriched or different than the natural ratio such as deuterium 2 H (or D) in place of hydrogen 1H (or H) or use of 13 C enriched material in place of 12 C and the like. Similar substitutions can be employed for N, O and S. The use of isotopes may assist in analytical as well as therapeutic aspects of the invention. For example, use of deuterium may increase the in vivo half-life by altering the metabolism (rate) of the compounds of the invention. These compounds can be prepared in accord with the preparations described by use of isotopically enriched reagents.
The following examples are for illustrative purposes only and are not intended, nor should they be construed as limiting the invention in any manner. Those skilled in the art will appreciate that variations and modifications of the following examples can be made without exceeding the spirit or scope of the invention.
As will be evident to those skilled in the art, individual isomeric forms can be obtained by separation of mixtures thereof in conventional manner. For example, in the case of diasteroisomeric isomers, chromatographic separation may be employed.
Compound names were generated with ACD version 12.5. In general, characterization of the compounds is performed according to the following methods, NMR spectra are recorded on 300 or 600 MHz Varian and acquired at room temperature. Chemical shifts are given in ppm referenced either to internal TMS or to the solvent signal.
All the reagents, solvents, catalysts for which the synthesis is not described are purchased from chemical vendors such as Sigma Aldrich, Fluka, Bio-Blocks, Combi-blocks, TCI, VWR, Lancaster, Oakwood, Trans World Chemical, Alfa, Fisher, Maybridge, Frontier, Matrix, Ukrorgsynth, Toronto, Ryan Scientific, SiliCycle, Anaspec, Syn Chem, Chem-Impex, MIC-scientific, Ltd; however some known intermediates, were prepared according to published procedures.
Usually the compounds of the invention were purified by medium pressure liquid chromatography, unless noted otherwise.
The following abbreviations are used in the examples:
Et 3 N
triethylamine
CH 2 Cl 2
dichloromethane
CDCl 3
deuterated chloroform
MeOH
methanol
CD 3 OD
deuterated methanol
Na 2 SO 4
sodium sulfate
DMF
N,N dimethylformamide
EDCl
1-ethyl-3-(3-dimethylaminopropyl) carbodiimide
HOBt
Hydroxybenzotriazole
THF
tertahydrofuran
ClCO 2 Et
ethylchloroformate
NH 3
ammonia
The following synthetic schemes illustrate how compounds according to the invention can be made. Those skilled in the art will be routinely able to modify and/or adapt the following schemes to synthesize any compound of the invention covered by Formula II.
Example 1
Intermediate 1
tert-Butyl (2S)-2-{[(4-Bromophenyl)carbamoyl]amino}-3-phenylpropanoate
To a solution of L-phenyl-alanine tert-butyl ester hydrochloride (100 mg, 0.41 mmol) and 6 mL of methylene chloride at 25° C. was added 4-bromo-phenyl isocyanate (81 mg, 0.41 mmol) and triethylamine (62 mg, 0.62 mmol). The resulting mixture was stirred at 25° C. for 30 minutes. The mixture was concentrated and the residue was purified by medium pressure liquid chromatography on silica gel using ethyl acetate:hexane (20:80) to yield Intermediate 1, as a white solid.
1 H NMR (CDCl 3 , 300 MHz) δ: 7.20-7.35 (m, 5H), 7.13-7.20 (m, 2H), 7.01-7.10 (m, 2H), 6.79 (br. s., NH), 5.52 (br. s., NH), 4.70 (t, J=6.2 Hz, 1H), 2.91 (ddd, J=19.0 Hz, J=6.0 Hz, 2H), 1.47 (m, 9H).
Intermediates 2, 3 and 4 were prepared from the corresponding amino acid in a similar manner to the procedure described in Example 1 for Intermediate 1, starting with the appropriate amino acid. The results are described below in Table 1.
TABLE 1
Interm.
IUPAC name
No.
Structure
1 H NMR δ (ppm)
2
tert-Butyl (2S,3S)-2-{[(4-bromo phenyl)carbamoyl]amino}-3- methylpentanoate
1 H NMR (CDCl 3 , 300 MHz) δ: 7.29- 7.39 (m, 2H), 7.10-7.22 (m, 2H), 6.83 (br. s., 1H), 4.44 (d, J = 4.4 Hz, 1H), 1.81-1.99 (m, 1H), 1.36-1.46 (m, 1H), 1.08-1.31 (m, 1H), 0.86-1.02 (m, 6H).
3
tert-Butyl (2S)-2-{[(4- bromophenyl) carbamoyl]amino}-pentanoate
1 H NMR (CDCl 3 , 300 MHz) δ: 7.26- 7.36 (m, 2H), 7.09-7.18 (m, 2H), 6.95 (br. s., NH), 4.40-4.50 (m, 1H), 1.73-1.89 (m, 1H), 1.52- 1.72 (m, 1H), 1.25-1.46 (m, 2H), 0.95 (t, 2H).
4
tert-butyl (2S)-2-{[(4-bromo phenyl) carbamoyl]amino}-4- methylpentanoate
1 H NMR (CDCl 3 , 300 MHz) δ: 7.20- 7.33 (m, 2H), 7.04-7.15 (m, 2H), 4.44 (dd, J = 9.1, 5.3 Hz, 1H), 1.74 (dd, J = 12.9, 6.4 Hz, 1H), 1.54-1.68 (m, 1H), 1.50 (s, 9H), 1.40-1.47 (m, 1H), 0.97 (d, J = 3.5 Hz, 3H), 0.95 (d, 3H).
Example 2
Intermediate 5
(2S)-2-{[(4-Bromophenyl)carbamoyl]amino}-3-phenylpropanoic Acid
A solution of Intermediate 1 (60 mg, 0.15 mmol) and 0.5 mL of formic acid was stirred at 25° C. for 3 hours. The resulting mixture was quenched with water (1 mL) then extracted with ethyl acetate. The organic layer was washed with water, brine, dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The residue was rinsed 4 times with methylene chloride:hexane (1:1) to yield Intermediate 5 as a white solid.
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.29 (s, NH), 7.40-7.50 (m, 2H), 7.32-7.40 (m, 2H), 7.18-7.31 (m, 5H), 5.98 (d, J=7.9 Hz, NH), 4.67 (m, 1H), 3.02 (ddd, J=19.0 Hz, J=6.0 Hz, 2H).
Intermediates 6, 7 and 8 and Compounds 1 through 6 were prepared from the corresponding urea derivative in a similar manner to the procedure described in Example 2 for Intermediate 5. The results are described below in Table 2.
TABLE 2
Interm.
IUPAC name
No.
Structure
1 H NMR δ (ppm)
6
(2S,3S)-2-{[(4-bromophenyl) carbamoyl]amino}-3- methylpentanoic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.24 (br. s., 1H), 7.44-7.53 (m, 2H), 7.32-7.42 (m, 2H), 6.08 (d, J = 8.8 Hz, 1H), 4.44 (dd, J = 8.6, 4.8 Hz, 1H), 1.86-2.00 (m, J = 9.1, 6.9, 4.6, 4.6 Hz, 1H), 1.43-1.61 (m, 1H), 1.15- 1.33 (m, 1H), 0.88-1.04 (m, 6H).
7
(2S)-2-{[(4-bromophenyl) carbamoyl]amino}-pentanoic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.20 (s, NH), 7.43-7.52 (m, 2H), 7.33- 7.41 (m, 2H), 6.08 (d, J = 9.1 Hz, NH), 4.38-4.50 (m, 1H), 1.77-1.92 (m, 1H), 1.61-1.76 (m, 1H), 1.36- 1.53 (m, 2H), 0.89-1.00 (m, 3H).
8
(2S)-2-{[(4-bromophenyl) carbamoyl]amino}-4- methylpentanoic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.17 (s, NH), 7.43-7.51 (m, 2H), 7.35- 7.41 (m, 2H), 6.04 (d, J = 9.1 Hz, NH), 4.42-4.53 (m, 1H), 1.73-1.88 (m, 1H), 1.53-1.73 (m, 2H), 0.97 (d, J = 2.1 Hz, 3H), 0.95 (d, 3H).
Comp.
IUPAC name
No.
Structure
1 H NMR δ (ppm)
1
{[(2S)-2-{[(4- bromophenyl)carbamoyl] amino}-3- phenylpropanoyl]amino} acetic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.26 (s, NH), 7.71 (br. s., NH), 7.32- 7.46 (m, 4H), 7.13-7.31 (m, 5H), 6.03 (d, J = 8.5 Hz, NH), 4.71 (td, J = 7.7, 5.4 Hz, 1H), 3.98 (d, J = 5.9 Hz, 2H), 3.14-3.26 (m, 1 H), 3.01 (dd, 1H).
2
3-{[(2S)-2-{[(4- bromophenyl)carbamoyl] amino}-3- phenylpropanoyl]amino} propanoic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.27 (s, NH), 7.44 (s, NH), 7.33-7.43 (m, 4H), 7.15-7.30 (m, 5H), 6.03 (d, J = 7.9 Hz, NH), 4.53-4.65 (m, 1H), 3.34-3.51 (m, 2H), 2.93-3.15 (m, 2H), 2.47 (td, 2H).
3
{[(2S,3S)-2-{[(4-bromo-2- fluorophenyl)carbamoyl] amino}-3- methylpentanoyl]amino} acetic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.28 (t, J = 8.9 Hz, 1H), 8.16 (br. s., NH), 7.67 (br. s., NH), 7.34 (dd, J = 11.0, 2.2 Hz, 1H), 7.23-7.30 (m, 1H), 6.57 (d, J = 9.4 Hz, NH), 4.37 (dd, J = 8.6, 5.7 Hz, 1H), 3.89-4.08 (m, 2H), 1.86-1.98 (m, 1H), 1.53-1.67 (m, 1H), 1.10-1.27 (m, 1H), 0.98 (d, J = 6.7 Hz, 3H), 0.85-0.94 (m, 3H).
4
{[(2S,3S)-2-{[(4- bromophenyl)carbamoyl] amino}-3- methylpentanoyl]amino} acetic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.27 (s, NH), 7.66 (br. s., NH), 7.42- 7.51 (m, 2H), 7.32-7.41 (m, 2H), 6.08 (d, J = 8.2 Hz, NH), 4.34 (dd, J = 8.6, 5.7 Hz, 1 H), 3.88-4.09 (m, 2H), 1.81- 1.96 (m, 1H), 1.49-1.67 (m, 1H), 1.06- 1.27 (m, 1H), 0.97 (d, J = 6.7 Hz, 3H), 0.86-0.93 (m, 3H).
5
{[(2S)-2-{[(4- bromophenyl)carbamoyl] amino}pentanoyl]amino}acetic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.25 (s, NH), 7.67 (br. s., NH), 7.41- 7.51 (m, 2H), 7.34-7.41 (m, 2H), 6.13 (d, J = 7.9 Hz, NH), 4.42 (td, J = 7.7, 5.4 Hz, 1 H), 3.89-4.08 (m, 2H), 1.73- 1.89 (m, 1H), 1.54-1.69 (m, 1H), 1.34- 1.51 (m, 2H), 0.91 (t, J = 7.3 Hz, 3H).
6
{[(2S)-2-{[(4- bromophenyl)carbamoyl] amino}-4- methylpentanoyl]amino}acetic acid
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.19 (s, NH), 7.70 (br. s., NH), 7.42- 7.51 (m, 2H), 7.33-7.41 (m, 2H), 6.07 (d, J = 7.6 Hz, NH), 4.46 (ddd, J = 9.6, 8.3, 5.0 Hz, 1H), 3.87-4.07 (m, 2H), 1.72-1.86 (m, 1H), 1.61-1.72 (m, 1H), 1.46-1.59 (m, 1H), 0.95 (s, 3H), 0.93 (s, 3H).
Example 3
Compound 7
tert-Butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-3-phenylpropanoyl]amino}acetate
To a solution of Intermediate 5 (80 mg, 0.22 mmol) and 2 mL of anhydrous DMF at 25° C. was added EDCI (64 mg, 0.33 mmol), HOBt (45 mg, 0.33 mmol), glycine tert-butyl ester (44 mg, 0.33 mmol) and N-methylmorpholine (44 mg, 0.44 mmol). The resulting mixture was stirred at 25° C. for 12 hours. The mixture was quenched with water (1 mL), and the product was extracted with ethyl acetate (20 mL). The layers were separated, and the organic layer was washed with water, brine, dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting product was purified by medium pressure liquid chromatography on silica gel using ethyl acetate:hexane (40:60) to yield Compound 7 as a white solid.
1 H NMR (CDCl 3 , 300 MHz) δ: 7.18-7.35 (m, 7H), 7.03 (d, J=8.5 Hz, 2H), 6.85 (br. s., 1H), 4.69 (t, J=7.5 Hz, 1H), 3.74-3.96 (m, 2H), 2.98-3.19 (m, 2H), 1.42 (s, 9H).
Compounds 8 through 27 and Intermediate 9 were prepared from the corresponding urea derivative in a similar manner to the procedure described in Example 3 for Compound 7. The results are described below in Table 3.
TABLE 3
Comp.
IUPAC name
No.
Structure
1 H NMR δ (ppm)
8
1 H NMR (CDCl 3 , 300 MHz) δ: 7.18-7.35 (m, 7H), 7.08-7.17 (m, 2H), 4.54-4.64 (m, 1H), 3.28- 3.52 (m, 2H), 2.94-3.17 (m, 2H), 2.18-2.40 (m, 2H), 1.41 (s, 9H).
9
1 H NMR (CD 3 OD, 300 MHz) δ: 7.30-7.37 (m, 2H), 7.17-7.30 (m, 7H), 4.50 (dd, J = 7.8, 6.3 Hz, 1H), 3.44-3.59 (m, 2H), 3.23- 3.30 (m, 2H), 3.05-3.15 (m, 1H), 2.90-3.01 (m, 1H).
10
1 H NMR (CDCl 3 , 300 MHz) δ: 7.92-7.99 (t, J = 8.9 Hz, 1H), 7.40 (br. s., NH), 7.07-7.16 (m, 2H), 6.67 (s, NH), 6.54 (br. s., NH), 4.21-4.27 (m, 1H), 4.05- 4.15 (m, 1H), 3.83-3.92 (m, 1H), 1.79-1.88 (m, 1H), 1.57-1.64 (m, 1H), 1.47 (s, 9H), 1.19-1.24 (m, 1H), 1.00 (d, J = 6.7 Hz, 3H), 0.92 (t, 3H).
11
1 H NMR (CD 3 OD, 300 MHz) δ: 8.55 (s, NH), 8.36 (br. s., NH), 7.33-7.40 (m, 2H), 7.26-7.33 (m, 2H), 6.28 (d, J = 8.5 Hz, NH), 4.20 (dd, J = 8.6, 6.3 Hz, 1H), 3.72-3.97 (m, 2H), 1.80-1.94 (m, 1H), 1.56-1.70 (m, 1H), 1.45 (s, 9H), 1.13-1.31 (m, 1H), 1.01 (d, J = 6.7 Hz, 3H), 0.92-0.98 (m, 3H).
12
1 H NMR (CD 3 OD, 300 MHz) δ: 7.34-7.41 (m, 2H), 7.26-7.34 (m, 2H), 4.22 (d, J = 6.2 Hz, 1H), 4.05 (d, J = 8.2 Hz, 2H), 2.14 (s, 3H), 1.80-1.94 (m, 1H), 1.53- 1.68 (m, 1H), 1.14-1.26 (m, 1H), 0.81-1.07 (m, 6H).
13
1 H NMR (CD 3 OD, 300 MHz) δ: 7.99 (t, J = 8.8 Hz, 1H), 7.31 (dd, J = 10.7, 2.2 Hz, 1H), 7.16-7.27 (m, 1H), 4.22 (d, J = 5.9 Hz, 1H), 3.94-4.14 (m, 2H), 2.14 (s, 3H), 1.84-1.96 (m, 1H), 1.52-1.67 (m, 1H), 1.14-1.32 (m, 1H), 1.01 (d, J = 7.0 Hz, 3H), 0.92-0.98 (m, 3H).
14
1 H NMR (CD 3 OD, 300 MHz) δ: 7.33-7.42 (m, 2H), 7.26-7.33 (m, 2H), 4.12 (d, J = 6.4 Hz, 1H), 3.55-3.65 (m, 2H), 3.32-3.37 (m, 1H), 1.76-1.91 (m, 1H), 1.48- 1.63 (m, 1H), 1.09-1.31 (m, 2H), 0.90-0.99 (m, 6H).
15
1 H NMR (CD 3 OD, 300 MHz) δ: 7.99 (t, J = 8.6 Hz, 1H), 7.31 (dd, J = 10.8, 2.3 Hz, 1H), 7.18-7.27 (m, 1H), 4.13 (d, J = 6.4 Hz, 1H), 3.56-3.65 (m, 2H), 3.31-3.37 (m, 1H), 1.77-1.89 (m, 1H), 1.50- 1.61 (m, 1H), 1.10-1.26 (m, 1H), 0.88-1.01 (m, 6H).
16
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.23 (s, NH), 7.59 (br. s., NH), 7.32-7.47 (m, 4H), 7.15-7.29 (m, 5H), 6.01 (d, J = 8.2 Hz, NH), 4.70 (td, J = 7.7, 5.7 Hz, 1H), 4.05 (d, J = 5.3 Hz, 2H), 3.12- 3.24 (m, 1H), 2.95-3.06 (m, 1H), 2.10 (s, 3H).
17
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.22 (t, J = 8.9 Hz, 1H), 8.12 (br. s., NH), 7.61 (br. s., NH), 7.32 (dd, J = 11.0, 2.2 Hz, 1H), 7.15-7.29 (m, 6H), 6.51 (d, J = 7.3 Hz, NH), 4.72 (td, J = 7.9, 5.6 Hz, 1H), 4.05 (dd, J = 5.6, 1.2 Hz, 2H), 3.14-3.24 (m, 1H), 2.95- 3.05 (m, 1H), 2.10 (s, 3H).
18
1H NMR (acetone-d 6 , 300 MHz) δ: 8.20 (s, NH), 7.60 (br. s., NH), 7.42-7.51 (m, 2H), 7.32-7.41 (m, 2H), 6.07 (d, J = 7.6 Hz, NH), 4.41 (td, J = 7.9, 5.3 Hz, 1H), 3.75-3.99 (m, 2H), 1.73-1.89 (m, 1H), 1.53-1.70 (m, 1H), 1.43 (s, 9H), 1.37-1.48 (m, 2H), 0.92 (t, J = 7.3 Hz, 3H).
19
1 H NMR (CD 3 OD, 300 MHz) δ: 7.91 (t, J = 8.6 Hz, 1H), 7.17- 7.34 (m, 7H), 4.50 (dd, J = 8.2, 6.2 Hz, 1H), 3.44-3.59 (m, 2H), 3.23-3.27 (m, 2H), 3.05-3.17 (m, 1H), 2.87-2.99 (m, 1H).
20
1 H NMR (CD 3 OD, 300 MHz) δ: 7.33-7.41 (m, 2H), 7.25-7.33 (m, 2H), 4.23 (dd, J = 8.2, 5.6 Hz, 1H), 3.56-3.63 (m, 2H), 1.69- 1.84 (m, 1H), 1.54-1.68 (m, 1H), 1.29-1.51 (m, 2H), 0.91-1.02 (m, 3H).
21
1 H NMR (CD 3 OD, 300 MHz) δ: 7.97 (t, J = 8.6 Hz, 1H), 7.31 (dd, J = 10.7, 2.2 Hz, 1H), 7.19-7.27 (m, 1H), 4.23 (dd, J = 8.1, 5.4 Hz, 1H), 3.56-3.66 (m, 2H), 1.68- 1.83 (m, 1H), 1.54-1.68 (m, 1H), 1.34-1.51 (m, 2H), 0.91-1.03 (m, 3H).
22
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.19 (s, NH), 7.71 (br. s., NH), 7.42-7.52 (m, 2H), 7.31-7.42 (m, 2H), 6.07 (d, J = 8.2 Hz, NH), 4.34-4.47 (m, 1H), 3.86-4.10 (m, 2H), 3.66 (s, 3H), 1.73-1.87 (m, 1H), 1.55-1.71 (m, 1H), 1.35- 1.51 (m, 2H), 0.92 (t, 3H).
23
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.19 (s, NH), 7.69 (br. s., NH), 7.42-7.50 (m, 2H), 7.32-7.40 (m, 2H), 6.07 (d, J = 8.2 Hz, NH), 4.42 (td, J = 7.9, 5.6 Hz, 1H), 4.13 (q, J = 7.2 Hz, 2H), 3.85- 4.06 (m, 2H), 1.73-1.88 (m, 1H), 1.55-1.69 (m, 1H), 1.34-1.51 (m, 2H), 1.20 (t, J = 7.3, 3H), 0.92 (t, J = 7.3, 3H).
24
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.20 (s, NH), 7.67 (br. s., NH), 7.43-7.51 (m, 2H), 7.33-7.42 (m, 2H), 6.07 (d, J = 9.7 Hz, NH), 4.97 (dt, J = 12.5, 6.2 Hz, 1H), 4.41 (td, J = 7.8, 5.4 Hz, 1H), 3.82-4.04 (m, 2H), 1.73-1.89 (m, 1H), 1.55-1.70 (m, 1H), 1.34- 1.50 (m, 2H), 1.22 (s, 3H), 1.20 (s, 3H), 0.92 (t, J = 7.3, 3H).
25
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.16 (s, NH), 7.62 (br. s., NH), 7.42-7.49 (m, 2H), 7.33-7.40 (m, 2H), 6.03 (d, J = 8.8 Hz, NH), 4.40-4.51 (m, 1H), 3.76-3.95 (m, 2H), 1.72-1.84 (m, 1H), 1.60- 1.73 (m, 1H), 1.45-1.58 (m, 1H), 0.95 (s, 3H), 0.93 (s, 3H).
26
1 H NMR (CD 3 OD, 300 MHz) δ: 7.34-7.41 (m, 2H), 7.26-7.33 (m, 2H), 4.24-4.33 (m, 1H), 3.55- 3.64 (m, 2H), 3.32-3.35 (m, 2H), 1.64-1.79 (m, 1H), 1.48- 1.62 (m, 2H), 0.98 (d, J = 4.1 Hz, 3H), 0.96 (d, J = 3.8 Hz, 3H).
27
1 H NMR (acetone-d 6 , 300 MHz) δ: 8.17 (s, NH), 7.61 (br. s., NH), 7.42-7.50 (m, 2H), 7.32-7.42 (m, 2H), 6.06 (d, J = 8.5 Hz, NH), 4.45 (ddd, J = 9.7, 8.1, 5.0 Hz, 1H), 4.04 (d, J = 5.6 Hz, 2H), 2.12 (s, 3H), 1.72-1.84 (m, 1H), 1.60-1.72 (m, 1H), 1.45-1.58 (m, 1H), 0.95 (s, 3H), 0.93 (s, 3H).
28
1 H NMR (acetone-d 6 , 300 MHz) δ: 10.27 (br. s., OH), 8.18 (br. s., NH), 8.03 (s, NH), 7.42-7.50 (m, 2H), 7.32-7.41 (m, 2H), 6.11 (d, J = 9.1 Hz, NH), 4.23-4.34 (m, 1H), 1.52-1.80 (m, 2H), 1.27- 1.49 (m, 2H), 0.87-0.95 (t, J = 7.3 Hz, 3H).
Example 4
Compound 28
(2S,3S)—N-(2-amino-2-oxoethyl)-2-{[(4-bromophenyl)carbamoyl]amino}-3-methylpentanamide
To a solution of Compound II (50 mg, 0.13 mmol) and 5 mL of anhydrous tetrahydrofuran under argon at −78° C. was added triethylamine (24 mg, 0.17 mmol) and ethyl chloroformate (17 mg, 0.16 mmol). The mixture was stirred at −78° C. for 30 minutes, and then ammonia gas was bubbled into reaction flask for 1 minute. The resulting mixture was stirred at 25° C. for 2 hours. The reaction was quenched with water (1 mL), and the residue was extracted with ethyl acetate (20 mL). The layers were separated, and the organic layer was washed with water, brine, dried over Na 2 SO 4 , filtered, and the filtrate was concentrated under reduced pressure. The resulting product was purified by medium pressure chromatography on silica gel using an eluent of methanol:dichloromethane (10:90) to yield to yield Compound 28 as a white solid.
1 H NMR (CD 3 OD, 300 MHz) δ: 7.33-7.40 (m, 2H), 7.26-7.33 (m, 2H), 4.05 (d, J=6.7 Hz, 1H), 3.85 (q, J=17.0 Hz, 2H), 1.78-1.91 (m, 1H), 1.54-1.69 (m, 1H), 1.16-1.33 (m, 1H), 0.99 (d, J=6.7 Hz, 3H), 0.92-0.98 (m, 3H).
Compounds 29 through 85 as well as Intermediates 10 through 35 were prepared from the corresponding acid derivative in a similar manner to the procedure described in Example 4 for Compound 28.
TABLE 4 Comp. IUPAC name No. Structure 1 H NMR δ (ppm) 29 1 H NMR (CD 3 OD, 300 MHz) δ: 8.00 (t, J = 8.6 Hz, 1H), 7.32 (dd, J = 10.7, 2.2 Hz, 1H), 7.18-7.26 (m, 1H), 4.05 (d, J = 6.4 Hz, 1H), 3.74- 3.95 (m, 2H), 1.80-1.91 (m, 1H), 1.51-1.69 (m, 1H), 1.18-1.32 (m, 1H), 1.00 (d, J = 7.0 Hz, 3H), 0.92- 0.98 (m, 3H). 30 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.27 (s, NH), 7.70 (br. s., NH), 7.41- 7.48 (m, 2H), 7.33-7.41 (m, 2H), 7.02 (s, NH), 6.30 (s, NH), 6.22 (d, J = 5.3 Hz, NH), 4.22-4.32 (m, 1H), 3.72-3.91 (m, 2H), 1.73-1.88 (m, 1H), 1.56-1.71 (m, 1H), 1.37-1.53 (m, 2H), 0.88-0.97 (m, 3H). 31 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.23 (t, J = 8.8 Hz, 1H), 8.13 (br. s., NH), 7.72 (s, NH), 7.35 (dd, J = 10.8, 2.3 Hz, 1H), 7.26 (dt, J = 8.9, 1.9 Hz, 1H), 7.00 (s, NH), 6.66 (d, J = 6.7 Hz, NH), 6.34 (s, NH), 4.29 (dd, J = 12.2, 8.1 Hz, 1H), 3.82 (dd, J = 5.9, 1.8 Hz, 2H), 1.75-1.90 (m, 1H), 1.58-1.73 (m, 1H), 1.37-1.53 (m, 2H), 0.89-0.98 (m, 3H). 32 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.20 (s, NH), 7.77 (br. s., NH), 7.40- 7.47 (m, 2H), 7.32-7.39 (m, 2H), 7.04 (br. s., NH), 6.38 (br. s., NH), 6.18 (d, J = 7.3 Hz, NH), 4.31 (ddd, J = 9.4, 7.0, 5.3 Hz, 1H), 3.71-3.93 (m, 2H), 1.69-1.85 (m, 1H), 1.49- 1.69 (m, 2H), 0.96 (d, J = 3.2 Hz, 3H), 0.93 (d, J = 3.2 Hz, 3H). 33 1 H NMR (CDCl 3 , 300 MHz) δ: 7.89 (t, J = 8.8 Hz, 1H), 7.55 (br. s., NH), 7.07 (dd, J = 10.7, 2.2 Hz, 1H), 6.95- 7.04 (m, 1H), 6.84 (br. s., NH), 4.43 (br. s., NH), 4.00-4.16 (m, 1H), 3.81-3.92 (m, 1H), 1.69-1.88 (m, 1H), 1.56-1.70 (m, 2H), 1.47 (s, 9H), 0.97 (d, J = 4.7 Hz, 3H), 0.95 (d, 3H). 34 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.27 (t, J = 8.8 Hz, 1H), 8.07 (br. s., NH), 7.71 (br. s., NH), 7.34 (dd, J = 10.8, 2.1 Hz, 1H), 7.27 (dt, J = 8.8, 1.8 Hz, 1H), 6.54 (d, J = 8.8 Hz, NH), 4.42-4.53 (m, 1H), 3.93-4.01 (m, 2H), 1.72-1.86 (m, 1H), 1.63- 1.74 (m, 1H), 1.46-1.60 (m, 1H), 0.96 (s, 3H), 0.93 (s, 3H). 35 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.30 (t, J = 8.8 Hz, 1H), 8.06 (br. s., NH), 7.62 (br. s., NH), 7.31-7.38 (m, 2H), 7.24-7.30 (m, 2H), 6.52 (d, J = 8.2 Hz, NH), 4.39-4.53 (m, 1H), 4.04 (d, J = 5.6 Hz, 2H), 2.10- 2.15 (m, 3H), 1.70-1.86 (m, 1H), 1.61-1.71 (m, 1H), 1.47-1.62 (m, 1H), 0.96 (s, 3H), 0.93 (s, 3H). 36 1 H NMR (CD 3 OD, 300 MHz) δ: 7.97 (t, J = 8.8 Hz, 1H), 7.31 (dd, J = 10.8, 2.3 Hz, 1H), 7.18-7.27 (m, 1H), 4.28 (dd, J = 9.2, 5.4 Hz, 1H), 3.56-3.64 (m, 2H), 3.32-3.37 (m, 2H), 1.64-1.80 (m, 1H), 1.50-1.62 (m, 2H), 0.98 (d, J = 4.4 Hz, 3H), 0.96 (d, 3H). 37 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.22 (t, J = 8.8 Hz, 1H), 8.09 (br. s., NH), 7.77 (br. s., NH), 7.34 (dd, J = 11.0, 2.2 Hz, 1H), 7.25 (dt, J = 8.9, 1.7 Hz, 1H), 6.99 (br. s., NH), 6.62 (d, J = 7.0 Hz, NH), 6.37 (br. s., NH), 4.33 (ddd, J = 9.6, 7.0, 5.1 Hz, 1H), 3.72-3.92 (m, 2H), 1.68-1.86 (m, 1H), 1.49-1.70 (m, 2H), 0.96 (d, J = 3.5 Hz, 3H), 0.94 (d, 3H). 38 1 H NMR (CDCl 3 , 300 MHz) δ: 7.90 (t, J = 8.8 Hz, 1H), 7.45 (br. s., NH), 7.02-7.15 (m, 2H), 6.92 (s, NH), 6.61 (br. s., NH), 4.37-4.54 (m, 2H), 1.79 (dt, J = 13.2, 6.9 Hz, 1H), 1.56-1.69 (m, 2H), 1.46 (s, 9H), 1.40 (d, J = 7.3 Hz, 3H), 0.97 (s, 3H), 0.95 (s, 3H). 39 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.26 (t, J = 8.9 Hz, 1H), 8.08 (br. s., NH), 7.67 (d, J = 7.0 Hz, NH), 7.33 (dd, J = 10.8, 2.3 Hz, 1H), 7.27 (dt, J = 8.8, 1.8 Hz, 1H), 6.52 (d, J = 9.1 Hz, NH), 4.40-4.54 (m, 2H), 1.72- 1.87 (m, 1H), 1.59-1.72 (m, 1H), 1.45-1.57 (m, 1H), 1.39 (d, J = 7.3 Hz, 3H), 0.95 (s, 3H), 0.93 (s, 3H). 40 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.25 (t, J = 8.8 Hz, 1H), 8.09 (br. s., NH), 7.57 (d, J = 5.6 Hz, NH), 7.35 (dd, J = 11.0, 2.2 Hz, 1H), 7.22- 7.31 (m, 1H), 6.92 (br. s., NH), 6.54 (d, J = 7.3 Hz, NH), 6.29 (br. s., NH), 4.30-4.44 (m, 2H), 1.73-1.90 (m, 1H), 1.47-1.72 (m, 2H), 1.30 (d, J = 7.0 Hz, 3H), 0.95 (d, J = 1.5 Hz, 3H), 0.93 (d, 3H). 41 1 H NMR (CDCl 3 , 300 MHz) δ: 7.62 (br. s., NH), 7.21-7.29 (m, 2H), 7.08-7.16 (m, 2H), 6.90 (br. s., NH), 4.39-4.50 (m, 1H), 4.35 (t, J = 7.0 Hz, 1H), 1.73-1.86 (m, 1H), 1.54-1.67 (m, 2H), 1.45 (s, 9H), 1.38 (d, 3H), 0.97 (d, J = 2.9 Hz, 3H), 0.95 (d, J = 2.9 Hz, 3H). 42 1 H NMR (CDCl 3 , 300 MHz) δ: 7.45 (br. s., NH), 7.21-7.30 (m, 2H), 7.10-7.18 (m, 2H), 4.45 (t, J = 7.2 Hz, 1H), 4.32 (dd, J = 8.5, 5.0 Hz, 1H), 2.07-2.20 (m, 1H), 1.77 (dt, J = 13.3, 6.8 Hz, 1H), 1.56-1.67 (m, 2H), 1.47 (s, 9H), 0.98 (d, J = 2.3 Hz, 3H), 0.96 (d, 3H), 0.93 (s, 3H), 0.91 (s, 3H). 43 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.22 (s, NH), 7.66 (d, J = 6.4 Hz, NH), 7.43-7.50 (m, 2H), 7.34-7.41 (m, 2H), 6.05 (d, J = 7.9 Hz, NH), 4.39-4.52 (m, 2H), 2.81 (br. s., 4H), 1.71-1.86 (m, 1H), 1.57-1.71 (m, 1H), 1.43-1.57 (m, 1H), 1.39 (d, J = 7.3 Hz, 3H), 0.94 (s, 3H), 0.92 (s, 3H). 44 1 H NMR (acetone-d 6 , 300 MHz) δ: 7.45 (br. s., NH), 7.21-7.30 (m, 2H), 7.10-7.18 (m, 2H), 4.45 (t, J = 7.2 Hz, 1H), 4.32 (dd, J = 8.5, 5.0 Hz, 1H), 2.07-2.20 (m, 1H), 1.77 (dt, J = 13.3, 6.8 Hz, 1H), 1.56- 1.67 (m, 2H), 1.47 (s, 9H), 0.98 (d, J = 2.3 Hz, 3H), 0.96 (d, 3H), 0.93 (s, 3H), 0.91 (s, 3H). 45 1 H NMR (acetone-d 6 , 300 MHz) δ: 8.21 (s, NH), 7.56 (s, NH), 7.42- 7.49 (m, 2H), 7.33-7.40 (m, 2H), 6.06-6.12 (s, NH), 4.28-4.44 (m, 2H), 1.70-1.89 (m, 1H), 1.59-1.70 (m, 1H), 1.47-1.59 (m, 1H), 1.30 (d, J = 7.3 Hz, 3H), 0.95 (s, 3H), 0.92 (s, 3H). 46 1 H NMR (CD 3 OD, 300 MHz) δ: 7.34- 7.40 (m, 2H), 7.26-7.33 (m, 2H), 4.34 (dd, J = 9.5, 5.4 Hz, 1H), 4.21 (d, J = 7.0 Hz, 1H), 2.02-2.16 (m, 1H), 1.67-1.79 (m, 1H), 1.51-1.65 (m, 1H), 0.94-1.00 (m, 9H). 47 1 H NMR (CD 3 OD, 300 MHz) δ: 7.93 (s, NH), 7.33-7.40 (m, 2H), 7.26- 7.33 (m, 2H), 6.28 (br. s., NH), 4.25- 4.36 (m, 1H), 3.15-3.27 (m, 2H), 1.67-1.81 (m, 1H), 1.50-1.67 (m, 2H), 1.17 (s, 6H), 0.99 (d, J = 4.7 Hz, 3H), 0.97 (d, 3H). 48 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.41 (m, 2H), 7.26-7.33 (m, 2H), 4.30 (dd, J = 9.4, 5.6 Hz, 1H), 3.86- 3.96 (m, 1H), 3.62 (t, J = 5.6 Hz, 4H), 1.67-1.81 (m, 1H), 1.52-1.67 (m, 2H), 0.98 (d, J = 3.8 Hz, 3H), 0.96 (d, 3H). 47 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.41 (m, 2H), 7.27-7.34 (m, 2H), 4.28 (dd, J = 8.9, 5.1 Hz, 1H), 3.64- 3.76 (m, 1H), 3.46-3.52 (m, 2H), 3.33-3.42 (m, 1H), 3.15-3.27 (m, 1H), 1.67-1.80 (m, 1H), 1.48-1.67 (m, 2H), 0.98 (d, J = 4.7 Hz, 3H), 0.96 (d, 3H). 48 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.40 (m, 2H), 7.26-7.32 (m, 2H), 4.26 (dd, J = 8.2, 6.7 Hz, 1H), 3.88- 3.99 (m, 1H), 3.49 (dd, J = 5.4, 1.3 Hz, 2H), 1.72 (dt, J = 13.3, 6.8 Hz, 1H), 1.50-1.60 (m, 2H), 1.14 (d, J = 6.7 Hz, 3H), 0.98 (d, J = 3.8 Hz, 3H), 0.96 (d, 3H). 49 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.39 (m, 2H), 7.27-7.32 (m, 2H), 4.36 (dd, J = 9.5, 5.4 Hz, 1H), 4.26 (dd, J = 8.6, 5.4 Hz, 1H), 1.49-1.84 (m, 6H), 1.45 (s, 9H), 1.36-1.43 (m, 1H), 0.99 (d, J = 4.4 Hz, 3H), 0.97 (d, J = 4.1 Hz, 3H), 0.90-0.96 (m, 3H). 50 1 H NMR (CD 3 OD, 300 MHz) δ: 7.32- 7.43 (m, 6H), 7.25-7.31 (m, 2H), 4.41 (dd, J = 9.4, 5.3 Hz, 1H), 1.72- 1.81 (m, 1H), 1.49-1.70 (m, 2H), 1.40 (s, 9H), 1.17-1.19 (m, 0H), 0.99 (t, J = 6.7 Hz, 6H). 51 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.40 (m, 2H), 7.25-7.33 (m, 2H), 4.32-4.44 (m, 2H), 1.35-1.90 (m, 7H), 0.99 (d, J = 3.8 Hz, 3H), 0.97 (d, J = 3.8 Hz, 3H), 0.91-0.96 (m, 3H). 52 1 H NMR (CD 3 OD, 300 MHz) δ: 7.40- 7.47 (m, 2H), 7.23-7.39 (m, 7H), 4.41 (dd, J = 9.4, 5.3 Hz, 1H), 1.70- 1.84 (m, 1H), 1.48-1.69 (m, 2H), 0.98 (t, 6H). 53 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.41 (m, 2H), 7.26-7.33 (m, 2H), 4.30 (ddd, J = 16.0, 9.4, 5.1 Hz, 1H), 1.50-1.86 (m, 5H), 1.33-1.48 (m, 2H), 0.95-1.01 (m, 6H), 0.89- 0.96 (m, 3H). 54 1 H NMR (CD 3 OD, 300 MHz) δ: 7.41- 7.48 (m, 2H), 7.24-7.42 (m, 7H), 4.36 (dd, J = 9.7, 5.0 Hz, 1H), 1.52- 1.82 (m, 3H), 0.92-1.02 (m, 6H). 55 1 H NMR (CDCl 3 , 300 MHz) δ: 7.30- 7.39 (m, 2H), 7.15-7.23 (m, 2H), 6.82 (br. s., 1H), 2.15-2.32 (m, 1H), 1.68-1.79 (m, 2H), 1.63 (s, 3H), 1.48 (s, 9H), 0.93 (d, J = 6.4 Hz, 3H), 0.89 (d, J = 6.2 Hz, 3H). 56 1 H NMR (CD 3 OD, 300 MHz) δ: 7.31 (d, J = 14.4 Hz, 2H), 3.92 (d, J = 1.2 Hz, 2H), 2.03-2.15 (m, 1H), 1.70- 1.86 (m, 2H), 1.58 (s, 3H), 0.95 (d, J = 6.4 Hz, 3H), 0.91 (d, J = 6.4 Hz, 3H). 57 1 H NMR (CD 3 OD, 300 MHz) δ: 7.247.39 (m, 2H), 7.24 (m, 2H), 6.50 (s, NH), 3.85 (s, 2H), 2.21- 2.40 (m, 2H), 1.82 (dq, J = 14.2, 7.3 Hz, 2H), 1.45 (s, 9H), 0.85 (t, J = 7.3 Hz, 6H). 58 1 H NMR (CD 3 OD, 600 MHz) δ: 7.35 (d, J = 8.8 Hz, 2H), 7.26-7.30 (m, 2H), 3.92 (s, 2H), 2.23-2.34 (m, 2H), 1.78-1.89 (m, 2H), 0.85 (t, J = 7.5 Hz, 6H). 59 1 H NMR (CDCl 3 , 300 MHz) δ: 7.23 (m, 2H), 7.39 (m, 2H), 3.81 (s, 2H), 1.52 (s, 6H), 1.45 (s, 9H). 60 1 H NMR (CDCl 3 , 300 MHz) δ: 7.23- 7.40 (m, 4H), 3.81 (s, 2H), 1.51 (s, 6H). 61 1 H NMR (CD 3 OD, 300 MHz) δ: 7.34- 7.39 (m, 2H), 7.28-7.33 (m, 2H), 4.36 (dd, J = 10.0, 4.7 Hz, 1H), 3.97- 4.13 (m, 2H), 3.03 (s, 3H), 2.94 (s, 3H), 1.51-1.83 (m, 3H), 0.94-1.03 (m, 6H). 62 1 H NMR (CD 3 OD, 300 MHz) δ: 7.49- 7.56 (m, 4H), 4.36 (dd, J = 9.7, 5.3 Hz, 1H), 3.70-3.95 (m, 2H), 1.69- 1.86 (m, 1H), 1.51-1.68 (m, 2H), 1.43-1.46 (m, 9H), 0.99 (dd, J = 6.4, 4.1 Hz, 6H). 63 1 H NMR (CD 3 OD, 300 MHz) δ: 7.50- 7.56 (m, 4H), 6.37 (d, J = 7.6 Hz, NH), 4.38 (dd, J = 9.7, 5.0 Hz, 1H), 3.79-4.04 (m, 2H), 1.69-1.87 (m, 1H), 1.50-1.70 (m, 2H), 0.99 (dd, J = 6.4, 3.8 Hz, 6H). 64 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.39 (m, 2H), 7.26-7.32 (m, 2H), 6.29 (s, NH), 4.17-4.24 (m, 0H), 3.73-3.95 (m, 2H), 1.87 (dtd, J = 9.8, 6.5, 3.2 Hz, 0H), 1.61 (ddt, J = 17.0, 7.4, 3.6 Hz, 0H), 1.43-1.47 (m, 9H), 1.11-1.27 (m, 0H), 0.90- 1.03 (m, 6H). 65 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.39 (m, 2H), 7.27-7.32 (m, 2H), 6.29 (s, NH), 4.19-4.26 (m, 1H), 3.81-4.00 (m, 2H), 1.84-1.94 (m, 1H), 1.60 (ddd, J = 13.2, 7.6, 3.5 Hz, 1H), 1.13-1.30 (m, 2H), 1.13- 1.30 (m, 2H), 0.96 (d, J = 17.6 Hz, 3H). 66 1 H NMR (CD 3 OD, 600 MHz) δ: 7.35- 7.38 (m, 2H), 7.28-7.31 (m, 2H), 4.34 (dd, J = 10.0, 5.0 Hz, 1H), 3.75- 3.91 (m, 2H), 1.73-1.80 (m, 1H), 1.63-1.68 (m, 1H), 1.53-1.59 (m, 1H), 1.44-1.47 (m, 9H), 0.99 (d, J = 6.7 Hz, 3H), 0.97 (d, J = 6.7 Hz, 3H). 67 1 H NMR (CD 3 OD, 600 MHz) δ: 7.34- 7.39 (m, 2H), 7.26-7.32 (m, 2H), 4.32-4.38 (m, 1H), 3.84-4.00 (m, 2H), 1.72-1.81 (m, 1H), 1.63-1.70 (m, 1H), 1.52-1.60 (m, 1H), 0.99 (d, J = 6.7 Hz, 3H), 0.97 (d, J = 6.7 Hz, 3H). 68 1 H NMR (CD 3 OD, 300 MHz) δ: 7.27- 7.34 (m, 2H), 7.17-7.24 (m, 2H), 6.24 (d, J = 7.9 Hz, NH), 4.30-4.40 (m, 1H), 3.72-3.95 (m, 2H), 2.40- 2.43 (m, 3H), 1.69-1.84 (m, 1H), 1.50-1.68 (m, 2H), 1.44-1.47 (m, 9H), 0.99 (dd, J = 6.4, 4.7 Hz, 6H). 69 1 H NMR (CD 3 OD, 300 MHz) δ: 8.27 (s, NH), 7.52 (d, J = 19.9 Hz, 4H), 6.29 (d, J = 8.5 Hz, NH), 4.27-4.43 (m, 1H), 1.70-1.85 (m, 1H), 1.45- 1.67 (m, 8H), 0.98 (dd, J = 6.4, 2.9 Hz, 6H). 70 1 H NMR (CD 3 OD, 300 MHz) δ: 7.26- 7.34 (m, 2H), 7.17-7.24 (m, 2H), 4.30-4.41 (m, 1H), 3.80-4.03 (m, 2H), 2.39-2.43 (m, 3H), 1.49-1.84 (m, 3H), 0.98 (dd, J = 6.4, 4.1 Hz, 6H). 71 1 H NMR (CD 3 OD, 300 MHz) δ: 7.52- 7.57 (m, 2H), 7.47-7.52 (m, 2H), 4.32-4.40 (m, 1H), 3.72-3.95 (m, 2H), 1.69-1.84 (m, 1H), 1.50-1.68 (m, 2H), 1.42-1.47 (m, 9H), 0.99 (dd, J = 6.3, 4.2 Hz, 6H). 72 1 H NMR (CD 3 OD, 300 MHz) δ: 7.47- 7.57 (m, 4H), 4.37 (dd, J = 9.5, 5.1 Hz, 1H), 3.83-4.02 (m, 2H), 1.70- 1.83 (m, 1H), 1.51-1.68 (m, 2H), 0.99 (d, J = 3.8 Hz, 3H), 0.97 (d, J = 3.8 Hz, 3H). 73 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.38 (m, 2H), 7.26-7.32 (m, 2H), 4.31 (dd, J = 9.1, 5.6 Hz, 1H), 1.67- 1.80 (m, 1H), 1.45-1.63 (m, 2H), 1.39-1.44 (m, 15H), 0.97 (dd, J = 6.6, 3.1 Hz, 6H). 74 1 H NMR (CD 3 OD, 300 MHz) δ: 8.46 (s, NH), 8.26 (s, NH), 7.33-7.38 (m, 2H), 7.25-7.31 (m, 2H), 4.32 (dd, J = 9.2, 5.4 Hz, 1H), 1.68-1.80 (m, 1H), 1.51-1.65 (m, 2H), 1.49 (s, 3H), 1.48 (s, 3H), 0.98 (d, J = 3.5 Hz, 3H), 0.96 (d, J = 3.5 Hz, 3H). 75 1 H NMR (CD 3 OD, 300 MHz) δ: 7.61 (s, 4H), 4.37 (dd, J = 9.8, 5.1 Hz, 1H), 3.72-3.96 (m, 2H), 2.77 (s, 3H), 1.69-1.85 (m, 1H), 1.51-1.69 (m, 2H), 1.45 (s, 9H), 0.94-1.05 (m, 6H). 76 1 H NMR (CD 3 OD, 300 MHz) δ: 7.77- 7.86 (m, 2H), 7.57-7.67 (m, 2H), 4.37 (dd, J = 9.7, 5.0 Hz, 1H), 3.71- 3.96 (m, 2H), 3.07 (s, 3H), 1.69- 1.83 (m, 1H), 1.51-1.70 (m, 2H), 1.40-1.49 (m, 9H), 0.94-1.03 (m, 6H). 77 1 H NMR (CD 3 OD, 300 MHz) δ: 7.57- 7.66 (m, 4H), 4.38 (dd, J = 9.7, 5.0 Hz, 1H), 3.81-4.03 (m, 2H), 2.77 (s, 3H), 1.69-1.85 (m, 1H), 1.48- 1.68 (m, 2H), 0.92-1.03 (m, 6H). 78 1 H NMR (CD 3 OD, 300 MHz) δ: 7.76- 7.87 (m, 2H), 7.57-7.68 (m, 2H), 6.43 (d, J = 8.5 Hz, NH), 4.32-4.45 (m, 1H), 3.81-4.04 (m, 2H), 3.07 (s, 3H), 1.71-1.83 (m, 1H), 1.49- 1.70 (m, 2H), 0.98 (dd, J = 6.4, 3.5 Hz, 6H). 79 1 H NMR (CD 3 OD, 300 MHz) δ: 7.46- 7.58 (m, 2H), 4.33 (dd, J = 9.2, 5.7 Hz, 1H), 1.69-1.86 (m, 1H), 1.46- 1.66 (m, 2H), 1.36-1.46 (m, 15H), 0.94-1.04 (m, 6H). 80 1 H NMR (CD 3 OD, 300 MHz) δ: 7.24- 7.41 (m, 4H), 4.44 (dd, J = 7.8, 5.4 Hz, 1H), 3.70-3.99 (m, 2H), 2.54- 2.68 (m, 2H), 2.12-2.18 (m, 1H), 2.11 (s, 3H), 1.85-2.02 (m, 1H), 1.41-1.50 (m, 9H). [a]D = −21.8 (c = 1.00, MeOH) 81 1 H NMR (CD 3 OD, 300 MHz) δ: 7.26- 7.43 (m, 4H), 4.43-4.57 (m, 1H), 3.70-4.03 (m, 2H), 3.24 (s, 2H), 2.99 (s, 4H), 2.28-2.42 (m, 1H), 2.11-2.26 (m, 1H), 1.47 (s, 9H). 82 1 H NMR (CD 3 OD, 300 MHz) δ: 7.25- 7.44 (m, 4H), 6.55 (d, J = 7.3 Hz, NH), 4.53 (m, 1H), 3.79-4.10 (m, 2H), 3.26 (m., 2H), 2.98 (s, 3H), 2.26-2.42 (m, 1H), 2.20 (m, 1H). 83 1 H NMR (CD 3 OD, 300 MHz) δ: 7.26- 7.42 (m, 4H), 6.55 (d, J = 7.3 Hz, NH), 4.47-4.58 (m, 1H), 3.80-4.11 (m, 2H), 3.25 (m, 2H), 2.98 (s, 3H), 2.28-2.43 (m, 1H), 2.11-2.27 (m, 1H). 84 1 H NMR (CD 3 OD, 300 MHz) δ: 7.61 (s, 1H), 7.21-7.41 (m, 4H), 6.94 (s, 1H), 4.51-4.64 (m, 1H), 3.75-3.96 (m, 2H), 3.07-3.22 (m, 1H), 2.93- 3.06 (m, 1H), 1.49 (s, 9H). 85 1 H NMR (DMSO-D 6 , 300 MHz) δ: 8.93 (NH, 1H), 8.42 (br. s., NH), 7.67 (s, 1H), 7.34 (d, J = 4.1 Hz, 4H), 6.88 (s, 1H), 6.28 (d, J = 7.3 Hz, NH), 4.44 (m., 1H), 3.55-3.90 (m, 2H), 2.93 (m., 2H). 86 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33- 7.38 (m, 2H), 7.26-7.32 (m, 2H), 4.31 (dd, J = 9.1, 5.6 Hz, 1H), 1.67- 1.80 (m, 1H), 1.45-1.63 (m, 2H), 1.39-1.44 (m, 15H), 0.97 (dd, J = 6.6, 3.1 Hz, 6H). 87 1 H NMR (CD 3 OD, 300 MHz) δ: 8.46 (s, NH), 8.23 (s, 2NH), 7.33-7.39 (m, 2H), 7.26-7.31 (m, 2H), 6.19 (d, J = 8.2 Hz, NH), 4.31 (m 1H), 1.73 (m, 1H), 1.51-1.65 (m, 2H), 1.49 (s, 3H), 1.48 (s, 3H), 0.98 (d, J = 3.8 Hz, 6H), 0.96 (d, J = 3.5 Hz, 6H). 88 1 H NMR (CD 3 OD, 300 MHz) δ: 7.27- 7.42 (m, 4H), 4.69 (t, J = 6.0 Hz, 1H), 3.75-3.94 (m, 2H), 2.70-2.78 (m, 2H), 1.45 (s, 9H). 89 1 H NMR (CD 3 OD, 300 MHz) δ: 7.26- 7.44 (m, 4H), 4.62 (t, J = 5.3 Hz, 1H), 2.70-2.94 (m, 2H). 90 1 H NMR (CD 3 OD, 300 MHz) δ: 7.56- 7.61 (m, 1H), 7.30-7.36 (m, 3H), 7.23-7.26 (m, 2H), 7.16 (s, NH), 7.08 (td, J = 7.6, 1.2 Hz, 1H), 6.95- 7.02 (m, 1H), 6.13 (d, J = 7.3 Hz, NH), 4.60-4.68 (m, 1H), 3.80 (s, 2H), 3.32-3.38 (m, 1H), 3.11-3.23 (m, 1H), 1.43-1.47 (m, 9H). 91 1 H NMR (CD 3 OD, 300 MHz) δ: 7.27- 7.42 (m, 4H), 4.69 (t, J = 6.0 Hz, 1H), 3.75-3.94 (m, 2H), 2.70-2.78 (m, 2H), 1.45 (s, (9H). Interm. IUPAC name No. Structure 1 H NMR δ (ppm) 10 1 H NMR (CD 3 OD, 300 MHz) δ: 7.33-7.41 (m, 2H), 7.26-7.33 (m, 2H), 4.18 (d, J = 6.2 Hz, 1H), 1.74- 1.91 (m, 1H), 1.50-1.66 (m, 1H), 1.11-1.33 (m, 1H), 0.99 (d, J = 7.0 Hz, 3H), 0.91-0.97 (m, 3H). 11 1 H NMR (CD 3 OD, 300 MHz) δ: 7.99 (t, J = 8.8 Hz, 1H), 7.31 (dd, J = 10.7, 2.2 Hz, 1H), 7.19-7.27 (m, 1H), 4.18 (d, J = 6.2 Hz, 1H), 1.78- 1.95 (m, 1H), 1.49-1.65 (m, 1H), 1.10-1.27 (m, 1H), 1.00 (d, J = 6.7 Hz, 3H), 0.91-0.98 (m, 3H). 12 1 H NMR (acetone-d6, 300 MHz) δ: 8.28 (t, J = 8.8 Hz, 1H), 8.12 (br. s., NH), 7.33 (dd, J = 11.0, 2.2 Hz, 1H), 7.26 (dt, J = 8.9, 1.9 Hz, 1H), 7.07 (br. s., NH), 6.55 (d, J = 7.0 Hz, NH), 6.40 (br. s., NH), 4.38 (td, J = 7.8, 5.3 Hz, 1H), 1.73-1.89 (m, 1H), 1.54-1.70 (m, 1H), 1.24-1.49 (m, 2H), 0.92 (t, J = 7.3 Hz, 3H). 13 1 H NMR (acetone-d6, 300 MHz) δ: 8.17 (s, NH), 7.41-7.50 (m, 2H), 7.33-7.40 (m, 2H), 6.03 (d, J = 8.2 Hz, NH), 4.39 (ddd, J = 9.4, 8.2, 5.0 Hz, 1H), 3.58 (q, J = 5.6 Hz, 2H), 3.26-3.37 (m, 2H), 1.66-1.81 (m, 1H), 1.44-1.67 (m, 2H), 0.94 (d, J = 1.5 Hz, 3H), 0.92 (d, J = 1.4 Hz, 3H). 14 1 H NMR (acetone-d6, 300 MHz) δ: 8.27 (t, J = 8.9 Hz, 1H), 8.06 (br. s., NH), 7.34 (dd, J = 10.8, 2.3 Hz, 1H), 7.25-7.31 (m, 1H), 6.53 (d, J = 7.0 Hz, NH), 4.43-4.55 (m, 1H), 1.73- 1.87 (m, 1H), 1.53-1.71 (m, 2H), 0.98 (d, J = 1.5 Hz, 3H), 0.96 (d, J = 1.5 Hz, 3H). 15 1 H NMR (acetone-d6, 300 MHz) δ: 8.28 (t, J = 8.9 Hz, 1H), 8.07 (br. s., NH), 7.33 (dd, J = 10.8, 2.3 Hz, 1H), 7.23-7.30 (m, 1H), 7.10 (br. s., NH), 6.50 (d, J = 8.2 Hz, NH), 6.38 (br. s., NH), 4.42 (ddd, J = 9.6, 8.3, 5.0 Hz, 1H), 1.70-1.87 (m, 1H), 1.59-1.70 (m, 1H), 1.44-1.59 (m, 1H), 0.95 (d, J = 1.5 Hz, 3H), 0.93 (d, 3H). 16 1 H NMR (CDCl 3 , 300 MHz) δ: 7.89 (t, J = 8.8 Hz, 1H), 7.14 (dd, J = 10.4, 2.2 Hz, 1H), 7.06 (d, J = 9.1 Hz, 1H), 6.80 (d, J = 2.6 Hz, NH), 5.79 (br. s., NH), 4.45 (dd, J = 8.8, 5.0 Hz, 1H), 1.69-1.85 (m, 1H), 1.57-1.69 (m, 1H), 1.52 (s, 9H), 1.41-1.48 (m, 1H), 0.97 (d, J = 3.5 Hz, 3H), 0.95 (d, 3H). 17 1 H NMR (CD 3 OD, 300 MHz) δ: 7.31- 7.39 (m, 2H), 7.22-7.30 (m, 2H), 1.80-1.92 (m, 2H), 1.71-1.82 (m, 1H), 1.56-1.67 (m, 2H), 1.44 (s, 3H), 0.98 (d, J = 1.2 Hz, 3H), 0.95 (d, J = 1.2 Hz, 3H). 18 1 H NMR (CD 3 OD, 300 MHz) δ: 9.29 (br. s., NH), 8.58-8.75 (m, 4H), 7.33 (br. s., NH), 2.65-2.75 (m, 9H). 19 1H NMR (CD3OD, 300 MHz) δ: 7.32-7.37 (m, 2H), 7.24-7.29 (m, 2H), 1.52 (s, 6H). 20 1 H NMR (acetone-d6, 300 MHz) δ: 8.76 (br. s., 1H), 7.44-7.52 (m, 2H), 7.31-7.40 (m, 2H), 6.30 (br. s., 1H), 2.29-2.48 (m, 2H), 1.75- 1.92 (m, 2H), 0.76-0.86 (m, 6H) . 21 1 H NMR (CD 3 OD, 300 MHz) δ: 7.50 (s, 4H), 4.27 (dd, J = 9.1, 5.6 Hz, 1H), 1.68-1.86 (m, 1H), 1.52-1.66 (m, 2H), 1.45-1.50 (s, 9H), 0.95 (t, J = 6.9 Hz, 6H). 22 1 H NMR (CD 3 OD, 300 MHz) δ: 7.49- 7.57 (m, 4H), 4.38 (dd, J = 9.4, 5.0 Hz, 1H), 1.69-1.87 (m, 1H), 1.51- 1.69 (m, 2H), 0.92-1.01 (m, 6H). 23 1 H NMR (CD 3 OD, 300 MHz) δ: 7.30- 7.39 (m, 2H), 7.17-7.28 (m, 1H), 4.25 (dd, J = 8.9, 5.7 Hz, 1H), 1.74 (dd, J = 13.6, 7.5 Hz, 1H), 1.51- 1.67 (m, 2H), 1.47 (s, 9H), 0.97 (t, J = 6.9 Hz, 6H). 24 1 H NMR (CD 3 OD, 300 MHz) δ: 7.29- 7.38 (m, 2H), 7.17-7.27 (m, 2H), 4.36 (dd, J = 9.4, 5.0 Hz, 1H), 1.73 (dd, J = 18.3, 5.7 Hz, 1H), 1.51- 1.68 (m, 2H), 0.98 (dd, J = 6.4, 3.5 Hz, 6H). 25 1 H NMR (CD 3 OD, 300 MHz) δ: 7.50- 7.59 (m, 2H), 7.12-7.23 (m, 2H), 4.25 (m, 1H), 1.73 (m, 1H), 1.49- 1.63 (m, 2H), 1.47 (s, 9H), 0.91- 1.03 (m, 6H). 26 1 H NMR (CD 3 OD, 300 MHz) δ: 7.50- 7.58 (m, 2H), 7.13-7.21 (m, 2H), 4.35 (dd, J = 9.4, 5.0 Hz, 1H), 1.50- 1.86 (m, 2H), 1.01 (m, 6H). 27 1 H NMR (CD 3 OD, 300 MHz) δ: 7.35- 7.39 (m, 2H), 7.28-7.32 (m, 2H), 4.32 (d, J = 4.7 Hz, 1H), 1.92 (dq, J = 6.8, 4.6 Hz, 1H), 1.46-1.60 (m, 1H), 1.16-1.33 (m, 1H), 0.93-1.02 (m, 6H). 28 1 H NMR (CDCl 3 , 300 MHz) δ: 7.33 (d, J = 8.5 Hz, 2H), 7.17 (s, 2H), 4.43 (dd, J = 9.1, 5.3 Hz, 1H), 1.68- 1.79 (m, 1H), 1.56-1.67 (m, 1H), 1.48 (s, 9H), 1.44 (s, 1H), 0.97 (d, J = 4.1 Hz, 3H), 0.95 (d, J = 4.4 Hz, 3H). 29 1 H NMR (acetone-D6, 300 MHz) δ: 8.17 (s, NH), 7.43-7.50 (m, 2H), 7.33-7.41 (m, 2H), 6.04 (d, J = 7.9 Hz, NH), 4.42-4.52 (m, 1H), 1.71- 1.87 (m, 1H), 1.52-1.69 (m, 2H), 0.97 (d, J = 2.1 Hz, 3H), 0.95 (d, J = 2.3 Hz, 3H). 30 1 H NMR (CD3OD, 300 MHz) δ: 7.27- 7.32 (m, 2H), 7.18-7.23 (m, 2H), 4.22-4.29 (m, 1H), 2.42 (s, 3H), 1.70-1.79 (m, 1H), 1.51-1.61 (m, 2H), 1.47 (s, 9H), 0.97 (t, J = 6.7 Hz, 6H). 31 1 H NMR (CD3OD, 300 MHz) δ: 7.25- 7.31 (m, 2H), 7.14-7.20 (m, 2H), 4.37 (dd, J = 9.2, 5.1 Hz, 1H), 2.39 (s, 3H), 1.68-1.83 (m, 1H), 1.51- 1.67 (m, 2H), 0.96 (dd, J = 6.2, 2.3 Hz, 6H). 32 1 H NMR (CD3OD, 300 MHz) δ: 7.52- 7.58 (m, 2H), 7.47-7.52 (m, 2H), 4.37 (dd, J = 9.4, 5.0 Hz, 1H), 1.70- 1.82 (m, 1H), 1.53-1.69 (m, 2H), 0.99 (d, J = 3.2 Hz, 3H), 0.97 (d, J = 3.2 Hz, 3H). 33 1 H NMR (CD3OD, 300 MHz) δ: 7.53- 7.57 (m, 2H), 7.47-7.51 (m, 2H), 4.26 (dd, J = 8.9, 5.7 Hz, 1H), 1.74 (td, J = 13.6, 6.7 Hz, 1H), 1.51- 1.65 (m, 2H), 1.47 (s, 9H), 0.97 (t, J = 6.7 Hz, 6H). 34 1 H NMR (CD 3 OD, 300 MHz) δ: 7.23- 7.41 (m, 4H), 4.31-4.42 (m, 1H), 2.56 (d, J = 15.5 Hz, 2H), 2.12- 2.23 (m, 1H), 2.08 (s, 3H), 1.98 (dt, J = 14.0, 7.2 Hz, 1H). 35 1 H NMR (CD 3 OD, 300 MHz) δ: 8.76 (s, 1H), 7.23-7.40 (m, 6H), 4.65 (m, 1H), 3.03-3.27 (m, 2H).
Biological Data
Biological activity of compounds according to Formula II is set forth in Table 5 below. CHO-Gα16 cells stably expressing FPRL1 were cultured in (F12, 10% FBS, 1% PSA, 400 μg/ml geneticin and 50 μg/ml hygromycin) and HEK-Gqi5 cells stable expressing FPR1 were cultured in (DMEM high glucose, 10% FBS, 1% PSA, 400 μg/ml geneticin and 50 μg/ml hygromycin). In general, the day before the experiment, 18,000 cells/well were plated in a 384-well clear bottom poly-d-lysine coated plate. The following day the screening compound-induced calcium activity was assayed on the FLIPR Tetra . The drug plates were prepared in 384-well microplates using the EP3 and the MultiPROBE robotic liquid handling systems. Compounds were tested at concentrations ranging from 0.61 to 10,000 nM. Results are expressed as EC 50 (nM) and efficacy values.
TABLE 5
FPRL-1
Ga16-CHO
IUPAC Name
EC 50 (nM)
Compound
(Rel. eff.)
{[2-{[(4-bromophenyl)carbamoyl]amino}-
10.0
(0.95)
3-(1H-imidazol-4-yl)propanoyl]amino}acetic acid
tert-butyl {[2-{[(4-bromophenyl)carbamoyl]ami-
263
(0.95)
no}-3-(1H-imidazol-4-yl)propanoyl]amino}acetate
{[(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-
247
(1.01)
4-(methylsulfonyl)butanoyl]amino}acetic acid
tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
1238
(0.97)
no}-4-(methylsulfonyl)butanoyl]amino}acetate
{[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
7
(1.03)
no}-4-(methylsulfanyl)butanoyl]amino}acetic acid
tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
127
(0.98)
no}-4-(methylsulfanyl)butanoyl]amino}acetate
2-methyl-2-{[(2S)-4-methyl-2-({[4-
2.3
(0.92)
(trifluoromethyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}propanoic acid
tert-butyl 2-methyl-2-{[(2S)-4-methyl-2-({[4-
1016
(1.07)
(trifluoromethyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}propanoate
{[(2S)-4-methyl-2-({[4-
459
(1.12)
(methylsulfonyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetic acid
tert-butyl {[(2S)-4-methyl-2-({[4-
1083
(0.90)
(methylsulfonyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetate
{[(2S)-4-methyl-2-({[4-
358
(1.21)
(methylsulfinyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetic acid
tert-butyl {[(2S)-4-methyl-2-({[4-
668
(0.97)
(methylsulfinyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetate
2-{[(2S)-2-({[(4-bromophenyl)ami-
1
(0.96)
no]carbamoyl}amino)-4-methylpentanoyl]amino}-
2-methylpropanoic acid
tert-butyl 2-{[(2S)-2-{[(4-
133
(1.16)
bromophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}-2-methylpropanoate
({(2S)-4-methyl-2-[({4-
560
(1.07)
[(trifluoromethyl)sulfanyl]phenyl}carbamoyl)ami-
no]pentanoyl}amino)acetic acid
tert-butyl ({(2S)-4-methyl-2-[({4-
3103
(0.78)
[(trifluoromethyl)sulfanyl]phenyl}carbamoyl)ami-
no]pentanoyl}amino)acetate
{[(2S)-4-methyl-2-({[4-
2.95
(1.05)
(methylsulfanyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetic acid
tert-butyl {[(2S)-4-methyl-2-({[4-
116
(0.98)
(methylsulfanyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetate
{[(2R)-2-{[(4-bromophenyl)carbamoyl]ami-
1229
(0.97)
no}-4-methylpentanoyl]amino}acetic acid
tert-butyl {[(2R)-2-{[(4-bromophenyl)carbamoyl]ami-
3657
(0.92)
no}-4-methylpentanoyl]amino}acetate
{[(2R,3R)-2-{[(4-bromophenyl)carbamoyl]ami-
19315
(0.45)
no}-3-methylpentanoyl]amino}acetic acid
tert-butyl {[(2R,3R)-2-{[(4-
3974
(0.44)
bromophenyl)carbamoyl]amino}-3-
methylpentanoyl]amino}acetate
{[(2S)-4-methyl-2-({[4-
1.8
(0.99)
(trifluoromethyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetic acid
tert-butyl {[(2S)-4-methyl-2-({[4-
309
(0.81)
(trifluoromethyl)phenyl]carbamoyl}ami-
no)pentanoyl]amino}acetate
{[(2R)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
1489
(0.87)
no}-4-methylpentanoyl]amino}acetic acid
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
1.4
(0.90)
no}-N-[2-(dimethylamino)-2-oxoethyl]-4-
methylpentanamide
[(2-{[(4-bromophenyl)carbamoyl]ami-
480
(0.99)
no}-2-methylpropanoyl)amino]acetic acid
tert-butyl [(2-{[(4-bromophenyl)carbamoyl]ami-
114
(1.02)
no}-2-methylpropanoyl)amino]acetate
[(2-{[(4-bromophenyl)carbamoyl]amino}-
19
(1.04)
2-ethylbutanoyl)amino]acetic acid
tert-butyl [(2-{[(4-bromophenyl)carbamoyl]ami-
31
(1.03)
no}-2-ethylbutanoyl)amino]acetate
[(2-{[(4-bromophenyl)carbamoyl]ami-
22
(0.98)
no}-2,4-dimethylpentanoyl)amino]acetic acid
tert-butyl [(2-{[(4-bromophenyl)carbamoyl]ami-
58
(0.98)
no}-2,4-dimethylpentanoyl)amino]acetate
(2S)-N-[(1S)-2-amino-2-oxo-1-phenylethyl]-2-{[(4-
84
(0.99)
bromophenyl)carbamoyl]amino}-4-methyl-
pentanamide
(2S)-{[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
9.1
(1.08)
no}-4-methylpentanoyl]amino}(phenyl)ethanoic acid
tert-butyl (2S)-{[(2S)-2-{[(4-
122
(1.02)
bromophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}(phenyl)ethanoate
(2S)-N-[(2S)-1-amino-1-oxopentan-2-yl]-2-{[(4-
6.4
(1.03)
bromophenyl)carbamoyl]amino}-4-methyl-
pentanamide
(2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
1.0
(0.89)
no}-4-methylpentanoyl]amino}pentanoic acid
tert-butyl (2S)-2-{[(2S)-2-{[(4-
13
(1.06)
bromophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}pentanoate
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
3.0
(1.00)
no}-N-[(2R)-1-hydroxypropan-2-yl]-4-
methylpentanamide
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
5.1
(0.98)
no}-N-(2,3-dihydroxypropyl)-4-methyl-
pentanamide
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
7.4
(0.96)
no}-N-(1,3-dihydroxypropan-2-yl)-4-
methylpentanamide
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
2.1
(1.01)
no}-N-(2-hydroxy-2-methylpropyl)-4-
methylpentanamide
(2S)-N-[(2S)-1-amino-3-methyl-1-oxobutan-2-
1.3
(1.03)
yl]-2-{[(4-bromophenyl)carbamoyl]ami-
no}-4-methylpentanamide
(2S)-2-{[(2S)-2-{[(4-bromo-
1.83
(1.13)
phenyl)carbamoyl]amino}-4-methyl-
pentanoyl]amino}-3-methylbutanoic acid
tert-butyl (2S)-2-{[(2S)-2-{[(4-
68
(0.98)
bromophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}-3-methylbutanoate
(2S)-N-[(2S)-1-amino-1-oxopropan-2-yl]-2-{[(4-
24
(0.96)
bromophenyl)carbamoyl]amino}-4-methyl-
pentanamide
(2S)-2-{[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
11
(1.05)
no}-4-methylpentanoyl]amino}propanoic acid
tert-butyl (2S)-2-{[(2S)-2-{[(4-
147
(0.96)
bromophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}propanoate
(2S)-N-[(2S)-1-amino-1-oxopropan-2-yl]-2-
31
(1.05)
{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-
4-methylpentanamide
(2S)-2-{[(2S)-2-{[(4-bromo-2-
12
(0.95)
fluorophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}propanoic acid
tert-butyl (2S)-2-{[(2S)-2-{[(4-bromo-2-
174
(1.00)
fluorophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}propanoate
(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
77
(1.05)
no}-N-(2-hydroxyethyl)-4-methylpentanamide
(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
20
(0.99)
no}-4-methyl-N-(2-oxopropyl)pentanamide
(2S)-N-(2-amino-2-oxoethyl)-2-{[(4-bromo-2-
4.5
(0.95)
fluorophenyl)carbamoyl]amino}-4-methyl-
pentanamide
{[(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
3.6
(1.10)
no}-4-methylpentanoyl]amino}acetic acid
tert-butyl {[(2S)-2-{[(4-bromo-2-
134
(1.19)
fluorophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}acetate
(2S)-N-(2-amino-2-oxoethyl)-2-{[(4-bromo-2-
5.2
(0.98)
fluorophenyl)carbamoyl]amino}pentanamide
(2S)-N-(2-amino-2-oxoethyl)-2-{[(4-
2.5
(0.97)
bromophenyl)carbamoyl]amino}pentanamide
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
4.7
(0.82)
no}-4-methyl-N-(2-oxopropyl)pentanamide
(2S)-N-(2-amino-2-oxoethyl)-2-{[(4-
1.05
(1.08)
bromophenyl)carbamoyl]amino}-4-methyl-
pentanamide
{[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
0.88
(0.91)
no}-4-methylpentanoyl]amino}acetic acid
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
11
(0.92)
no}-N-(2-hydroxyethyl)-4-methyl-
pentanamide
tert-butyl {[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
140
(0.85)
no}-4-methylpentanoyl]amino}acetate
{[(2S)-2-{[(4-bromo-2-
4.8
(0.92)
fluorophenyl)carbamoyl]amino}pentanoyl]ami-
no}acetic acid
tert-butyl {[(2S)-2-{[(4-bromo-2-
83
(0.95)
fluorophenyl)carbamoyl]amino}pentanoyl]ami-
no}acetate
(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]amino}-
92
(0.92)
N-(2-oxopropyl)pentanamide
(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
35
(1.05)
no}-N-(2-oxopropyl)pentanamide
propan-2-yl {[(2S)-2-{[(4-
14
(1.04)
bromophenyl)carbamoyl]amino}pentanoyl]ami-
no}acetate
ethyl {[(2S)-2-{[(4-
57
(1.18)
bromophenyl)carbamoyl]amino}pentanoyl]ami-
no}acetate
methyl {[(2S)-2-{[(4-
17
(0.88)
bromophenyl)carbamoyl]amino}pentanoyl]ami-
no}acetate
(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
105
(0.87)
no}-N-(2-hydroxyethyl)pentanamide
(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-
38
(0.92)
N-(2-hydroxyethyl)pentanamide
(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
16
(0.98)
no}-N-(2-hydroxyethyl)-3-phenylpropanamide
{[(2S)-2-{[(4-
3.2
(0.91)
bromophenyl)carbamoyl]amino}pentanoyl]ami-
no}acetic acid
tert-butyl {[(2S)-2-{[(4-
31
(0.95)
bromophenyl)carbamoyl]amino}pentanoyl]ami-
no}acetate
(2S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
12
(0.94)
no}-N-(2-oxopropyl)-3-phenylpropanamide
(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-
29
(0.96)
N-(2-oxopropyl)-3-phenylpropanamide
(2S,3S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
62
(1.00)
no}-N-(2-hydroxyethyl)-3-methylpentanamide
(2S,3S)-2-{[(4-bromophenyl)carbamoyl]amino}-
24
(1.00)
N-(2-hydroxyethyl)-3-methylpentanamide
(2S,3S)-2-{[(4-bromo-2-fluorophenyl)carbamoyl]ami-
36
(1.01)
no}-3-methyl-N-(2-oxopropyl)pentanamide
(2S,3S)-2-{[(4-bromophenyl)carbamoyl]amino}-
10
(0.97)
3-methyl-N-(2-oxopropyl)pentanamide
(2S,3S)-N-(2-amino-2-oxoethyl)-2-{[(4-bromo-2-
10
(1.00)
fluorophenyl)carbamoyl]amino}-3-methylpentanamide
(2S,3S)-N-(2-amino-2-oxoethyl)-2-{[(4-
4.6
(0.81)
bromophenyl)carbamoyl]amino}-3-methylpentanamide
{[(2S,3S)-2-{[(4-bromophenyl)carbamoyl]amino}-
2.7
(1.00)
3-methylpentanoyl]amino}acetic acid
tert-butyl {[(2S,3S)-2-{[(4-
280
(0.85)
bromophenyl)carbamoyl]amino}-3-
methylpentanoyl]amino}acetate
{[(2S,3S)-2-{[(4-bromo-2-
5.5
(0.95)
fluorophenyl)carbamoyl]amino}-3-
methylpentanoyl]amino}acetic acid
tert-butyl {[(2S,3S)-2-{[(4-bromo-2-
757
(0.86)
fluorophenyl)carbamoyl]amino}-3-
methylpentanoyl]amino}acetate
(2S)-2-{[(4-bromophenyl)carbamoyl]amino}-
6
(0.92)
N-(2-hydroxyethyl)-3-phenylpropanamide
3-{[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
18
(0.98)
no}-3-phenylpropanoyl]amino}propanoic acid
tert-butyl 3-{[(2S)-2-{[(4-
255
(1.00)
bromophenyl)carbamoyl]amino}-3-
phenylpropanoyl]amino}propanoate
{[(2S)-2-{[(4-bromophenyl)carbamoyl]ami-
7.7
(0.99)
no}-3-phenylpropanoyl]amino}acetic acid
tert-butyl {[(2S)-2-{[(4-bromo-
118
(0.91)
phenyl)carbamoyl]amino}-3-phenyl-
propanoyl]amino}acetate
tert-butyl 2-{[(2R)-2-{[(4-
2725
(0.74)
bromophenyl)carbamoyl]amino}-4-
methylpentanoyl]amino}-2-methylpropanoate
2-{[(2R)-2-{[(4-bromophenyl)carbamoyl]ami-
490
(0.74)
no}-4-methylpentanoyl]amino}-2-methylpropanoic
acid
{[2-{[(4-bromophenyl)carbamoyl]amino}-
0.73
(0.97)
3-(1H-indol-3-yl)propanoyl]amino}acetic acid
tert-butyl {[2-{[(4-bromophenyl)carbamoyl]ami-
305
(1.03)
no}-3-(1H-indol-3-yl)propanoyl]amino}acetate
[(4-amino-2-{[(4-
2938
(0.81)
bromophenyl)carbamoyl]amino}-4-
oxobutanoyl)amino]acetic acid
tert-butyl [(4-amino-2-{[(4-
2306
(0.90)
bromophenyl)carbamoyl]amino}-4-
oxobutanoyl)amino]acetate | The present invention relates to novel amide derivatives of N-urea substituted amino acids, processes for preparing them, pharmaceutical compositions containing them and their use as pharmaceuticals as modulators of the N-formyl peptide receptor like-1 (FPRL-1) receptor. | 0 |
[0001] This application is a divisional of co-pending U.S. application Ser. No. 11/026,859, filed Dec. 30, 2004, which is a continuation-in-part of, and claims the benefit of priority to, U.S. application Ser. No. 10/355,955, filed Jan. 31, 2003, which claims the benefit of and priority to U.S. Provisional Application Ser. No. 60/354,098, filed Feb. 4, 2002, the disclosure of which is hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to Spinal Cord Stimulation (SCS) systems and more particularly to methods for efficiently searching for an effective SCS system stimulation parameter sets. An SCS system treats chronic pain by providing electrical stimulation pulses through the electrodes of an electrode array placed epidurally next to a patient's spinal cord. The stimulation parameter set determines the characteristics of the stimulation pulses provided through the electrode array, and the electrodes used to provide the stimulation pulses, which determines the electric field that is created by the stimulation. The optimal stimulation parameter set for a specific patient may be determined from the response of the patient to various sets of stimulation parameters. There is, however, an extremely large number of possible combinations of stimulation parameters, and evaluating all possible sets is very time consuming, and impractical.
[0003] Spinal cord stimulation is a well accepted clinical method for reducing pain in certain populations of patients. An SCS system typically includes an Implantable Pulse Generator (IPG), electrodes, electrode lead, and electrode lead extension. The electrodes are implanted along the dura of the spinal cord, and the IPG generates electrical pulses that are delivered, through the electrodes, to the dorsal column and dorsal root fibers within the spinal cord. Individual electrode contacts (the “electrodes”) are arranged in a desired pattern and spacing in order to create an electrode array. Individual wires within one or more electrode leads connect with each electrode in the array. The electrode leads exit the spinal column and generally attach to one or more electrode lead extensions. The electrode lead extensions, in turn, are typically tunneled around the torso of the patient to a subcutaneous pocket where the IPG is implanted.
[0004] Spinal cord stimulators and other stimulation systems are known in the art. For example, an implantable electronic stimulator is disclosed in U.S. Pat. No. 3,646,940 issued Mar. 7, 1972 for “Implantable Electronic Stimulator Electrode and Method” that provides timed sequenced electrical impulses to a plurality of electrodes. As another example, U.S. Pat. No. 3,724,467 issued Apr. 3, 1973 for “Electrode Implant For The Neuro-Stimulation of the Spinal Cord,” teaches an electrode implant for the neuro-stimulation of the spinal cord. A relatively thin and flexible strip of physiologically inert plastic is provided as a carrier on which a plurality of electrodes are formed. The electrodes are connected by leads to an RF receiver, which is also implanted.
[0005] In U.S. Pat. No. 3,822,708, issued Jul. 9, 1974 for “Electrical Spinal Cord Stimulating Device and Method for Management of Pain,” another type of electrical spinal cord stimulation device is taught. The device disclosed in the '708 patent has five aligned electrodes which are positioned longitudinally on the spinal cord. Electrical pulses applied to the electrodes block perceived intractable pain, while allowing passage of other sensations. A patient operated switch allows the patient to adjust the stimulation parameters.
[0006] Most of the electrode arrays used with known SCS systems employ between 4 and 16 electrodes. Electrodes are selectively programmed to act as anodes, cathodes, or left off, creating a stimulating group. The number of stimulation groups available, combined with the ability of integrated circuits to generate a variety of complex stimulation pulses, presents a huge selection of stimulation parameter sets to the clinician. When an SCS system is implanted, a “fitting” procedure is performed to select an effective stimulation parameter set for a particular patient.
[0007] A known practice is to manually test one parameter set, and then select a new stimulation parameter set to test, and compare the results. Each parameter set is painstakingly configured, and ramped up in amplitude gradually to avoid patient discomfort. The clinician bases their selection of a new stimulation parameter set on their personal experience and intuition. There is no systematic method to guide the clinician. If the selected stimulation parameters are not an improvement, the clinician repeats these steps, using a new stimulation parameter set, based only on dead-reckoning. The combination of the time required to test each parameter set, and the number of parameter sets tested, results in a very time consuming process.
[0008] An example of another stimulation system that is known in the art is a cochlear implant, such as the implant and system described in U.S. Pat. No. 5,626,629, issued May 6, 1997, entitled “Programming of a Speech Processor for an Implantable Cochlear Stimulator” and incorporated herein by reference. The '629 patent describes a method for fitting a cochlear implant to a patient. The method involves determining estimated and threshold stimulation levels of one of the channels of the implant using an objective measurement, such as a measured electrically evoked physiological response. This information is used as a starting point to make further adjustments to stimulation parameters in response to subjective feedback from the patient.
[0009] Another known practice is current steering, a process that is more fully described in U.S. Pat. No. 6,393,325, incorporated herein by reference. This process greatly reduces the amount of time required to test a parameter set because the stimulation moves gradually along the array and does not need to be ramped down and then up again in between the testing of different parameter sets as in a conventional system. For example, one embodiment disclosed in the U.S. Pat. No. 6,393,325 (noted above) uses a table having stimulation parameters and a directional input device which the patient uses to navigate through the table.
[0010] What is needed is a method for selection of trial stimulation parameter sets that guides the clinician towards an effective stimulation parameter set(s). What is also needed is an algorithm to maintain constant paresthesia while stimulation is transitioned from one electrode to another.
SUMMARY OF THE INVENTION
[0011] In accordance with the present inventions, a method of transitioning stimulation energy (e.g., electrical stimulation pulses) between a plurality of electrodes implanted within a patient is provided. In method, the electrodes may be carried by one or more leads implanted adjacent spinal cord tissue.
[0012] The method comprises selecting a plurality of stimulation output values (e.g., electrical current amplitude values) for each of the electrodes. The method further comprises selecting a plurality of different modification values for at least one of the electrodes, respectively multiplying the stimulation output values and the modification values to determine modified stimulation output values for the electrode(s), which may optionally be stored in a steering table, and incrementally transitioning the stimulation energy to or from the electrode(s) in accordance with the modified stimulation output values. The modified stimulation output values are stored in a steering table. The modification values may be selected in a manner that maintains paresthesia when transitioning the stimulation energy between the electrodes.
[0013] In one method, selection of the modification values comprises generating the modification values using a modifying function. The modifying function may be, e.g., a linear function or a non-linear function. The modifying function may depend upon a percentage output of the electrode(s). For example, the percentage output may range from 0% to 100%, in which case, the modification values generated by the modifying function may be greater at the percentage outputs of 0% and 100% than at percentage outputs between 0% and 100%. For example, the modification values generated by the modifying function may increase from a percentage output of 0% to a percentage output of 50% and decrease from a percentage output of 50% to a percentage output of 100%. The method may further comprise selecting a multiplier value to be applied to the electrode(s), in which case, the modifying function may also depend upon the multiplier value. For example, the modifying function may generate the modification values in accordance with the equation M N −2*(M N −1)*|0.5−X N |, where N is the electrode number, M N is the multiplier value for the electrode E N , and X N is the percentage output of the electrode E N . The multiplier value may be selected in any one or more of a variety of manners. For example, the multiplier value may be selected based on a spacing between the electrodes, an impedance measurement, a comparison of a measured dual cathode threshold to a single cathode threshold for two of the electrodes, or a patient feedback during an un-modified transition of stimulation energy between the electrodes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The above and other aspects of the present invention will be more apparent from the following more particular description thereof, presented in conjunction with the following drawings wherein:
[0015] FIG. 1 shows a Spinal Cord Stimulation (SCS) system;
[0016] FIG. 2 depicts the SCS system of FIG. 1 implanted in a spinal column;
[0017] FIG. 3 depicts a stimulation parameter set flow chart according to one embodiment of the present invention;
[0018] FIG. 4 depicts a portion of the electrode array 18 shown in FIG. 2 as well a target of stimulation;
[0019] FIG. 5 depicts a graph showing stimulation levels during a transition in stimulation without the use of an SEQ algorithm;
[0020] FIG. 6 depicts the output of a linear modifying function applied to electrode E l ;
[0021] FIG. 7 depicts the output of a linear modifying function applied to electrode E 2 ;
[0022] FIG. 8 depicts a graph showing stimulation levels during a transition in stimulation when an SEQ algorithm is used; and
[0023] FIG. 9 depicts a lead having electrodes located at varying distances from a spinal cord.
[0024] Corresponding reference characters indicate corresponding components throughout the several views of the drawings.
[0025] Appendix A, comprising 2 pages including a cover, is an example of a Simplified Measurement Table.
[0026] Appendix B, comprising 13 pages including a cover, is an example of a Simplified Steering Table.
[0027] Appendices A and B are incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The following description is of the best mode presently contemplated for carrying out the invention. This description is not to be taken in a limiting sense, but is made merely for the purpose of describing the general principles of the invention. The scope of the invention should be determined with reference to the claims.
[0029] The method of the present invention provides a systematic approach for selecting a Spinal Cord Stimulation (SCS) stimulation parameter set. The method leads a clinician through a selection process that efficiently locates locally optimum stimulation parameter sets.
[0030] A typical Spinal Cord Stimulation (SCS) system 10 is shown in FIG. 1 . The SCS system 10 typically comprises an Implantable Pulse Generator (IPG) 12 , a lead extension 14 , an electrode lead 16 , and an electrode array 18 . The IPG 12 generates stimulation current for implanted electrodes that make up the electrode array 18 . A proximal end of the lead extension 14 is removably connected to the IPG 12 and a distal end of the lead extension 14 is removably connected to a proximal end of the electrode lead 16 , and electrode array 18 is formed on a distal end of the electrode lead 16 . The in-series combination of the lead extension 14 and electrode lead 16 , carry the stimulation current from the IPG 12 to the electrode array 18 .
[0031] The SCS system 10 described in FIG. 1 above, is depicted implanted in the epidural space 20 in FIG. 2 . The electrode array 18 is implanted at the site of nerves that are the target of stimulation, e.g., along the spinal cord 21 . Due to the lack of space near the location where the electrode lead 16 exits the spinal column, the IPG 12 is generally implanted in the abdomen or above the buttocks. The lead extension 14 facilitates locating the IPG 12 away from the electrode lead exit point.
[0032] A more detailed description of a representative SCS system that may be used with the present invention is described in U.S. Pat. No. 6,516,227, issued 4 Feb. 2003, incorporated herein by reference. It is to be emphasized, however, that the invention herein described may be used with many different types of stimulation systems, and is not limited to use only with the representative SCS system described in the U.S. Pat. No. 6,516,227.
[0033] A flow chart representing one embodiment of a method for stimulation parameter set selection in accordance with the present invention is depicted in FIG. 3 . As with most flow charts, each step or act of the method is represented in a “box” or “block” of the flow chart. Each box or block, in turn, has a reference number associated with it to help explain the process in the description that follows.
[0034] At the start 22 of the method, a measurement table, or equivalent, and a steering table, or equivalent, are provided. The measurement table typically comprises rows, with each row defining one set of stimulation parameters. In a preferred embodiment, each row specifies the polarity on each electrode of the electrode array 18 ( FIGS. 1 and 2 ) that the stimulation system determines should be applied to the patient for a particular purpose. The electrode array 18 preferably comprises eight or sixteen electrodes, but the measurement table may only utilize a subset of the electrode array 18 , for example four electrodes. Those skilled in the art will recognize that a measurement table may include stimulation parameter sets with various variations, such as pulse duration or pulse frequency, and a measurement table with such other variations is intended to come within the scope of the present invention. An exemplary simplified measurement table that may be used with the invention is found in Appendix A.
[0035] The steering table, or equivalent, typically includes a larger number of rows than does the measurement table. An exemplary steering table, containing 541 rows, that may be used with the invention is found in Appendix B. The rows in the steering table typically reflect the same variation as the rows in the measurement table, however, those skilled in the art will recognize that the steering table may also include other degrees of variation not included in the measurement table, and these variations are also intended to come within the scope of the invention. At least one row in the steering table will however correspond to one of the rows in the measurement table, as will be made apparent by the following description.
[0036] The rows in the steering table are arranged in order based on the physical characteristics of the stimulation provided by each stimulation parameter set, so that “transitioning” i.e., moving from one row to the next in the steering table, represents a gradual, and somewhat uniform, change in the parameters of the delivered stimulation. In other words, stepping from one row to an adjacent row in the steering table causes the stimulation applied to the tissue through the individual electrodes of the electrode array 18 to gradually move in a desired direction. This type of current steering is described more fully in U.S. Pat. No. 6,393,325, noted above.
[0037] As described in more detail below, the steering table initially provided may be modified or “filled in” following testing of the trial stimulation parameter sets, determination of the maximum comfortable step size, or determination of the desired electric field shift resolution in order to optimize the step sizes that are employed for transitioning from one stimulation parameter set in the steering table to the next.
[0038] Once the desired measurement table and steering table have been provided, the first step in the method is selection of a trial stimulation parameter set for testing (block 24 ). Generally, the first row of the measurement table will be tested first, followed in order by the remaining rows. However, the order of row selection is not essential, and the rows may be selected in any order. Next, the selected stimulation parameter set is used to provide stimulation to the patient (block 26 ). Generally, to avoid uncomfortable “jolting” and over-stimulation, the amplitude of the stimulation provided is initially set to a relatively low level, i.e., below the level that will result in the patient perceiving paresthesia. The amplitude is then gradually increased. The stimulation level at which the patient begins to perceive paresthesia is called the perception or perceptual threshold. See e.g., U.S. Pat. No. 6,393,325, noted above. The stimulation is then increased until it begins to become uncomfortable for the patient. This level is called the maximum or discomfort threshold. See e.g., U.S. Pat. No. 6,393,325, noted above. These pre-steering measured thresholds may be noted and used later in the steering process. Alternatively, these thresholds may be determined based on pre-established values, or based on previously-measured thresholds for the patient.
[0039] The patient provides feedback as to the effectiveness of the stimulation that is applied using the trial stimulation parameter set. Alternative means (e.g., objective measurements of various physiological parameters of the patient, such as perspiration, muscle tension, respiration rate, heart rate, and the like) may also be used to judge the effectiveness of the applied stimulation. A determination is then made if all of the trial sets have been tested (block 28 ). The steps of selecting a trial set of stimulation parameters (block 24 ) and providing stimulation in accordance with the selected trial set of stimulation parameters (block 26 ) are repeated until all of the trial stimulation parameter sets have been tested.
[0040] After all of the trial stimulation parameter sets have been tested, the trial stimulation parameter sets are ranked (block 30 ) based upon the patient's evaluation (and/or based upon alternative evaluation of selected physiological parameters of the patient) of the effectiveness of each trial stimulation parameter set.
[0041] The testing and ranking of the trial stimulation parameter sets provides a coarse approximation of the stimulation which may be most effective. Because the trial stimulation parameter set is only a coarse approximation, the implication is that fine adjustments of such parameter sets may also be effective, and perhaps even more effective. Hence, once the trial stimulation parameter sets have been ranked, the highest ranked trial stimulation parameter set becomes a first specified ranked set that functions as a first “benchmark,” or starting point, for a much finer search for the most effective stimulation parameter set. The finer search for a stimulation parameter set begins by selecting a row in the steering table that corresponds to the highest ranked set in the measurement table (block 32 a ). This selected highest ranked trial stimulation parameter set is then used to provide stimulation (block 34 a ) to the patient. Again, the patient evaluates the effectiveness of the stimulation, and/or alternative means (e.g., measuring physiological parameters of the patient) are used to evaluate the effectiveness of the stimulation. Then, a row next to the row just tested, e.g., moving in a first direction in the steering table, such as down, is selected as a possible new stimulation parameter set (block 36 ), and this new row is then used to provide stimulation (block 34 b ). The results of the new stimulation are then compared to the results of the previous stimulation (block 38 a ). If the results improve (YES branch of block 38 a ) the steps set forth in blocks 36 and 34 b are repeated, i.e., the row in the steering table adjacent to the most recently used row, moving in the same direction in the table as before, is used to define a new stimulation parameter set (block 36 ) and that stimulation parameter set is used to provide stimulation (block 34 b ). As long as the stimulation results continue to improve, this process of stepping to the next row in the steering table and retesting is continued, thereby fine tuning the stimulation parameter set until no further improvements are detected.
[0042] As soon as the results fail to improve (NO branch of block 38 ), the method goes back to the “benchmark” parameter set, i.e., that row in the steering table corresponding to the highest ranked set (block 32 b ) and stimulation is again provided (block 34 c ). This is actually a repeat of the stimulation performed at blocks 32 a and 34 a , but inasmuch as one or more stimulation parameter sets have been provided since the benchmark stimulation was provided at steps 32 a and 34 a , this repeat stimulation provides the patient with a reminder or refresher of what the benchmark stimulation was like. (Alternatively, of course, this repeat of the benchmark stimulation could be skipped.) Then, a process almost identical to that described above is performed to again fine tune the benchmark stimulation parameter set, only in the other direction. That is, the row adjacent to the row that defines the benchmark stimulation parameter set is selected as the row that defines the stimulation parameter set (block 40 ), moving in the opposite direction, e.g., up, from the direction used in the step performed at block 36 . Once a row is selected, stimulation is provided using the parameters of the selected row (block 34 d ). Thus, the fine tuning that occurs at steps 40 and 34 d in FIG. 3 occurs while moving in the opposite direction in the steering table than was used previously.
[0043] The results of the new stimulation applied at step 34 d are compared to the results of the previous stimulation (block 38 b ). If the results improve (YES branch of block 38 b ), the steps set forth in blocks 40 and 34 d are repeated, i.e., the row in the steering table adjacent to the most recently used row, moving in the same direction in the table as before, are used to define a new stimulation parameter set (block 40 ), and that stimulation parameter set is used to provide stimulation (block 34 d ). As long as the stimulation results continue to improve, this process of stepping to the next row in the steering table, and retesting is continued, thereby fine tuning the stimulation parameter set until no further improvements are detected.
[0044] Hence, it is seen that thus far in the method, two sets of effective stimulation parameters have been identified: one by moving in a first direction from the benchmark row (of the specified ranked set) in the steering table (determined using the steps at blocks 36 , 34 b and 38 a ), and another by moving from the benchmark row in a second direction in the steering table (determined using the steps at blocks 40 , 34 d and 38 b ). These two possible stimulation sets are then evaluated to see if one comprises the most effective stimulation set (block 42 ). If so (YES branch of block 42 ), then that set is selected as the best parameter stimulation set for the stimulation that is to be provided (block 46 ) whenever the operating program of the SCS system (or other neural system) determines stimulation is needed. If not (NO branch of block 42 ), then the search continues for the most effective stimulation set by selecting the row in the steering table corresponding to the next highest ranked set (block 44 ), e.g., the second ranked stimulation set. The next highest ranked set thus defines a new specified “benchmark” stimulation set from which additional fine tuning is performed as described above (blocks 32 a through 38 b ).
[0045] It is thus seen that unless an effective stimulation parameter set is found at block 42 , the process described in FIG. 3 is repeated for the next highest ranked trial stimulation parameter set, until the most effective stimulation parameter set is identified.
[0046] By way of a simple example, consider the Simplified Measurement Table found in Appendix A and the Simplified Steering Table found in Appendix B. After testing each of the stimulation parameter sets defined by the rows in the Simplified Measurement Table in Appendix A, the following “coarse” ranking in effectiveness of the stimulation sets is found:
Stimulation Set Rank 3 1 1 2 2 3 4 4
[0047] Starting with the highest ranked Stimulation Set (from the Simplified Measurement Table in Appendix A), which uses Electrode Number 3 as an anode (+) and Electrode Number 5 as a cathode (−) to provide a stimulus to the patient, a corresponding row in the Simplified Steering Table (in Appendix B) is found to be Stimulation Set No. 301, which shows that the current flow from Electrode 3 is “1” and the current flow from Electrode 5 is “−1”. This means that all of the current applied by the stimulator is applied from Electrode 3 as an anode to Electrode 5 as a cathode. (The amplitude of the current applied may, of course, be adjusted as required.) Thus, the coarse adjustment provided by the measurement table leads one to Stimulation Set No. 301 in the Simplified Steering Table. Stimulation Set No. 301 thus serves as the first “benchmark” stimulation set.
[0048] Once the first benchmark stimulation set is identified, the method then fine tunes this selection by applying the stimulation set(s) adjacent the benchmark set. For example, going “down” in the Simplified Steering Table, Stimulation Set No. 302 is applied, then No. 303, and then No. 304, and so on, until the patient (or other means) determines that no further improvement results. In this example, Stimulation Set No. 302 is found to be the most effective set.
[0049] In a similar manner, going “up” in the Simplified Steering Table from the benchmark set (No. 301), Stimulation Set No. 300 is applied, then No. 299, then No. 298, and so on, until the patient (or other means) determines that no further improvement results. In this example, Stimulation Set 298 is found to be the most effective set to use.
[0050] Once the two Stimulation Sets No. 298 and 302 have been identified, then a determination is made as to which one is the most effective to use for stimulation. If one of these two is the most effective, e.g., Stimulation Set No. 298, then that Stimulation Set is selected as the best one to use for stimulation in this instance, and the search ends. If, however, neither is found to be the most effective, then the process continues by locating the second-highest ranked benchmark stimulation set (corresponding to Stimulation Set No. 1 in the Simplified Measurement Table) in the Simplified Steering Table. As seen from the Simplified Measurement Table, Stimulation Set No. 1 defines Electrode No. 1 as a cathode and Electrode No. 3 as an anode. This corresponds to Stimulation Set No. 21 in the Simplified Steering Table. Hence, fine tuning of this benchmark stimulation set is conducted by first going “down,” and then “up” from Stimulation Set No. 21 until the stimulation set is found that does not result in any further improvement.
[0051] The two stimulation sets identified from fine tuning the second benchmark stimulation set (one by moving “down” from the benchmark row and the other by moving “up” from the benchmark row) are then evaluated to determine if one if the most effective to use for stimulation. If one of these two is the most effective, then that stimulation set is selected as the best one to use for stimulation in this instance, and the search ends. If, however, neither is found to be the most effective, then the process continues by locating the third-highest ranked benchmark stimulation set (corresponding to Stimulation Set No. 2 in the Simplified Measurement Table) in the Simplified Steering Table, and the process continues as described.
[0052] Those skilled in the art will recognize that various variations exist to the method described herein. For example, a gradient method may be utilized to evaluate the slope of stimulation parameter set effectiveness around each trial stimulation parameter set. A combination of the relative effectiveness of each trial stimulation parameter set, and the slope of the effectiveness in the neighborhood of the trial stimulation parameter set may be used to select which trial stimulation parameter set to test around. The basic core of the present invention is to use a table, or equivalent, of a small number of trial stimulation parameter sets (a coarse table) to determine a starting point, and a larger table (a fine table), or equivalent, of predetermined stimulation parameter sets to guide the search for a local optimum. Any method for finding an effective stimulation parameter set that uses a combination of a small coarse table, and a large fine table, is intended to come within the scope of the invention.
[0053] In order to make the search for the optimal stimulation parameters even more efficient, a method for selecting the step sizes in the fine table is used. This method takes into account various factors, such as the maximum and perception thresholds at various points in the table, in order to determine the most efficient step size.
[0054] In the fine table provided in Appendix B, step sizes of a fixed percentage (e.g., or 10%) are used. In clinical practice, fixed step sizes of 10% are often used. However, a fixed step size of 10% may be too large under certain circumstances, and may exceed the patient's maximum comfortable step size, resulting in discomfort to the patient. If a lower fixed step size were chosen (e.g., 1%), that step size may be too small under certain circumstances, and may be smaller than the resolution of the spinal cord stimulator. Similarly, a smaller step size (e.g., 1%) may be so small that time is wasted transitioning from one row in the table to the next in the course of evaluating stimulation parameters that produce similar, potentially ineffective results.
[0055] The example of a patient being treated for severe back pain illustrates this problem. It would not be unusual for such a patient to require stimulation having a cathodic amplitude of 8 milliamperes (mA) and a pulse width of 1000 microseconds (μs). A 10% step size (i.e., a change of 0.8 mA in each step) would result in a change in stimulation charge of 800 nanocoulombs per pulse (nC/pulse). Empirical estimates using clinical data suggest that the typical maximum comfortable step size is one that results in a 100 nC/pulse change in stimulation charge. An 800 nC/pulse change is well above this estimated maximum and would almost certainly result in an uncomfortable “jolt” to the patient. Repeated “jolting” may become so uncomfortable that the patient and/or clinician will refuse to use current steering in the fitting process. Thus, a more appropriate step size given these stimulation parameters would be 1%. A 1% step size would result in an 80 nC/pulse change in stimulation charge, which is below the estimated 100 nC/pulse maximum.
[0056] However, when lower levels of stimulation are used, a fixed 1% step size is inappropriate. In the case where a patient requires stimulation having an amplitude of 3 mA and pulse width of 1000 μs, a 1% step size would produce a 0.03 mA change in amplitude. This is less than the resolution of many spinal cord stimulation systems. Furthermore, such small step sizes would mean that a greater number of steps would be required when transitioning through this portion of the table. If this portion of the table were not producing effective results, then a great deal of time would be wasted “passing through” stimulation configurations that are not beneficial in order to get to better configurations.
[0057] The example shown in FIG. 9 also illustrates this point. In FIG. 9 , the various electrodes E 1 48 , E 2 50 , E 3 76 and E 4 78 are located at different distances from the spinal cord 21 . This is not uncommon as electrode arrays, once implanted, are often not perfectly parallel to and aligned with the spinal cord. As a result, in this example, the nominal amplitude required for each electrode alone to provide adequate stimulation to induce paresthesia in the spinal cord may be as follows: E l =3 mA, E 2 =4 mA, E 3 =6 mA, E 4 =8 mA. As explained above, no single fixed percentage step size for transitioning from E l to E 4 would be appropriate. A 5 or 10% step size could produce a “jolt” for current amplitudes near those associated with E 4 , while a 1% step size would be too small for currents near those associated with E 1 , wasting clinical time (if the spinal cord stimulator even had a resolution small enough to make 1% step sizes in this current range).
[0058] In order to determine appropriate and efficient step sizes for a particular portion of a steering table, the perception threshold and maximum threshold levels for one or more trial stimulation parameter sets are first determined, as discussed above. Trial stimulation parameter sets usually define stimulation pulses spaced somewhat equally along the electrode array, so as to provide meaningful data for different portions of the array. The optimal stimulation level is somewhere between the perception and maximum thresholds, and may vary at different positions along the array.
[0059] Once thresholds for trial stimulation parameter sets are determined, the process of “filling in” the steering table for those configurations between the trial stimulation parameter sets can begin. Some number of intermediate configurations or “steps” are required to smoothly transition from one trial stimulation parameter set along the array without causing discomfort to the patient. The patient's maximum comfortable step size can be used as a factor to determine the number of steps needed. An estimated maximum comfortable step size may be used, such as 100 nC/pulse, or the individual's maximum comfortable step size may be measured in the clinic, such as by gradually increasing the step size of a test transition until the patient reports that it is uncomfortable. Each step in the steering table would be required to be smaller than this maximum comfortable step size. For areas along the array having relatively high thresholds, i.e., areas where higher stimulation currents are required to induce paresthesia, this requirement will result in relatively smaller percentage changes in stimulation amplitude between steps. For areas along the array having relatively lower thresholds, a larger percentage change in stimulation amplitude between steps may be used without exceeding the maximum comfortable step size.
[0060] An additional factor that may be used to determine step size is the desired electric field shift resolution or spatial resolution. Each time the stimulation parameter set is changed, the electric field produced by the stimulation changes, or “shifts.” The electric field shift resolution is the minimum change in stimulation parameters required to produce a noticeable physiological difference in the effects of stimulation. It is unproductive to test multiple stimulation parameter sets that will all produce the same physiological response. Thus, the step size should be at least as large as the minimum electric field shift resolution in order to test truly “different” stimulation parameter sets and to avoid wasting clinical time. See discussion in U.S. Pat. No. 6,393,325, noted above.
[0061] Similarly, smaller step sizes may be used in regions along the array that have been previously identified as providing the best results. In such regions, the desired electric field shift resolution is small. For example, relatively smaller steps sizes (i.e., values close to the minimum electric field shift resolution) may be used when steering parameter values around (or relatively closer to) the trial stimulation parameter set that produced the best results. Additionally, if the patient identifies a region in the steering table that provides good results during the steering process, the step sizes in and around that region might be decreased, even down to the limit of the smallest programmable step size in the stimulator, so that an even more optimal stimulation parameter set may be identified.
[0062] In contrast, for those regions identified as not providing effective stimulation parameters (e.g., trial stimulation parameter sets that the patient identified as less effective), the step size should be increased to a relatively larger size (i.e., to near the maximum comfortable stimulation step size) in order to reduce the time spent “passing through” such stimulation parameters. Thus, if an initial trial stimulation parameter set does not produce effective results, large step sizes should be used in that region, up to the maximum comfortable step size. Likewise, relatively larger step sizes may be used for stimulation parameters sets that are relatively farther from trial stimulation parameter sets that the patient identified as effective.
[0063] Clinical studies of current steering have shown that shifts in anodic pulse parameters often do not produce the same paresthesia variability as cathodic shifts on stimulation arrays with relatively large electrode spacing. Thus, relatively larger step sizes may be chosen for anodic current shifts. However, the same methods for determining optimal step size described above may be applied to anodic shifts as well as cathodic shifts. Additionally, the same methods may be applied to other stimulation parameters, such as voltage amplitude, pulse width, pule rate, etc.
[0064] In another embodiment, the pre-steering measured thresholds (perception threshold and maximum threshold) may be used to select a fixed percentage table stored in memory. In this embodiment, the programmer or implant device memory contains numerous fixed percentage tables. The pre-steering measured thresholds are used to select which table provides the appropriate step size to provide meaningful spatial resolution but also to avoid exceeding the maximum comfortable step size. Variations of this embodiment are also possible. For example, the pre-steering measured thresholds may be used to select various portions of tables stored in memory for different portions of the electrode array. Combinations of these embodiments are also possible. For example, the pre-steering measured thresholds may be used to “fill-in” the entries of a steering table such that the step size is based on these thresholds. The optimal stimulation level for a trial stimulation parameter set is selected at a level between the perception threshold and the maximum threshold. This optimal level is then used to create fixed percentage steps in a steering table, provided that those steps fall within a range not exceeding the maximum comfortable step size or falling below the desired electric field shift resolution. If the fixed percentage steps do fall outside of this range, then the step size is adjusted so as to fall within the range.
[0065] Furthermore, the methods described above are not limited to use with a steering table. Although these methods may be used to “fill in” or select a current steering table, they may also be implemented using equations with variable weighting factors. For example, the estimated or maximum comfortable step size may be weighted against the desired electric field resolution to provide a step size during current steering in which no table is used. Similarly, analog or digital hardware with variable component values may be used to provide a step size during a fitting procedure.
[0066] One primary goal in current steering is to maintain paresthesia at a relatively constant intensity while transitioning stimulation provided by cathodes (and anodes) from one electrode to the next. However, the amount of current needed to create a particular level of paresthesia varies depending on the distance of the electrode (or electrodes) providing stimulation from the target of stimulation and the characteristics of the surrounding tissue. An algorithm that transitions the energy from one electrode to another in a linear fashion by only maintaining a total emission energy (e.g., 100%-0%, 90%-10%, . . . , 10%-90%, 0%-100%) will result in an unequal current density pattern.
[0067] Thus, an electrode that is at an appreciably further distance from the target tissue will require a higher output in order to provide the same level of paresthesia than one that is closer to the target tissue. On the other hand, if electrodes are closely spaced on a lead, the gradual transition of stimulation from one electrode to an adjacent electrode is likely to result in a lesser change in the perceived intensity of the stimulation, because both the new and old electrode are approximately the same distance from the target tissue. However, if electrodes are spaced far apart on a lead, the gradual transition of stimulation from one electrode to an adjacent electrode may result in loss of paresthesia during the transition, because the total stimulation reaching a particular location may fall below the perception threshold.
[0068] In order to maintain a constant level of paresthesia, the patient or clinician often must constantly adjust the stimulation amplitude “up” to avoid a loss of paresthesia and then “down” to avoid an over-stimulation condition during the fitting process. This is a time-consuming and often uncomfortable process that increases the time spent steering and the stress on the patient. As the fitting process becomes longer and more difficult, the typical patient's willingness and ability to provide meaningful feedback decreases. Thus, a fitting process in which more sets of stimulation parameters can be tested in a shorter amount of time with less discomfort to the patient has a greater chance of providing a better “fit” or end result to the patient.
[0069] In order to maintain paresthesia while electrodes are gradually transitioned, a superposition equalization (SEQ) algorithm may be used. In this method, for each change in the current distribution, there is a multiplier that is used to compensate for the physical characteristics of the lead array, i.e., electrode separation and size. A modifying function is used to apply this multiplier to the electrode energy output during transition to maintain a relatively constant current density.
[0070] The need for such an SEQ algorithm can be understood from an examination of conventional steering without the use of an SEQ algorithm. FIG. 4 shows a portion of a conventional lead having at least two electrodes E l 48 and E 2 50 . The targets of stimulation are shown as points P 1 52 A and P 2 52 B, which may be assumed to have the same threshold. FIG. 5 shows a line 54 representing the stimulation perceived by the patient as stimulation is transitioned from E l to E 2 in a linear fashion, e.g., E l =100%, E 2 =0%; E l =95%, E 2 =5%, . . . , E 1 =0%, E 2 =100%, shown by lines 56 and 58 , respectively. An example of such a transition is given in the simplified steering table shown in Appendix B. Lines 21 to 41 in that table show a linear transition from electrode 3 providing 100% of the anodic stimulation to electrode 4 providing 100% of the anodic stimulation in steps of 5%.
[0071] The dashed line marked T 60 is the threshold stimulation level necessary to induce paresthesia by stimulation at either point P 1 or P 2 . The intensity of perceived paresthesia, as represented by the line 54 , is generally a curved line, because paresthesia is primarily due to activation of fibers near each electrode, and the typical range of stimulation is about 50% above the perception threshold. In this example, the curved line 54 is shown as symmetrical, parabolic-shaped curve. In practice, line 54 would tend to be uneven and unsymmetrical, depending on the physical characteristics of the tissue and limited superposition effect of the stimulation provided by each electrode.
[0072] In this example, the curved line 54 falls below the threshold stimulation level 60 during part of the transition from E 1 to E 2 . This results in the patient perceiving a loss of paresthesia at point A 62 and during the transition through the electrode combinations between point A and point B 64 . Because the patient would sense no paresthesia, the patient would be unable to provide any feedback regarding whether those configurations were effective.
[0073] In order for the patient to be able to provide effective feedback, the patient or clinician would need to be given the ability to manually adjust the stimulation amplitude upward in order to create the perception of paresthesia. In fact, the patient or clinician would need to increase the stimulation amplitude between point A and point C 66 . This need for repeated manual adjustment of stimulation amplitude can be time-consuming and frustrating for the patient.
[0074] The use of an SEQ algorithm to maintain paresthesia at a relatively constant level during transition between electrodes addresses this problem. The SEQ algorithm adapts the total energy output to compensate for the change in current density based upon the electrode separation and electrode size. For each change in the current distribution, a modifying function uses a multiplier (M) to compensate for the lead array to maintain a relatively constant paresthesia intensity. This multiplier is applied via the modifying function to each electrode energy output during electrode transitions. In the preferred embodiment, the multiplier is applied to each electrode current output during cathodic transitions, but the multiplier may also be applied during anodic transitions or during both cathodic and anodic transitions and may be applied to other parameters such as voltage, pulse width, and pulse rate.
[0075] Relatively larger inter-electrode spacing on a lead generally requires the use of a larger multiplier, while closer inter-electrode spacing on a lead requires relatively smaller multipliers. This is due to the fact that there is less superposition effect as the inter-electrode spacing on a lead increases.
[0076] There are many different possible methods for choosing an appropriate multiplier and the examples provided below are not intended to be limiting. Any method that produces a meaningful multiplier is intended to fall within the scope of the invention.
[0077] One method for determining an appropriate multiplier is the use of a software user interface application containing a database of various electrode types. The clinician simply enters the electrode model number and/or electrode size and spacing information. The software then retrieves the appropriate multiplier corresponding to that lead model or those lead characteristics. The database may also contain the algorithm for implementing that multiplier, as discussed below.
[0078] As already mentioned, electrodes having relatively larger inter-electrode spacing require a relatively larger multiplier. For example, the Medtronic model number 3487A lead has a relatively large 9 mm inter-electrode space. Such a lead might require a multiplier of 1.6. In contrast, the Advanced Bionics model number ABSC2108 lead has a relatively smaller 4 mm inter-electrode space. This lead would require a relatively smaller multiplier, e.g., 1.2.
[0079] The multiplier may also be measured physiologically, either directly or indirectly by measuring inter-electrode spacing. For example, the clinician could measure the inter-electrode distance between two electrodes using an impedance measurement technique. This distance could then be used to select an appropriate multiplier. This method is useful for measuring appropriate multipliers for electrodes on two different leads, where the inter-electrode distance depends on where the leads were implanted and to what extent the leads have moved since surgery and whether the inter-electrode distance changes as a function of the patient's body movements. Inter-electrode spacing could also be measured using one of the many well-known standard imaging techniques, such as those involving x-rays and fluoroscopes.
[0080] The multiplier may also be measured more directly by measuring the stimulation threshold for two single cathodes and then the threshold when both of those cathodes are stimulated and then comparing the two to determine the multiplier.
[0081] Yet another way to measure the multiplier is by use of a “real time” determination using input from the patient. One electrode is stimulated and then the stimulation is transitioned to another electrode without the use of a multiplier. During the transition, the patient is told to manually adjust the level of stimulation to maintain a constant level of paresthesia throughout the transition. The adjustments made by the patient are recorded, and the multiplier can be determined from those adjustments.
[0082] Once a multiplier is selected, the SEQ algorithm can be used to maintain constant paresthesia during electrode transitions. The use of the multiplier in the SEQ algorithm is described below. In the described embodiment below, the SEQ algorithm applies the multiplier using a linear modifying function during the transition. However, one skilled in the art will appreciate that this multiplier could be applied in a non-linear fashion as well. Additionally, in the embodiment described below, the SEQ algorithm applies the multiplier to the amplitude of the current provided by the spinal cord stimulator. However, one skilled in the art will appreciate that a multiplier could also be applied to the voltage, pulse width, pulse rate, or other characteristic of the stimulation being provided, and could apply to other types of devices in addition to spinal cord stimulators.
[0083] FIGS. 6 and 7 illustrate the application of a multiplier to each of electrodes E 1 and E 2 during a transition from 100% stimulation on E l to 100% stimulation on E 2 . Although E l 48 and E 2 50 are shown as adjacent electrodes on a single lead, they could be any two electrodes on a single lead or could be located on different leads. FIG. 6 illustrates the application of a multiplier (M l ) to E l as the stimulation is transitioned from 100% on E 1 to 0% on E 1 . For each percentage value between 100 and 0, the modifying function is defined by the graph shown in FIG. 6 . For example, when E l is providing 100% of the stimulation, the modifying function provides a value of 1. As E 1 provides a lower relative percentage of stimulation, the modifying function value increases, until it equals M 1 when E 1 is providing 50% of the stimulation. As E 1 transitions to provide less than 50% of the stimulation, the modifying function value decreases, until it returns to 1 at E l =0%.
[0084] FIG. 7 illustrates the application of a multiplier (M 2 ) to E 2 as the stimulation is transitioned from 0% to 100% on E 2 . For each percentage value between 0 and 100, the modifying function is defined by the graph shown in FIG. 7 . For example, when E 2 is providing 0% of the stimulation, the modifying function provides a value of 1. As E 2 provides a greater relative percentage of stimulation, the modifying function value increases, until it equals M 2 when E 2 is providing 50% of the stimulation. As E 2 transitions to provide more than 50% of the stimulation, the modifying function value decreases, until it returns to 1 at E 2 =100%.
[0085] Table 1 below illustrates the value of the modifying function for electrodes E l and E 2 as stimulation is transitioned between them when M 1 =M 2 =1.2
TABLE 1 % Modifying Function Modifying Function Output of E 1 % Output of E 2 (E 1 ) (E 2 ) 100% 0% 1.0 1.0 90% 10% 1.04 1.04 80% 20% 1.08 1.08 . . . . . . . . . . . . 50% 50% 1.2 1.2 . . . . . . . . . . . . 10% 90% 1.04 1.04 0% 100% 1.0 1.0
[0086] When the modifying function is a linear function, it can also be expressed by the
[0000] M N −2*( M N −1)*|0.5 −X N |;
[0000] wherein N is the electrode number; M N is the multiplier for electrode E N and X N is the percentage output of that electrode E N from 0 to 1.
[0087] In order to maintain a steady level of paresthesia during a transition from E l to E 2 , the un-modified output (or output that would be obtained in a simple, linear transition) of each electrode is multiplied by the output of the modifying function for that electrode. The output of E l is shown in Table 2, where the optimal stimulation level for E 1 when that electrode is providing 100% of the stimulation is 2 mA and the multiplier M is 1.2:
TABLE 2 Output of E 1 After Modifying Un-modified SEQ is Applied % Output of E 1 Function E 1 Output of E 1 (mA) (mA) 100 1.0 2.0 2 90 1.04 1.8 1.872 80 1.08 1.6 1.728 70 1.12 1.4 1.568 60 1.16 1.2 1.392 50 1.20 1.0 1.2 40 1.16 0.8 0.928 30 1.12 0.6 0.672 20 1.08 0.4 0.432 10 1.04 0.2 0.208 0 1.0 0 0
[0088] Table 3 shows the results for E 2 where the optimal stimulation level for E 2 when that electrode is providing 100% of the stimulation is 2 mA and the multiplier M is 1.2:
TABLE 3 Output of E 2 After Modifying Un-modified SEQ is Applied % Output of E 2 Function E 2 Output of E 2 (mA) (mA) 0 1.0 0 0 10 1.04 0.2 0.208 20 1.08 0.4 0.432 30 1.12 0.6 0.672 40 1.16 0.8 0.928 50 1.20 1.0 1.2 60 1.16 1.2 1.392 70 1.12 1.4 1.568 80 1.08 1.6 1.728 90 1.04 1.8 1.872 100 1.0 2.0 2.0
[0089] When a linear modifying function is used, as in Tables 2 and 3, the output O N of an electrode E N can be determined by the following formula:
O N =A N *X N *( M N −(2 M N −2)*|0.5 −X N |)
where N is the electrode number; A N is the predetermined optimal stimulation level for a particular electrode E N ; M N is the multiplier for electrode E N and X N is the percentage output of electrode E N from 0 to 1.
[0090] FIG. 8 shows the stimulation output of E 1 and E 2 and the level of stimulation sensed when an SEQ algorithm is used. The output of E 1 68 and the output of E 2 70 are shaped as curves instead of straight lines as in FIG. 5 . The stimulation intensity perceived by the patient is shown as a straight line 72 . Because of the use of the multiplier to maintain a relatively constant current density during transition, the stimulation perceived is constant, and remains at a level above the threshold stimulation level shown as dashed line T 74 .
[0091] In practice, line P 72 is not a perfectly straight line due to factors such as the heterogeneity of tissue near the site of stimulation and the approximation of the superposition effect due to the use of a multiplier that is not independently measured for each change in stimulation parameters. However, one of skill in the art will appreciate that the use of an SEQ algorithm that minimizes the number of times that the perceived stimulation drops below the threshold level or rises above the maximum comfortable level during steering will improve the steering process by reducing the need for the patient or clinician to manually adjust the level of stimulation.
[0092] Although the example provided above involves a relatively simple transition from one electrode to another, the disclosed method applies equally well when more than two electrodes are involved in a transition. The same modifying functions can be used, and the same functions applying the output of the modifying function to the un-modified output of each electrode can be used. Additionally, the disclosed method applies equally well whether the un-modified transition is made in uniform step sizes (e.g. 5% as shown in Appendix B lines 21 to 41 ) or non-uniform step sizes (e.g., 2% then 4% then 6%, etc.).
[0093] While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims. | A method for selecting Spinal Cord Stimulation (SCS) stimulation parameter sets guides a clinician towards an effective set of stimulation parameters. The clinician first evaluates the effectiveness of a small number of trial stimulation parameters sets from a Measurement Table comprising for example, four stimulation parameter sets. Based on the patient's assessment, the trial stimulation parameter sets are ranked. Then the clinician selects a starting or benchmark row in a Steering Table corresponding to the highest ranked trial stimulation parameter set. The clinician moves either up or down form the starting row, testing consecutive parameter sets. The clinician continues as long as the patient indicates that the stimulation results are improving. When a local optimum is found, the clinician returns to the benchmark row, and tests in the opposite direction for another local optimum. If an acceptable set of stimulation parameters is found, the selection process is complete. If an acceptable set is not found, a new starting row in the Steering Table is selected based on the next ranked trial set from the Measurement Table, and the process of searching for local optima is repeated. | 8 |
RELATED APPLICATIONS
The present application is based on and claims priority under 35 U.S.C. §119(a)-(d) to Japanese Patent Application No. 2005-026039, filed on Feb. 2, 2005, the entire contents of which are hereby expressly incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a snow lubrication device for a snowmobile. Preferably, the snow lubrication device is attached to the front of the snowmobile and lubricates the gap between a track belt and a part of the snowmobile that is in contact with the track belt by raking and scattering snow.
2. Description of the Related Art
Snowmobiles are conventionally used by people moving on snowfields or the like in snowy regions. In the snowmobile, a track belt is routed around and between a drive wheel and a rear wheel. The snowmobile runs forward as the track belt is driven and circulated by the drive of an engine. In some snowmobiles, part of the track belt in contact with the drive wheel or part of the track belt in contact with a slide rail is lubricated. A snow rake-up means on the front of the vehicle body or on the underside of the steering skis scatters snow toward the rear part of the track belt.
These known snow rake-up means include a swing arm that extends in up and down directions in a rotatable state to the underside part of the vehicle body. The snow rake-up means provides a stopper for preventing the swing arm from moving forward beyond a specified position and a spring for urging a lower part of the swing arm forward. Therefore, when the snowmobile runs, the lower end of the swing arm rakes up and scatters snow toward the rear. When the lower end of the swing arm strikes earth or small stones under the snow surface, the swing arm moves back against the resilience of the spring, which prevents shock from being transmitted to the vehicle body. However, the snow rake-up means is complicated and costly due to the parts such as the spring and stopper.
SUMMARY OF THE INVENTION
An aspect of the present invention is directed toward addressing one or more of these problems and provides a snow lubrication device having a simple structure that lubricates a drive belt. Preferably, the snow lubrication device is attached to the front of the snowmobile and lubricates the gap between a track belt and a part of the snowmobile in contact with the track belt by raking and scattering snow. A snow lubrication device, which is configured in accordance with the embodiments disclosed herein, is simpler, lower in cost, and is less likely to become dislodged from the vehicle body.
When the track belt is pressed against the snow surface, the snow lubrication device scatters snow on the snow surface to lubricate the contact part of the track belt and part of the snowmobile in contact with the track belt. The snow lubrication device comprises a fixing member made up of a fixing part fixed to the front side part of the vehicle body of the snowmobile. The fixing member includes a cylindrical member into which a rod-shaped member having elasticity with its one end part is inserted, clamped, and/or fixed. The snow lubrication device also includes a snow rake member with its root end part fixed to the other end part of the rod-shaped member. A front-end of the snowmobile is formed with a blade part for raking snow.
The rod-shaped member can be fixed to the fixing member by clamping and fixing one end part of the rod-shaped member by applying a force to the outside round surface of the cylindrical part in the state of one end part of the rod-shaped member being inserted into the cylindrical part of the fixing member. Therefore, it is possible to firmly fix the rod-shaped member and the fixing member. Further, clamping and fixing can be accomplished by a crimping process. The parts of the snowmobile in contact with the track belt of the snowmobile include the drive wheel, the slide rail, or the like.
The joint between the fixing member and the rod-shaped member can be covered with a seal member. In this way, water is prevented from finding its way into the joint. In embodiments where the rod-shaped member is made of metal, covering the joint with a seal member inhibits rust from forming. The seal member may also improve the appearance of the joint between the fixing member and the rod-shaped member.
The root end part of the snow rake member can be thinner than the other end part of the rod-shaped member. The rod-shaped member can be fixed to the snow rake member by putting the root end part of the snow rake member end to end with the other end of the rod-shaped member. A cylindrical fixing member can be fitted over the end-to-end joint and fixed by clamping. The gap between the cylindrical fixing member and the root end part of the snow rake member can be at least partially filled with adhesive. In this way, the snow rake member has a reduced size and weight. Further, because the gap between the cylindrical fixing member and the root end part of the snow rake member is at least partially filled with adhesive, the snow rake member is firmly fixed through the cylindrical fixing member to the rod-shaped member, although the root end part of the snow rake member is thinner than the other end part of the rod-shaped member.
The joint part of the cylindrical fixing member and the rod-shaped member can be covered with a seal member. Water is prevented from finding its way into the joint area between the cylindrical fixing member and the rod-shaped member. Further, if the rod-shaped member is made from a metal prone to rust corrosion, a seal member covering the outside surface of the rod-shaped member or part of the rod-shaped member joined to the cylindrical fixing member can inhibit such corrosion or rusting. By covering the joint area between the cylindrical fixing member and the rod-shaped member with the seal member, the external appearance also can be improved.
A snow lubrication device is also proposed in which a wire having pliability is used in place of the swing arm design described above. To fix the wire of this snow lubrication device to the vehicle body of the snowmobile, one end of the wire is inserted into a hole formed in a fixing member and stopped with a screw. The wire is fixed through the fixing member to the vehicle body. In some applications, vibrations or other conditions may cause the screw or other fattener to become dislodged. With this snow lubrication device, however, it is possible that the screw for fixing the wire to the fixing member may loosen, resulting in the wire being dislodged from the fixing member.
Another aspect is a snow lubrication device for a snowmobile for running on snow. The snow mobile has an endless track belt driven with a drive wheel by the drive of an engine, wherein the track belt is pressed against the snow surface, and wherein the snow lubrication device is configured to be attached to a front portion of the snowmobile for raking and scattering snow on the snow surface. The scattering snow lubricates a contact part between the track belt and a part of the snowmobile that is in contact with the track belt. The snow lubrication device comprises a fixing member comprising a fixing part fixed to the forward portion of the vehicle body of the snowmobile and a cylindrical member, a rod-shaped member having elasticity having a first end part coupled with the cylindrical part of the fixing member, and a snow rake member having a root end part coupled with a second end part of the rod-shaped member and having a front-end formed with a blade part for raking snow.
Another aspect is a snow lubrication device for a snowmobile having an endless track belt driven with a drive wheel by an engine, the snow lubrication device being attached to a front portion of the snowmobile. The snow lubrication device comprises a fixing member comprising a fixing part, the fixing part enabling the snow lubrication device to be fixed to the front portion of the snowmobile, an elastic rod-shaped member extending from the fixing member, and a snow rake member having a root end and a blade, the root end being fixed to the rod-shaped member, the blade being configured to rake and scatter snow to lubricate a contact region between the endless track belt and the snowmobile.
Another aspect is a snowmobile having a snow lubrication device attached to a front portion of the snowmobile and configured to rake and scatter snow to lubricate a contact region between an endless track belt and the snowmobile. The snowmobile comprises an engine, a drive wheel driven by the engine, an endless track belt driven by the drive wheel, and a seat located on a rear upper part of the snowmobile. The snowmobile further comprises handlebars configured for a rider to control a direction of movement for the snow mobile, a fixing member comprising a fixing part, the fixing part enabling the snow lubrication device to be fixed to the front portion of the snowmobile, an elastic rod-shaped member extending from the fixing member, and a snow rake member having a root end and a blade, the root end being fixed to the rod-shaped member, the blade being configured to rake and scatter snow to lubricate a contact region between the endless track belt and the snowmobile.
An aspect is a method for lubricating a contact region between an endless belt and a snowmobile having a snow lubrication device attached to a front portion of the snowmobile. The method comprises configuring an endless belt to contact against a snow surface so as to move a snowmobile in a forward direction, configuring to scatter snow at a location forward of the contact between the endless belt and the snow surface, configuring to direct the scattering snow rearward and toward said endless belt, configuring to lubricate the endless belt with the scattering snow, configuring to contact a snow lubrication device with a rock on the snow surface, and configuring to elastically deform the snow lubrication device as a result of the contact with the rock.
Another aspect is a method for manufacturing a snow lubrication device for a snowmobile, the snowmobile having an endless track belt driven with a drive wheel rotated by the drive of an engine. The method comprises providing a fixing member having a fixing part configured to be fixed to the snowmobile and a cylindrical member, inserting an end part of a rod-shaped member having elasticity into the cylindrical member of the fixing member, clamping the end part within the cylindrical member, and fixing a root end of a snow rake member to the other end part of the rod-shaped member, a rearward facing end of the snow rake member having a blade part configured to rake snow.
The systems and methods of the invention have several features, no single one of which is solely responsible for its desirable attributes. Without limiting the scope of the invention as expressed by the claims which follow, its more prominent features have been discussed briefly above. After considering this discussion, and particularly after reading the section entitled “Detailed Description of the Preferred Embodiments” one will understand how the features of the system and methods provide several advantages over traditional snow lubrication systems.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features, aspects and advantages of the present invention will now be described in connection with preferred embodiments of the invention, in reference to the accompanying drawings. The illustrated embodiments, however, are merely examples and are not intended to limit the invention. The following are brief descriptions of the drawings.
FIG. 1 is a side view of a snowmobile having a snow lubrication device according to a first embodiment of the invention.
FIG. 2 is a plan view of the snowmobile shown in FIG. 1 .
FIG. 3 is an enlarged front side view of the snowmobile and snow lubrication device according to the first embodiment.
FIG. 4 is a plan view of the snowmobile from FIG. 3 .
FIG. 5 is a front face view of a snow rake rod from the snow lubrication device for use on the left side of the snowmobile.
FIG. 6 is a side face view of the snow rake rod from FIG. 5 .
FIG. 7 is a front face view of a snow rake rod for use with the snow lubrication device on the right side of the snowmobile.
FIG. 8A is a front view of a fixing member.
FIG. 8B is a side view of the fixing member shown in FIG. 8A .
FIG. 9A is a plan view of the snow rake member.
FIG. 9B is a front view of the snow rake member shown in FIG. 9A .
FIG. 9C is a side view of the snow rake member shown in FIG. 9A .
FIG. 10 is an oblique view of a state in which the snow rake rod rakes up snow and ice on the snow surface.
FIG. 11 is a front face view of a snow rake rod for use with the snow lubrication device according to a second embodiment having one or more seal members.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The following detailed description is now directed to certain specific embodiments of the invention. However, the invention can be embodied in a multitude of different systems and methods. In this description, reference is made to the drawings wherein like parts are designated with like numerals throughout.
FIG. 1 is a side view of a snowmobile SM comprising a first embodiment of a snow lubrication device 20 . FIG. 2 is a plan view of the snowmobile SM shown in FIG. 1 having a vehicle body 10 . The snowmobile SM further comprises a windshield 11 located on the upper front part of the vehicle body 10 for averting wind. Handlebars 12 are located rearward of the windshield 11 and used to operate the snowmobile SM. A seat 13 for a rider is provided on a rear upper part of the vehicle body 10 .
Drive wheels (not shown) comprising sprockets are located on both sides of the front part of the vehicle body 10 . Rear wheels 14 are provided on both sides of the rear part of the vehicle body 10 . A track belt 15 is routed around the drive wheels and the rear wheels 14 . The track belt 15 has an outer circumferential surface with projections for engaging with the snow surface. As illustrated in FIG. 1 , slide rails 16 , free wheels 17 a, 17 b, etc. are located on a lower portion of the inside of the circumferential surface of the track belt 15 .
The slide rails 16 , free wheels 17 a, 17 b, etc. press the circulating track belt 15 against the snow surface. As a result, the track belt 15 circulates as the projections located on the underside of the track belt 15 engage with the snow surface to cause the snowmobile SM to move forward. Front suspensions 18 are connected to the handlebars 12 on both sides of the vehicle body 10 . For ease of explanation, members of the left front suspension 18 have the same reference numerals as members of the right front suspension 18 .
The front suspensions 18 comprise dampers 18 a on both left and right sides of the vehicle body 10 . Connecting rods 18 c on both left and right sides connect to the dampers 18 a through front suspension arms 18 b and extend below the vehicle body 10 . Corresponding skis 19 for steering are connected to the lower ends of the connecting rods 18 c. The shapes of the respective members of the left and right front suspensions 18 and the steering skis 19 have left-right symmetry.
FIG. 3 is an enlarged front side view of the snowmobile SM and snow lubrication device 20 . FIG. 4 is a plan view of the snowmobile SM from FIG. 3 . The front suspension 18 also comprises, as shown in FIGS. 3 and 4 , an arm part 18 d for turning the connecting rod 18 c about its axis. The arm part 18 d moves back and forth according to the operation of the handlebars 12 . With the back-and-forth motion, the steering ski 19 turns left and right. The steering ski 19 is connected to the connecting rod 18 c through a support shaft 19 a connected to the lower end of the connecting rod 18 c. The steering ski 19 comprises a main part 19 b in contact with the snow surface and a grip part 19 c. The grip part 19 c allows the steering ski 19 to be gripped by hand.
The snow lubrication device 20 is in the vicinity of each arm part 18 d of the vehicle body 10 . The snow lubrication device 20 comprises two fixing arms 21 , each extending from a position slightly behind the arm part 18 d of the vehicle body 10 obliquely in a downward and forward direction. The snow lubrication device 20 further comprises two snow rake rods 22 , 22 a (See FIG. 7 for 22 a ) fixed to the fixing arms 21 on the sides of the snowmobile SM. FIG. 5 is a front face view of the snow rake rod 22 for a left side of the vehicle body 10 . FIG. 6 is a side face view of the snow rake rod 22 from FIG. 5 , partially in section. FIG. 7 is a front face view of the snow rake rod 22 a for a right side of the vehicle body 10 . The snow rake rods 22 , 22 a are preferably used as a set on the snow lubrication device 20 . Of course the snow lubrication device 20 could employ a single fixing arm 21 and single snow rake rod 22 , but preferably employs two fixing arms and snow rake rods for both sides of the snowmobile.
As illustrated in FIG. 3 , the fixing arm 21 may be made of a plate-shaped rod member having one or more fixing holes 21 a along its length. The one or more fixing holes 21 a allow attachment of the snow rake rod 22 at multiple positions.
As illustrated in FIG. 5 , the snow rake rod 22 comprises an elastic rod-shaped member 23 , a fixing member 24 fixed to one end of the rod-shaped member 23 and a snow rake member 25 attached to the other end of the rod-shaped member 23 . A cylindrical fixing member 26 fixes the snow rake member 25 to the rod-shaped member 23 . The rod-shaped member 23 comprises a core member 23 a made from a wire covered with a plastic cover 23 b. The core member 23 a may be made from a metal iron wire or any other suitable, elastic material. In certain embodiments, the rod-shaped member 23 has an approximate length of 250 mm and a diameter of 8 mm.
FIG. 8A is a front view of the fixing member 24 . FIG. 8B is a side view of the fixing member 24 shown in FIG. 8A . The fixing member 24 is preferably made of metal and comprises a fixing part 24 a fixed to the fixing arm 21 , and a cylindrical part 24 b fixed to the rod-shaped member 23 .
The fixing part 24 a has a generally oval shape with an attachment hole 24 c extending therethrough. The attachment hole 24 c is offset from the center of the fixing part 24 a in a distal direction towards the fixing arm 21 . The cylindrical part 24 b has a generally cylindrical shape. The rounded end of the cylindrical part 24 b, as illustrated in FIG. 8A , is connected to the fixing part 24 a. As illustrated in FIG. 8B , a surface of the fixing part 24 a is flush with and coupled to a back side surface of the cylindrical part 24 b. As illustrated in FIG. 5 , the rod-shaped member 23 and the fixing part 24 a are fixed together by inserting one end of the rod-shaped member 23 into the cylindrical part 24 b. The cylindrical part 24 b is clamped around the inserted end using a crimping process.
FIG. 9A is a plan view of the snow rake member 25 . FIG. 9B is a front view of the snow rake member 25 shown in FIG. 9A . FIG. 9C is a side view of the snow rake member 25 . In certain embodiments, the snow rake member 25 comprises cemented carbide. As shown in FIG. 5 and FIGS. 9A-9C , a root end part 25 a is fixed to an end of the rod-shaped member 23 . A front-end side of the root end part 25 a is fixed to a blade part 25 b.
The thickness or horizontal width shown in FIG. 9A of the root end part 25 a is constant. The thickness of the blade part 25 b decreases near the end of the blade part 25 b. The width or vertical width shown in FIG. 9B is smaller at the root end part 25 a and increases from the root end part 25 a side and toward the front-end side. Both side surfaces are formed with irregular parts 25 c having a wavy irregular shape along a longitudinal direction. Both side surfaces intersect at right angles relative to the width direction of the root end part 25 a. The blade part 25 b is shaped to curve from the root end part 25 a side toward the front-end side.
As illustrated in FIG. 5 , the cylindrical fixing member 26 has a cylindrical shape. In certain embodiments, the cylindrical fixing member 26 is made of metal. The end of the rod-shaped member 23 is inserted into the end of the member 26 . The root end part 25 a of the snow rake member 25 is inserted into the other end of the member 26 and clamped by a crimping process to fix the rod-shaped member 23 to the snow rake member 25 . A gap between the root end part 25 a and the cylindrical fixing member 26 is filled with adhesive or other filler agent. The filler agent and the irregular parts 25 c formed on the root end part 25 a firmly fix the snow rake member 25 to the rod-shaped member 23 through the cylindrical fixing member 26 .
The snow rake rod 22 a illustrated in FIG. 7 is the same as the snow rake rod 22 illustrated in FIG. 5 except that the direction of curvature for the snow rake member 25 of the snow rake rod 22 a is opposite to the direction of curvature for the snow rake member 25 of the snow rake rod 22 . For ease of explanation, corresponding parts for the left and right sides of the snow mobile SM have the same reference numerals. The snow rake rods 22 and 22 a described above are fixed to the corresponding fixing arms 21 on the vehicle body 10 through bolts 27 and nuts or through other suitable fasteners. The snow rake rods 22 and 22 a are attached by first aligning the attachment holes 24 c of the snow rake rods 22 and 22 a with one of the fixing holes 21 a of the fixing arms 21 . The bolts 27 are inserted into both holes. The nuts are then attached to the bolts 27 .
A method of operation is described below. First, a switch located in the vicinity of the handlebars 12 is turned on. The switch starts the engine which drives the snowmobile SM. A throttle lever on the handlebar 12 controls the engine.
FIG. 10 is an oblique view of a state in which the snow rake rod 22 a (See FIG. 7 ) on the right side of the vehicle body 10 rakes up snow and ice on the snow surface. This same description applies equally to the snow rake rod 22 on the left side of the vehicle body 10 . The snow rake rod 22 a deflects rearward as the blade part 25 b of the snow rake rod 22 a comes into contact with the snow surface. The blade part 25 b rakes up snow and ice on the snow surface and scatters the snow rearward. The scattered snow adheres to the inner surface of the track belt 15 and finds its way into the gap between the track belt 15 and the slide rail 16 , and into the gap between the track belt 15 and the drive wheel.
The scattered snow located in the gaps between the track belt 15 and the slide rail 16 and between the track belt 15 and the drive wheel provides lubrication. The lubricated track belt 15 improves the operation of the snowmobile SM. Even if the lower part of the snow rake rod 22 a strikes a stone or the like, the elasticity of the rod-shaped member 23 allows the snow rake rod 22 a to deflect further rearward. Even if the snow rake rod 22 a strikes a stone or the like, the impact does not adversely affect operation of the snowmobile SM. When the snowmobile SM is made to run in reverse, the snow rake rod 22 a is free to deflect towards the front of the vehicle body 10 . Accordingly, the snow rake rod 22 a does not hinder operation of the snowmobile SM in forward or reverse directions.
As described above, the rod-shaped member 23 is fixed to the fixing member 24 by crimping one end of the rod-shaped member 23 in the cylindrical part 24 b of the fixing member 24 . The rod-shaped member 23 is firmly fixed to the fixing member 24 to prevent the rod-shaped member 23 from dislodging from the fixing member 24 . Further, since the root end part 25 a of the snow rake member 25 is thinner than the end part of the rod-shaped member 23 , the snow rake member 25 may have a small size and be light in weight.
As illustrated in FIG. 5 , the rod-shaped member 23 and the snow rake member 25 may be fixed together by abutting the end of the root end part 25 a of the snow rake member 25 against the end of the rod-shaped member 23 . The adjacent ends are fitted within the cylindrical fixing member 26 and clamped using a crimping process. Further, both surfaces of the root end part 25 a that are likely to experience shock from the snow surface or the like are formed with the irregular parts 25 c. The gap between the root end part 25 a and the cylindrical fixing member 26 is filled with adhesive. Therefore, the snow rake member 25 is firmly fixed to the rod-shaped member 23 . Further, by covering the outer circumference of the core member 23 a with a plastic cover 23 b, the core member 23 a is inhibited from developing rust.
FIG. 11 is a front face view of a snow rake rod 32 for use with the snow lubrication device according to a second embodiment. The snow rake rod 32 is the same as the snow rake rod 22 described with reference to FIG. 5 except that the snow rake rod 32 comprises seal members 38 , 39 . For ease of explanation, the same parts are provided with the same reference numerals without repeating their descriptions. Like the embodiment described with reference to FIG. 5 , the embodiment illustrated in FIG. 11 includes a pair of snow rake members 25 curving in opposite directions. The seal member 38 may be made of plastic and covers the joint between a rod-shaped part 23 and a fixing member 24 . The seal member 39 may be made of plastic and covers the joint between the rod-shaped part 23 and a cylindrical fixing member 26 .
The seal members 38 , 39 inhibit water from finding its way into the joints between the rod-shaped member 23 and the fixing member 24 and into the joint between the rod-shaped member 23 and the cylindrical fixing member 26 . The seal members 38 , 39 inhibit water from seeping into the plastic cover 23 b of the rod-shaped member 23 and inhibit the core member 23 a inside the cover from developing rust. Further, covering the joint between the rod-shaped member 23 and the fixing member 24 with the seal member 38 , and covering the joint between the rod-shaped member 23 and the cylindrical fixing member 26 with the seal member 39 , improves the external appearance of the snow rake rod 32 . The snow rake rod 32 performs the same function and effect of lubrication as the snow rake rod 22 described with reference to the first embodiment.
This invention is not limited to the above-described embodiments but may be appropriately modified and implemented accordingly. For example, while the plastic cover 23 b and the seal members 38 , 39 are made of plastic in certain embodiments, it is possible to make them from other materials. Further, in embodiments where the core member 23 a of the rod-shaped member 23 is made of a rust-free material such as stainless steel, the plastic cover 23 b may be omitted. Furthermore, shapes and materials of other parts of the snow lubrication device 20 related to this invention may be appropriately modified within the technical scope of this invention.
While the above detailed description has shown, described, and pointed out novel features of the invention as applied to various embodiments, it will be understood that various omissions, substitutions, and changes in the form and details of the device or process illustrated may be made by those skilled in the art without departing from the spirit of the invention. The scope of the invention is indicated by the appended claims rather than by the foregoing description. All changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope. | A snow lubrication device attaches to a vehicle body of a snowmobile and includes a pair of snow rake rods extending from the vehicle body to contact a snow surface. A snow rake member located at the end of the snow rake rod scatters snow. The scattered snow lubricates gaps between a track belt and the slide rail and/or between the track belt and the drive wheel. The lubrication of the track belt improves operation of the snowmobile if the lower part of the snow rake rod strikes a stone or the like, the snow rake rod temporarily deflects further rearward. The snow lubrication device has relatively few components, is low in cost, and is hard to dislodge from a snowmobile. | 8 |
FIELD OF THE INVENTION
The invention relates generally to oil field equipment, including reciprocating pumps and down-hole equipment useful for high-pressure well-service (e.g., well-stimulation). More specifically, the invention relates to origins, effects, and design criteria related to shock and vibration in well-stimulation systems.
INTRODUCTION
Selected improved designs described herein for reciprocating pumps and down-hole well-stimulation equipment reflect disparate applications of identical technical principles (relating to, e.g., the vibration spectrum of an impulse). In a high-pressure well-stimulation pump, for example, impulses originate in the fluid-end's suction and discharge check valves. The resulting valve-generated vibration spectra are controlled, suppressed and/or selectively damped (e.g., using tunable components) to limit destructive excitation of resonances which could otherwise cause fatigue cracking and premature pump failure.
In contrast, vibration spectra originating in a down-hole tunable hydraulic stimulator are tuned and beneficially directed to increase well production via stimulation (e.g., fracturing) of adjacent geologic materials. Such tuned vibration spectra originate in the mechanical shocks (i.e., impulses) of a hammer element striking a fluid interface of the stimulator. The resulting vibration spectra are tuned at their source (e.g., by altering hammer rebound cycle time for each hammer element strike) to maximize resonance excitation in geologic materials which surround the wellbore adjacent to explosively-formed perforations.
The following background materials discuss the vibration spectrum of an impulse, highlighting its importance with examples of the deleterious effects of mechanical shock and vibration in conventional high-pressure pump applications. Analogous-in-part vibration-related issues in the automotive industry are described to illustrate that positive or negative aspects of vibration in mechanical systems often become economically important, or even evident, only above certain power levels. Building on this background, subsequent sections describe selected alternative (modified) designs for high-pressure pumps and associated well-stimulation equipment (including down-hole tunable hydraulic stimulators) which address current operational issues of reliability, efficiency, and efficacy.
BACKGROUND
The necessity for operational modifications described herein is better appreciated after first considering certain limitations of conventional reciprocating high-pressure pumps. Commonly called fracking, frac or well-service pumps, they are often used in oil and gas fields for well-stimulation (e.g., hydraulic fracturing of rock formations to increase hydrocarbon yields). Such pumps are typically truck-mounted for easy relocation from well-to-well. And they are usually designed in two sections: the (proximal) power section (herein “power end”) and the (distal) fluid section (herein “fluid end”). Each pump fluid end comprises at least one subassembly (and commonly three or more in a single fluid end housing), with each subassembly comprising a suction valve, a discharge valve, a plunger or piston, and a portion of (or substantially the entirety of) a pump fluid end subassembly housing (shortened herein to “pump housing” or “fluid end housing” or “housing”, depending on the context.
For each pump fluid end subassembly, its fluid end housing comprises a pumping chamber in fluid communication with a suction bore, a discharge bore, and a piston/plunger bore. A suction valve (i.e., a check valve) within the suction bore, together with a discharge valve (i.e., another check valve) within the discharge bore, control bulk fluid movement from suction bore to discharge bore via the pumping chamber. Note that the term “check valve” as used herein refers to a valve in which a (relatively movable) valve body can close upon a (relatively stationary) valve seat to achieve substantially unidirectional bulk fluid flow through the valve.
Pulsatile fluid flow through the pump results from periodic pressurization of the pumping chamber by a reciprocating plunger or piston within the plunger/piston bore. Suction and pressure strokes alternately produce wide pressure swings in the pumping chamber (and across the suction and discharge check valves) as the reciprocating plunger or piston is driven by the pump power end.
Such pumps are rated at peak pumped-fluid pressures in current practice up to about 22,000 psi, while simultaneously being weight-limited due to the carrying capacity of the trucks on which they are mounted. (See, e.g., U.S. Pat. No. 7,513,759 B1, incorporated by reference).
Due to high peak pumped-fluid pressures, suction check valves experience particularly wide pressure variations between a suction stroke, when the valve opens, and a pressure stroke, when the valve closes. For example, during a pressure stroke with a rod load up to 350,000 pounds, a conventionally rigid/heavy check valve body may be driven longitudinally (by pressurized fluid behind it) toward metal-to-metal impact on a conventional frusto-conical valve seat at closing forces of about 50,000 to over 250,000 pounds (depending on valve dimensions). Total check valve-closure impact energy (i.e., the total kinetic energy of the moving valve body and fluid at valve seat impact) is thus converted to a short-duration high-amplitude valve-closure impulse (i.e., a mechanical shock). Repeated application of such a valve-closure shock with each pump cycle predisposes the check valve, and the fluid end housing in which it is installed, to vibration-induced (e.g., fatigue) damage. Cumulative shocks thus constitute a significant liability imposed on frac pump reliability, proportional in part to the rigidity and weight of the check valve body.
The emergence of new frac pump reliability issues has paralleled the inexorable rise of peak pumped-fluid pressures in new fracking applications. And insight into these new pump failure modes can be gained through review of earlier shock and vibration studies, data from which are cited herein. For example, a recent treatise on the subject describes a mechanical shock “ . . . in terms of its inherent properties, in the time domain or in the frequency domain; and . . . in terms of the effect on structures when the shock acts as the excitation.” (see p. 20.5 of Harris' Shock and Vibration Handbook , Sixth Edition, ed. Allan G. Piersol and Thomas L. Paez, McGraw Hill (2010), hereinafter Harris ). The above time and frequency domains are mathematically represented on opposite sides of equations generally termed Fourier transforms. And estimates of a shock's structural effects are frequently described in terms of two parameters: (1) the structure's undamped natural frequency and (2) the fraction of critical structural damping or, equivalently, the resonant gain Q (see Harris pp. 7.6, 14.9-14.10, 20.10). (See also, e.g., U.S. Pat. No. 7,859,733 B2, incorporated by reference).
Mathematical representations of time and frequency domain data play important roles in computer-assisted analysis of mechanical shock. In addition, shock properties are also commonly represented graphically as time domain impulse plots (e.g., acceleration vs. time) and frequency domain vibration plots (e.g., spectrum amplitude vs. frequency). Such graphical presentations readily illustrate the shock effects of metal-to-metal valve-closure, wherein longitudinal movement of a check valve body is abruptly stopped by a valve seat. Relatively high acceleration values and broad vibration spectra are prominent, each valve-closure impulse response primarily representing a violent conversion of kinetic energy to other energy forms.
Since energy cannot be destroyed, and since a conventional valve can neither store nor convert (i.e., dissipate) more than a small fraction of the valve-closure impulse's kinetic energy, most of that energy is necessarily transmitted to the pump housing. In a time domain plot, the transmitted energy appears as a high-amplitude impulse of short duration. And a corresponding frequency domain plot of transmitted energy reveals a broad-spectrum band of high-amplitude vibration. This means that nearly all of the check valve's cyclical valve-closure kinetic energy is converted to vibration energy. The overall effect of check valve closures may thus be compared to the mechanical shocks that would result from striking the valve seat repeatedly with a commercially-available impulse hammer, each hammer strike being followed by a rebound. Such hammers are easily configured to produce relatively broad-spectrum high-amplitude excitation (i.e., vibration) in an object struck by the hammer. (See, e.g., Introduction to Impulse Hammers at http://www.dytran.com/img/tech/a11.pdf, and Harris p. 20.10).
Summarizing then, relatively broad-spectrum high-amplitude vibration predictably results from a typical high-energy valve-closure impulse. And frac pumps with conventionally-rigid valves can suffer hundreds of these impulses per minute. Note that the number of impulses per minute (for example, 300 impulses per minute) corresponds to pump plunger strokes or cycles, and this number may be converted to impulses-per-second (i.e., 300/60=5). The number 5 is sometimes termed a frequency because it is given the dimensions of cycles/second or Hertz (Hz). But the “frequency” thus attributed to pump cycles themselves differs from the spectrum of vibration frequencies resulting from each individual pump cycle impulse. The difference is that impulse-generated (e.g., valve-generated) vibration occurs in bursts of broad spectra which may simultaneously contain many vibration frequencies ranging from a few Hz to several thousand Hz (kHz).
Nearly all of the (generally higher-frequency) valve-generated vibration energy is quickly transmitted to proximate areas of the fluid end or pump housing, where it can be expected to excite damaging resonances that predispose the housing to fatigue failures. (See, e.g., U.S. Pat. No. 5,979,242, incorporated by reference). If, as expected, a natural resonance frequency of the housing coincides with a frequency within the valve-closure vibration spectrum, fluid end vibration amplitude may be substantially increased and the corresponding vibration fatigue damage made much worse. (See Harris , p. 1.3).
Opportunities to limit fluid end damage begin with experiment-based redesign to control vibration fatigue. For example, a spectrum of vibration frequencies initially applied as a test can reveal structural resonance frequencies likely to cause trouble. Specifically, the applied vibration of a half-sine shock impulse of duration one millisecond has predominant spectral content up to about 2 kHz (see Harris , p. 11.22), likely overlapping a plurality of fluid end housing natural frequencies. Such tests particularly focus attention on blocking progression of fatigue crack growth to the critical size for catastrophic fracture. Note that stronger housings are not necessarily better in such cases, since increasing the housing's yield strength causes a corresponding decrease in critical crack size. (See Harris , p. 33.23).
It might be assumed that certain valve redesigns proposed in the past (including relatively lighter valve bodies) would have alleviated at least some of the above failure modes. (See, e.g., U.S. Pat. No. 7,222,837 B1, incorporated by reference). But such redesigns emerged (e.g., in 2005) when fluid end peak pressures were generally substantially lower than they currently are. In relatively lower pressure applications (e.g., mud pumps), rigid/heavy valve bodies performed well because the valve-closure shocks and associated valve-generated vibration were less severe compared to shock and vibration experienced more recently in higher pressure applications (e.g., fracking) Thus, despite their apparent functional resemblance to impulse hammers, relatively rigid/heavy valves have been pressed into service as candidates for use in frac pump fluid ends. Indeed, they have generally been the only valves available in commercial quantities during the recent explosive expansion of well-service fracking operations. Substantially increased fluid end failure rates (due, e.g., to cracks near a suction valve seat deck) have been among the unfortunate, and unintended, consequences.
Under these circumstances, it is regrettable but understandable that published data on a modern 9-ton, 3000-hp well-service pump includes a warranty period measured in hours, with no warranty for valves or weld-repaired fluid ends.
Such baleful vibration-related results in fluid ends might usefully be compared with vibration-related problems seen during the transition from slow-turning two-cylinder automobile engines to higher-speed and higher-powered inline six-cylinder engines around the years 1903-1910. Important torsional-vibration failure modes suddenly became evident in new six-cylinder engines, though they were neither anticipated nor understood at the time. Whereas the earlier engines had been under-powered but relatively reliable, torsional crankshaft vibrations in the six-cylinder engines caused objectionable noise (“octaves of chatter from the quivering crankshaft”) and unexpected catastrophic failures (e.g., broken crankshafts). (Quotation cited on p. 13 of Royce and the Vibration Damper , Rolls-Royce Heritage Trust, 2003). Torsional-vibration was identified as the culprit and, though never entirely eliminated, was finally reduced to a relatively minor maintenance issue after several crankshaft redesigns and the development of crankshaft vibration dampers pioneered by Royce and Lanchester.
Reducing the current fluid end failure rates related to valve-generated vibration in frac pumps requires an analogous modern program of intensive study and specific design changes. The problem will be persistent because repeatedly-applied valve-closure energy impulses cannot be entirely eliminated in check-valve-based fluid end technology. So the valve-closing impulses must be modified, and their associated vibrations damped, to reduce excitation of destructive resonances in valves, pump housings, and related fluid end structures. Alternate materials, applied via innovative designs, illuminate the path forward now as they have in the past. Broad application of such improvements promises higher frac pump reliability, an important near-term goal. Simultaneously, inhibition of corrosion fatigue throughout analogous fluid circuits would be advanced, a longer-term benefit in refineries, hydrocarbon crackers and other industrial venues that are also subjected to shock-related vibration.
Further, when considering well-stimulation systems comprising frac pumps together with down-hole equipment, additional opportunities for increased efficiency of stimulation arise. Concentration of stimulation resources near wellbore collection sites, together with feedback-controlled application of stimulation energy conserves time and money. And tailoring the forms of stimulation energy to well-specific geologic parameters contributes to operational flexibility, efficiency, and efficacy.
SUMMARY OF THE INVENTION
As described herein, control of vibration spectra associated with impulses (e.g., mechanical shocks) guides the design of both tunable fluid ends and tunable hydraulic stimulators for increased system reliability and productivity. Fundamental principles are invoked to explain improved operational characteristics for vibration control (in fluid ends) and for generation of tuned vibration spectra (in hydraulic stimulators). Tuned generation of vibration spectra in stimulators is considered first, because techniques for production of desired frequency bands (vibration spectra) and amplitudes (vibration energy) in stimulators will be seen subsequently to identify structures and parameters bearing on vibration control in fluid ends.
In a first example embodiment, a tunable hydraulic stimulator comprises a hollow cylindrical housing having a longitudinal axis, a first end, and a second end, the first end being closed by a fluid interface for transmitting and receiving vibration. A driver element reversibly seals the second end, and the fluid interface comprises at least one accelerometer for sensing (i.e., producing an accelerometer signal representing) vibration transmitted and received by the fluid interface. A hammer element is longitudinally movable within the housing between the driver element and the fluid interface, the hammer element being responsive to the driver element for striking, and rebounding from, the fluid interface.
The driver element comprises an electromagnet/controller having cyclical magnetic polarity reversal (and thus variable field strength) implemented via, for example, a passive timing network or an embedded microprocessor's stored program. Cyclical magnetic polarity reversal is characterized by a polarity reversal frequency which may be responsive to the accelerometer signal. Longitudinal movement of the hammer element is responsive (e.g., via electromagnetic attraction and repulsion) to the driver element's cyclical magnetic polarity reversal (analogous in part to a linear electrical motor). Further, longitudinal movement of the hammer element striking, and subsequently rebounding from, the fluid interface may be substantially in phase with the polarity reversal frequency to generate vibration transmitted by the fluid interface.
Each hammer strike is at least in part a function of magnetic field polarity and strength, and it is followed by a rebound which is at least in part a function of flexure due to elastic properties (e.g., modulus of elasticity) of the hammer and fluid interface. The rebound may also be a function (in part) of magnetic field polarity and strength. The duration of the entire flexure-rebound interval is termed herein “hammer rebound cycle time” and is measured in seconds. The inverse of hammer rebound cycle time has the same dimensions as frequency and is termed herein “hammer rebound characteristic frequency”. Each hammer strike/rebound applies a mechanical shock to the fluid interface which generates a spectrum of vibration frequencies that are transmitted by the fluid interface to the surrounding fluid. (See the Background section above).
Note that hammer rebound movement may be augmented or impeded by the driver element's magnetic field polarity, thereby changing hammer rebound cycle time and thus changing the character of vibration spectra generated. In other words, the driver element's electromagnet/controller can effectively, and in near-real time, tune each vibration spectrum transmitted by the fluid interface for application to geologic material adjacent to a wellbore. Such tuning may comprise, e.g., altering a transmitted vibration spectrum's bandwidth and/or changing the relative magnitudes of the vibration spectrum's frequency components. In other words, stimulation energy in the form of vibration spectra transmitted by a tunable hydraulic stimulator's fluid interface may be subject (in near-real time) to predetermined alterations.
Such alterations in the character of stimulation energy applied to geologic material (in the form of relatively broad-band vibration) may include, e.g., changes in vibration frequencies present and/or in relative energy levels of vibration frequency components. Such changes may be desirable while stimulation progresses through a continuum of fracturing of the geologic material. As progress of stimulation is reflected in progressive fracturing and/or fragmentation of the geologic material, such material's absorption of stimulation energy changes in a time-varying manner. Changes in absorbed energy, in turn, cause changes in backscattered vibration that may be sensed by the accelerometer at the fluid interface. The resulting accelerometer signal may then be fed back to the driver (e.g., by cable or wirelessly) as described herein.
The invention thus facilitates a form of closed-loop (feedback) control of the stimulation process that may be optimized (i.e., yielding better results from less stimulation). One might choose, for example, to emphasize relatively lower frequency stimulation energy initially, followed by adaptively increasing relatively higher frequency vibration spectrum components as stimulation progresses. Individual tunable hydraulic stimulators of the invention can support such an optimization strategy inherently because they naturally produce relatively broad vibration spectra (rather than single-frequency vibration). Should a greater frequency range be desired than that obtainable from a single tunable hydraulic stimulator, a plurality of such stimulators may be interconnected in a tunable hydraulic stimulator array. Operation of such an array may be controlled via, for example, communication among programmable microprocessors associated with the driver of each stimulator of an autonomous stimulator array. For example, the driver element polarity reversal frequency may be responsive to one accelerometer signal. Alternatively or additionally, the array may be subject to control via programmable devices elsewhere in a wellbore and/or at the wellhead.
Second and third example embodiments of tunable hydraulic stimulators are similar in several respects to the first example embodiment, with the fluid interface comprising at least one accelerometer for producing an accelerometer signal representing vibration of the fluid interface due to both transmitted and backscattered vibration. As in the first example, the driver element comprises an electromagnet/controller having cyclical magnetic polarity reversal (and thus variable field strength). Cyclical magnetic polarity reversal is characterized by a polarity reversal frequency which is variable. The driver element controller receives the accelerometer signal (via, e.g., a cable or wirelessly) and processes (e.g., via a microprocessor executing a stored program) the signal to produce excitation for the driver element electromagnet for control of its cyclical magnetic polarity reversal (and thus its polarity reversal frequency). The polarity reversal frequency is thus responsive to the accelerometer signal. And since the hammer element is responsive to the driver element, longitudinal movement of the hammer element may thus be substantially in phase with the polarity reversal frequency during predetermined portions of stimulation.
Further, longitudinal hammer element movement, as noted above, is associated with a hammer rebound characteristic frequency. In certain embodiments, the hammer rebound characteristic frequency may be similar to the polarity reversal frequency.
Note that part of the vibration sensed at the fluid interface includes backscattered vibration that may contain information on the progress of well-stimulation (e.g., the degree of rock fracturing and/or fragmentation, including the size of rock fragments) induced in part by vibration earlier transmitted from the fluid interface. (See U.S. Pat. No. 8,535,250 B2, incorporated by reference). Hence, the well-stimulation information can be used to augment control of transmitted vibration due to hammer strikes and rebounds.
Note also that the driver element's polarity and field strength may also or alternatively be responsive (e.g., via integrated control electronics and windings of the electromagnet) to vibration of the fluid interface. Such responsiveness may be mediated, e.g., via changes in the magnetic field permeability sensed by the control electronics, the permeability changes being in part functions of the amplitude and frequency of backscattered vibration received by the fluid interface. Reception of the backscattered vibration, in either case, allows near-real-time estimation of the degree of stimulation imposed by the tunable hydraulic stimulator.
An important determinant of imposed stimulation is the hammer element's striking face, which has a predetermined modulus of elasticity that may be relatively high (approximately that of mild steel, for example) if a relatively broad spectrum of stimulation vibration is desired. Conversely, a lower modulus of elasticity may be chosen to reduce the highest frequency components of stimulation vibration. For convenience, alternate hammer embodiments may comprise one of a plurality of interchangeable striking faces, each having one value within a predetermined range of modulus choices. Choice of that range will facilitate tuning of the stimulator to predetermined vibration spectra, of course, and the range of vibration spectra parameters will also be influenced by the fluid interface's modulus of elasticity and the design criteria vibration spectrum frequency range.
The spectra of stimulation vibration desired for a particular application will generally be chosen to encompass one or more of the resonant frequencies of the geologic structures being stimulated (including resonant frequencies before, during, and after stimulation). For example, it has been reported that vibration frequencies in the ultrasound range (i.e., >20 kHz) can improve the permeability of certain porous media surrounding a well. On the other hand, vibration frequencies <20 kHz may propagate with less loss, while still significantly increasing well flow rates. (See, e.g., U.S. patent publication number 2014/0027110 A1, incorporated by reference). Optimization of the stimulation process may be facilitated using estimates (obtained via, e.g., a programmable microprocessor in the electromagnet/controller) of vibration parameters detected by the accelerometer at the fluid interface. Such estimates may be based in part, e.g., on the portion(s) of the accelerometer signal representing backscattered vibration from stimulated porous media.
Note that the tunable hydraulic stimulator is intended for down-hole use within a fluid environment maintained in the wellbore via (1) fluids collected through explosively-formed perforations in the wellbore from the surrounding geologic formations and/or via (2) addition of fluid at the wellhead to equal or exceed the filtration rate (sometimes termed the leakoff rate). (See U.S. Pat. No. 8,540,024 B2, incorporated by reference). The fluid surrounding a stimulator may comprise water and/or petroleum oil, and it may be passively pressurized by the well's hydraulic head alone, or with additional pressure provided by one or more frac pumps. Since the tunable hydraulic stimulator can be completely sealed within its surrounding fluid, its use is not subject to dielectric strength and conductivity limitations that are common in pulsed power apparatus. (See also U.S. Pat. No. 8,616,302 B2, incorporated by reference).
Note also that a tunable resilient circumferential seal is electively provided to isolate predetermined explosively-formed perforations in portions of the wellbore, and also to provide a tuned coupling of the stimulator to the wellbore. The circumferential seal comprises a circular tubular area which may contain at least one shear-thickening fluid. And the fluid may further comprise nanoparticles which, in conjunction with the shear-thickening fluid, facilitate tuning of the seal as well as heat scavenging.
Having summarized certain improvements in the down-hole portion of a well-stimulation system, this description now shifts to improvements in the surface portion, with emphasis on the frac pump's fluid end. While the tunable hydraulic stimulator is intended to generate vibration to augment fracturing of rock formations, the focus in fluid ends is on control of valve-generated vibration for minimizing excitation of fluid end and/or pump resonances to avoid fatigue-mediated failures.
Tunable fluid ends reduce valve-generated vibration to increase fluid-end reliability. Tunable fluid end embodiments comprise a family, each family member comprising a pump housing with at least one installed tunable component chosen from: tunable check valve assemblies, tunable valve seats, tunable radial arrays and/or tunable plunger seals. Each tunable component, in turn, contributes to blocking excitation of fluid end resonances, thus reducing the likelihood of fluid end failures associated with fatigue cracking and/or corrosion fatigue. By down-shifting the frequency domain of each valve-closing impulse shock, initial excitation of fluid end resonances is minimized. Subsequent damping and/or selective attenuation of vibration likely to excite one or more predetermined (and frequently localized) fluid end resonances represents optimal employment of vibration-control resources.
Frequency domain down-shifting and damping both assist vibration control by converting valve-closure energy to heat and dissipating it in each tunable component present in a tunable fluid end embodiment. Effects of down-shifting on a valve-closure impulse shock include frequency-selective spectrum-narrowing that is easily seen in the frequency domain plot of each shock. That is, down-shifting effectively attenuates and/or limits the bandwidth(s) of valve-generated vibration. Subsequent (coordinated) damping assists in converting a portion of this band-limited vibration to heat.
Both down-shifting and damping are dependent in part on constraints causing shear-stress alteration (that is, “tuning”) imposed on one or more viscoelastic and/or shear-thickening elements in each tunable component. Additionally, hysteresis or internal friction (see Harris , p. 5.7) associated with mechanical compliance of certain structures (e.g., valve bodies or springs) may aid damping by converting vibration energy to heat (i.e., hysteresis loss). (See Harris , p. 2.18).
Tunable component resonant frequencies may be shifted (or tuned) to approximate predetermined values corresponding to measured or estimated pump or fluid end housing resonant frequencies (herein termed “critical” frequencies). Such coordinated tuning predisposes valve-generated vibration at critical frequencies to excite the tunable component (and thus be damped and dissipated as heat) rather than exciting the housing itself (and thus predispose it to vibration fatigue-related cracking).
To complement the above coordinated damping, frequency down-shifting functions to reduce the total amount of critical frequency vibration requiring damping. Such down-shifting is activated through designs enhancing mechanical compliance. In continuous pump operation, mechanical compliance is manifest, for example, in elastic valve body flexures secondary to repetitive longitudinal compressive forces (i.e., plunger pressure strokes). Each such flexure is followed by a hysteresis-limited elastic rebound, the duration of the entire flexure-rebound interval being termed herein “rebound cycle time.” The inverse of rebound cycle time is termed herein “rebound characteristic frequency.” Cumulative rebound cycle energy loss in the form of heat (e.g., hysteresis loss plus friction loss) is continuously transported for redistribution within the valve body and eventual rejection to the valve body surroundings (including, e.g., the pumped fluid). This heat loss represents a reduction in the available energy content (and thus the damage-causing potential) of the valve-closure energy impulse.
Note that lengthening rebound cycle time to beneficially narrow the valve-generated vibration spectrum is accomplished in various invention embodiments using mechanical/hydraulic/pneumatic analogs of electronic wave-shaping techniques. For example, lengthened rebound cycle time is substantially influenced by the tunable valve assembly's increased longitudinal compliance associated with rolling seal contact (i.e., comprising valve body flexure and rebound) described herein between the valve body's peripheral valve seat interface and the tunable valve seat's mating surface.
Briefly summarizing, as each tunable component present in a tunable fluid end embodiment absorbs, converts and redistributes (i.e., dissipates) a portion of valve closing impulse shock energy, only a fraction of the original closing impulse energy remains at critical frequencies capable of exciting destructive resonant frequencies in the fluid end. Following vibration down-shifting, a significant portion of valve-closure energy has been shifted to lower frequency vibration through structural compliance as described above. This attenuated vibration is then selectively damped (i.e., dissipated as heat) at shifted frequencies via one or more of the tunable components. While tunable components may be relatively sharply tuned (e.g., to act as tuned mass dampers for specific frequencies), they may alternately be more broadly tuned to account for a range of vibration frequencies encountered in certain pump operations. Flexibility in tuning procedures, as described herein with material and adjustment choices, is therefore desirable.
Note that vibration absorption at specific frequencies (e.g., via dynamic or tuned absorbers) may have limited utility in frac pumps because of the varying speeds at which the pumps operate and the relatively broad bandwidths associated with valve-closing impulse shocks. In contrast, the process of down-shifting followed by damping is more easily adapted to changes inherent in the pumps' operational environment. Damping may nevertheless be added to a dynamic absorber to increase its effective frequency range for certain applications. (See, e.g., tuned vibration absorber and tuned mass damper in ch. 6 of Harris ).
Selective damping of vibration frequencies near the resonant frequencies of fluid ends is desirable for the same reason that soldiers break step when they march over a bridge—because even relatively small amounts of vibration energy applied at the bridge's resonant frequency can cause catastrophic failure. Similar reasoning underlies the functions of selective vibration down-shifting and damping in tunable fluid ends. Various combinations of the tunable components described herein are particularly beneficial because they focus the functions of vibration-limiting resources on minimization of vibration energy present in a fluid end near its housing's critical frequencies. Cost and complexity of tunable components are thus minimized while the efficacy of each tunable component's function (i.e., vibration limitation at particular frequencies) is enhanced. Stated another way, a tunable component's selective vibration down-shifting and damping are optimized using metrics including cost, complexity, and damping factor (or degree of damping).
Note that a variety of optimization strategies for vibration attenuation and damping may be employed in specific cases, depending on parameters such as the Q (or quality) factor attributable to each fluid end resonance. The fluid end response to excitation of a resonance may be represented graphically as, for example, a plot of amplitude vs. frequency. Such a Q response plot typically exhibits a single amplitude maximum at the local fluid end resonance frequency, with decreasing amplitude values at frequencies above and below the resonance. At an amplitude value about 0.707 times the maximum value (i.e., the half-power point), the amplitude plot corresponds not to a single frequency but to a bandwidth between upper and lower frequency values on either side of the local fluid end resonance. The quality factor Q is then estimated as the ratio of the resonance frequency to the bandwidth. (See, e.g., pp. 2-18, 2-19 of Harris ). (See also U.S. Pat. No. 7,113,876 B2, incorporated by reference).
Lower Q connotes the presence of more damping and a wider bandwidth (i.e., a relatively broader band of near-resonant frequencies). And higher Q connotes less damping and a narrower bandwidth (ideally, zero damping and a single resonant frequency). Since ideal fluid end resonances are not encountered in practice, optimization strategies typically include choice of the peak resonant frequency and Q of the tunable component in light of the peak resonant frequency and Q of the fluid end resonance of interest. Tunable component resonant frequencies identified herein as “similar” to fluid end or pump housing resonances are thus understood to lie generally in the frequency range indicated by the upper and lower frequency values of the relevant Q response half-power bandwidth.
In tunable components of the invention, choice of Q depends on both materials and structure, especially structural compliances and the properties of viscoelastic and/or shear-thickening materials present in the component(s). Further, the peak (or representative) frequency of a tunable component or a fluid end resonance may not be unambiguously obtainable. Thus, optimization of tunable component vibration damping may be an iterative empirical process and may not be characterized by a single-valued solution. Note also that tunable component resonant frequencies may be intentionally “detuned” (i.e., adjusted to slightly different values from nominal resonant or peak frequencies) in pursuit of an overall optimization strategy.
To minimize fluid end fatigue failures then, resonant frequencies of each tunable component of the invention are adjusted (i.e., tuned) using analytical and/or empirical frequency measures. Such measures are considered in light of the resonant frequencies of any other tunable component(s) present, and also in light of critical resonances of the fluid end or pump itself. The objective is optimal attenuation and damping of the most destructive portion(s) of valve-generated vibration. In each case, optimal vibration limitation will be dependent on the component's capacity to dissipate heat generated through hysteresis, friction and/or fluid turbulence. Thus, certain predetermined portion(s) of valve-closure energy are dissipated at one or more predetermined pump housing resonant (critical) frequencies.
Note that the critical frequencies proximate to a fluid end suction bore may differ, for example, from the critical frequencies proximate to the same fluid end's plunger bore due to the different constraints imposed by structures proximate the respective bores. Such differences are accounted for in the adjustment of tunable components, particularly tunable valve seats and tunable plunger seals.
What follows are descriptions of the structure and function of each tunable component that may be present in a tunable fluid end embodiment, the fluid end having at least one fluid end resonant frequency. Each tunable fluid end embodiment comprises at least one subassembly, and each subassembly comprises a housing (e.g., a fluid end housing or pump housing with appropriate bores). Within each housing's respective bores are a suction valve, a discharge valve, and a plunger or piston. When a tunable fluid end comprises multiple subassemblies (which is the general case), the respective subassembly housings are typically combined in a single fluid end housing. And at least one subassembly has at least one tunable component. In specific tunable fluid end embodiments, tunable components may be employed singly or in various combinations, depending on operative requirements.
The first tunable component described herein is a tunable check valve assembly (one being found in each tunable check valve). Installed in a fluid end for high pressure pumping, a tunable check valve assembly comprises at least one vibration damper or, in certain embodiments, a plurality of (radially-spaced) vibration dampers disposed in a valve body. Each vibration damper constitutes at least one tunable structural feature. Since the fluid end has at least a first fluid end resonance frequency, at least one vibration damper has (i.e., is tuned to) at least a first predetermined assembly resonant frequency similar to the first fluid end resonance (i.e., resonant frequency). If, for example, the fluid end has a second fluid end resonance frequency (a common occurrence), a single vibration damper and/or at least one of a plurality of vibration dampers may have (i.e., be tuned to) at least a second predetermined assembly resonant frequency similar to the second fluid end resonance frequency. In general, the specific manner of damping either one or a plurality of fluid end resonance frequencies with either one or a plurality (but not necessarily the same number) of vibration dampers is determined during the optimization process noted above.
Each of the sample embodiments of tunable check valve assemblies schematically illustrated herein comprises a check valve body having guide means (to maintain valve body alignment during longitudinal movement) and a peripheral valve seat interface. A peripheral groove spaced radially apart from a central reservoir is present in certain embodiments, and a viscoelastic element may be present in the peripheral groove (i.e., the groove damping element). In one such embodiment, the assembly's vibration dampers comprise a plurality of radially-spaced viscoelastic body elements disposed in the groove and reservoir, the viscoelastic groove element comprising a groove circular tubular area. In alternative embodiments, the viscoelastic reservoir (or central) damping element may be replaced by a central spring-mass damper. A viscoelastic central damper may be tuned, for example, via a flange centrally coupled to the valve body. A spring-mass central damper may be tuned, for example, by adjusting spring constant(s) and/or mass(es), and may also or additionally be tuned via the presence of a viscous or shear-thickening liquid in contact with one or more damper elements.
A reservoir (or central) damping element tuning frequency may be, as noted above, a first predetermined assembly resonant frequency similar to a first fluid end resonance. Analogously, the groove circular tubular area may comprise at least one shear thickening material providing the means to tune the groove damping element to at least a second predetermined assembly resonant frequency similar, for example, to either a first or second fluid end resonant frequency. The choice of tuning frequencies for the reservoir and groove damping elements is not fixed, but is based on a chosen optimization strategy for vibration damping in each fluid end.
Note that phase shifts inherent in the (nonlinear) operation of certain vibration dampers described herein create the potential for a plurality of resonant frequencies in a single vibration damper.
Note also that the longitudinal compliance of a tunable check valve assembly affects its rebound cycle time and thus influences vibration attenuation (i.e., downshifting or spectrum narrowing), which constitutes a form of tuning. Further, vibration dampers in alternative tunable check valve assembly embodiments may comprise spring-mass combinations having discrete mechanical components in addition to, or in place of, viscoelastic and/or shear-thickening components. An example of such a spring-mass combination within a valve body central reservoir is schematically illustrated herein.
The second tunable component described herein is a tunable valve seat, certain embodiments of which may be employed with a conventional valve body or, alternatively, may be combined with a tunable check valve assembly to form a tunable check valve. A tunable valve seat in a fluid end for high pressure pumping comprises a concave mating surface and/or a lateral support assembly longitudinally spaced apart from a mating surface. A lateral support assembly, when present, is adjustably secured (e.g., on a lateral support mounting surface) or otherwise coupled to the mating surface. A lateral support assembly is a tunable structural feature for resiliently coupling the tunable valve seat to a fluid end housing (and thus damping vibrations therein). That is, a lateral support assembly (and thus a tunable valve seat of which it is a part) has at least one tunable valve seat resonant frequency similar to at least one fluid end resonant frequency. Further, a lateral support assembly may be combined with a concave mating surface to provide two tunable structural features in a single tunable valve seat. Tunability of the concave mating surface inheres in its influence on rebound cycle time through the predetermined orientation and degree of curvature of the concave mating surface. Since it constitutes a tunable structural feature, a concave mating surface may be present in a tunable valve seat without a lateral support assembly. In the latter case, the concave mating surface will be longitudinally spaced apart from a pump housing interface surface, rather than a lateral support mounting surface (examples of these two surfaces are schematically illustrated herein). In light of a tunable valve seat's potential for embodying either one or two tunable structural features, a plurality of tunable valve seat resonant frequencies may characterize a single tunable valve seat, with the respective frequencies being chosen in light of the fluid end resonance(s) and the valve closure impulse vibration spectrum.
Flexibility in the choice of tunable seat resonant frequencies is guided by optimization criteria for vibration control in a tunable fluid end. Such criteria will suggest specifics of a lateral support assembly's structure and/or the concave curvature of a mating surface. For example, a support assembly's one or more suitably-secured circular viscoelastic support elements comprise a highly adaptable support assembly design for resiliently coupling the tunable valve seat to a fluid end housing (and thus damping vibrations therein). At least one such viscoelastic support element comprises a support circular tubular area. And each support circular tubular area, in turn, comprises at least one shear thickening material having (i.e., being tuned to a resonance frequency similar to) at least one seat resonant frequency that may be chosen to be similar to at least one fluid end resonant frequency. As above, the choice of tuning frequency or frequencies for a tunable valve seat is not fixed, but is based on a predetermined optimization strategy for vibration damping in each fluid end
Note that in addition to individual tuning of a tunable check valve assembly and a tunable valve seat (forming a tunable check valve), the combination may be tuned as a whole. For example, a tunable check valve in a fluid end for high pressure pumping may alternatively or additionally be tuned for spectrum narrowing by ensuring that its rebound characteristic frequency (i.e., a function of rebound cycle time) is less than at least one fluid end resonant frequency. In such a case, for example, at least one tunable valve seat resonant frequency may be similar to at least one fluid end resonant frequency.
The third tunable component described herein is a tunable radial array disposed in a valve body. In a schematically illustrated embodiment, the valve body comprises guide means, a peripheral valve seat interface, and a fenestrated peripheral groove spaced radially apart from a central reservoir. A viscoelastic body element disposed in the groove (the groove element) is coupled to a viscoelastic body element disposed in the reservoir (the reservoir element) by a plurality of viscoelastic radial tension members passing through a plurality of fenestrations in the peripheral groove. Each radial tension member comprises at least one polymer composite and functions to couple the groove element with the reservoir element, a baseline level of radial tension typically arising due to shrinkage of the viscoelastic elements during curing. The tensioned radial members, as schematically illustrated herein, assist anchoring of the coupled groove element firmly within the peripheral seal-retention groove without the use of adhesives and/or serrations as have been commonly used in anchoring conventional valve seals. Radial tension members also create a damped resilient linkage of groove element to reservoir element (analogous in function to a spring-mass damper linkage). This damped linkage can be “tuned” to approximate (i.e., have a resonance similar to) one or more critical frequencies via choice of the viscoelastic and/or composite materials in the damped linkage. Note that radial tension members also furnish a transverse preload force on the valve body, thereby altering longitudinal compliance, rebound cycle time (and thus rebound characteristic frequency), and vibration attenuation.
The fourth tunable component described herein is a tunable plunger seal comprising at least one lateral support assembly (analogous to that of a tunable valve seat) securably and sealingly positionable along a plunger. Typically, a lateral support assembly will be installed in a packing box (sometimes termed a stuffing box) or analogous structure. The tunable plunger seal's lateral support assembly is analogous in structure and function to that of a tunable valve seat, as are the tuning procedures described above.
Note that the predetermined resonant frequency of each circular viscoelastic element of a lateral support assembly is affected by the viscoelastic material(s) comprising it, as well as by constraints imposed via adjacent structures (e.g., portions of a valve seat, fluid end housing, packing box or plunger). The choice of a variety of viscoelastic element inclusions includes, for example, reinforcing fibers, circular and/or central cavities within the viscoelastic element, and distributions of special-purpose materials (e.g., shear-thickening materials and/or graphene) within or in association with one or more viscoelastic elements.
Note also that the lateral support assembly of either a tunable valve seat or a tunable plunger seal resiliently links the respective valve seat or plunger with adjacent portions of a fluid end housing, effectively creating a spring-mass damper coupled to the housing. This damped linkage can be “tuned” to approximate one or more critical frequencies via, e.g., shear-thickening materials in the respective circular tubular areas as described herein.
Analogous damped linkages between the housing and one or more auxiliary masses may be incorporated in tunable fluid end embodiments for supplemental vibration damping at one or more fluid end resonant frequencies (e.g., auxiliary tuned vibration absorbers and/or tuned-mass dampers). Additionally or alternatively, one or more damping surface layers (applied, e.g., as metallic, ceramic and/or metallic/ceramic coatings) may be employed for dissipating vibration and/or for modifying one or more fluid end resonant frequencies in pursuit of an overall optimization plan for fluid end vibration control. Such damping surface layers may be applied to fluid ends by various methods known to those skilled in the art. These methods may include, for example, cathodic arc, pulsed electron beam physical vapor deposition (EB-PVD), slurry deposition, electrolytic deposition, sol-gel deposition, spinning, thermal spray deposition such as high velocity oxy-fuel (HVOF), vacuum plasma spray (VPS) and air plasma spray (APS). The surface layers may be applied to the desired fluid end surfaces in their entirety or applied only to specified areas. Each surface layer may comprise a plurality of sublayers, at least one of which may comprise, for example, titanium, nickel, cobalt, iron, chromium, silicon, germanium, platinum, palladium and/or ruthenium. An additional sublayer may comprise, for example, aluminum, titanium, nickel, chromium, iron, platinum, palladium and/or ruthenium. One or more sublayers may also comprise, for example, metal oxide (e.g., zirconium oxide and/or aluminum oxide) and/or a nickel-based, cobalt-based or iron-based superalloy. (See e.g., U.S. Pat. No. 8,591,196 B2, incorporated by reference).
Further as noted above, constraints on viscoelastic elements due to adjacent structures can function as a control mechanism by altering tunable component resonant frequencies. Examples of such effects are seen in embodiments comprising an adjustable flange coupled to the valve body for imposing a predetermined shear preload by further constraining a viscoelastic element already partially constrained in the reservoir. One or more tunable check valve assembly resonant frequencies may thus be predictably altered. Consequently, the associated valve-generated vibration spectrum transmissible to a housing may be narrowed, and its amplitude reduced, through hysteresis loss of valve-closure impulse energy at each predetermined assembly resonant frequency (e.g., by conversion of valve-closure impulse energy to heat energy, rather than vibration energy).
In addition to composite viscoelastic element inclusions, control mechanisms for alteration of tunable component resonant frequencies further include the number, size and spacing of peripheral groove fenestrations. When fenestrations are present, they increase valve assembly responsiveness to longitudinal compressive force while stabilizing viscoelastic and/or composite peripheral groove elements. Such responsiveness includes, but is not limited to, variations in the width of the peripheral groove which facilitate “tuning” of the groove together with its viscoelastic element(s).
Briefly summarizing, each embodiment of a tunable component attenuates and/or damps valve-generated vibration at one or more fluid end critical frequencies. The transmitted vibration spectrum is thus narrowed and its amplitude reduced through conversion and dissipation of valve-closure impulse (kinetic) energy as heat. One or more tunable component structural features are thus tunable to one or more frequencies similar to at least one fluid end resonant frequency to facilitate redistribution/dissipation of impulse kinetic energy, following its conversion to heat energy.
Continuing in greater detail, valve-closure impulse energy conversion in a tunable component primarily arises from hysteresis loss (e.g., heat loss) in viscoelastic and/or discrete-mechanical elements, but may also occur in related structures (e.g., in the valve body itself). Hysteresis loss in a particular structural feature is related in-part to that feature's compliance (i.e., the feature's structural distortion as a function of applied force).
Compliance arises in structural features of a tunable component, such as one or more viscoelastic elements, plus at least one other compliant portion. For example, a tunable check valve body distorts substantially elastically under the influence of a closing energy impulse, and its associated viscoelastic element(s) simultaneously experience(s) shear stress in accommodating the distortion. The resulting viscoelastic shear strain, however, is at least partially time-delayed. And the time delay introduces a phase-shift useful in damping valve-generated vibration (i.e., reducing its amplitude). Analogous time-delay phase shift occurs in a mass-spring damper comprising discrete mechanical elements.
In addition to vibration damping, a complementary function of a tunable component is narrowing of the spectrum of valve-generated vibration. Spectrum narrowing (or vibration down-shifting) is associated with compliance in the form of deformation over time in response to an applied force. Since each instance of compliance takes place over a finite time interval, the duration of a closing energy impulse is effectively increased (and the vibration spectrum correspondingly narrowed) as a function of compliance.
A narrowed valve-generated vibration spectrum, in turn, is less likely to generate destructive sympathetic vibration in adjacent regions of a fluid end housing. For this reason, compliant portions of a valve body are designed to elastically distort under the influence of the closing energy impulse (in contrast to earlier substantially-rigid valve designs). Compliance-related distortions are prominent in, but not limited to, the shapes of both the (peripheral) groove and the (relatively central) reservoir. Viscoelastic elements in the groove and reservoir resist (and therefore slow) the distortions, thus tending to beneficially increase the closing energy impulse's duration while narrowing the corresponding vibration spectrum.
Distortions of both groove and reservoir viscoelastic body elements result in viscoelastic stress and its associated time-dependent strain. But the mechanisms differ in the underlying distortions. In a peripheral groove, for example, proximal and distal groove walls respond differently to longitudinal compressive force on the tunable check valve assembly. They generally move out-of-phase longitudinally, thereby imposing time-varying compressive loads on the groove viscoelastic element. Thus the shape of the groove (and the overall compliance of the groove and its viscoelastic element) changes with time, making the groove as a whole responsive to longitudinal force on the assembly.
Peripheral groove fenestrations increase groove responsiveness to longitudinal force. As schematically illustrated herein, fenestrations increase groove responsiveness by changing the coupling of the proximal groove wall to the remainder of the valve body (see Detailed Description herein).
In the reservoir, in contrast, responsiveness to longitudinal force may be modulated by an adjustable preload flange centrally coupled to the valve body. The flange imposes a shear preload on the viscoelastic reservoir element (i.e., shear in addition to that imposed by the reservoir itself and/or by the closing energy impulse acting on the viscoelastic element via the pumped fluid). The amount of shear preload varies with the (adjustable) radial and longitudinal positions of the flange within the reservoir. The overall compliance and resonances of the reservoir and its viscoelastic element may be predictably altered by such a shear preload, which is imposed by the flange's partial constraint of the viscoelastic reservoir element. Note that when reservoir and groove viscoelastic body elements are coupled by a plurality of radial tension members, as in a tunable radial array, the radial tension members lying in groove wall fenestrations allow transmission of shear stress between the groove and reservoir viscoelastic elements.
Thus, in tunable radial array embodiments, at least a first predetermined resonant frequency may substantially replicate a (similar) pump housing resonant frequency via adjustment of shear preload on the reservoir viscoelastic element. The plurality of fenestration elements coupling the reservoir element with the groove element may have at least a second predetermined resonant frequency related to the first predetermined resonant frequency and optionally achieved through choice of tensile strength of the radial tension members (i.e., fenestration elements). And at least a third predetermined resonant frequency related to the first and second predetermined resonant frequencies may be achieved through choice of at least one shear thickening material in circular tubular areas of the groove viscoelastic element and/or one or more support circular tubular areas.
Note that any structural feature of a tunable check valve assembly or tunable radial array (e.g., a valve body or a viscoelastic element) may be supplemented with one or more reinforcement components to form a composite feature. Reinforcement materials tend to alter compliance and may comprise, for example, a flexible fibrous material (e.g., carbon nanotubes, graphene), a shear-thickening material, and/or other materials as described herein.
As noted above, alterations in compliance (with its associated hysteresis loss) contribute to predetermined vibration spectrum narrowing. Such compliance changes (i.e., changes in displacement as a function of force) may be achieved through adjustment of constraint. Constraint, in turn, may be achieved, e.g., via compression applied substantially longitudinally by the adjustable preload flange to a constrained area of the viscoelastic reservoir element. In embodiments comprising a central longitudinal guide stem, the constrained area may be annular. And adjacent to such an annular constrained area may be another annular area of the viscoelastic reservoir element which is not in contact with the adjustable preload flange (i.e., an annular unconstrained area). This annular unconstrained area is typically open to pumped fluid pressure.
Preload flange adjustment may change the longitudinal compliance of the tunable check valve assembly by changing the effective flange radius and/or the longitudinal position of the flange as it constrains the viscoelastic reservoir element. Effective flange radius will generally exceed actual flange radius due to slowing of (viscous) viscoelastic flow near the flange edge. This allows tuning of the check valve assembly to a first predetermined assembly resonant frequency for maximizing hysteresis loss. Stated another way, by constraining a vibrating structure (e.g., an area of the viscoelastic reservoir element), it is possible to force the vibrational energy into different modes and/or frequencies. See, e.g., U.S. Pat. No. 4,181,027, incorporated by reference.
The invention thus includes means for constraining one or more separate viscoelastic elements of a valve assembly, as well as means for constraining a plurality of areas of a single viscoelastic element. And such constraint may be substantially constant or time-varying, with correspondingly different effects on resonant frequencies. Peripherally, time-varying viscoelastic element constraint may be provided by out-of-phase longitudinal movement of peripheral groove walls. In contrast, time-varying viscoelastic element constraint may be applied centrally by a flange coupled to the valve body.
Flange radial adjustment is facilitated, e.g., via a choice among effective flange radii and/or flange periphery configurations (e.g., cylindrical or non-cylindrical). Flange longitudinal movement may be adjusted, for example, by (1) use of mechanical screws or springs, (2) actuation via pneumatic, hydraulic or electrostrictive transducers, or (3) heat-mediated expansion or contraction. Flange longitudinal movement may thus be designed to be responsive to operational pump parameters such as temperature, acceleration, or pressure. Since pump housing resonant frequencies may also respond to such parameters, tunable check valve assemblies and tunable check valves may be made at least partially self-adjusting (i.e., operationally adaptive or auto-adjusting) so as to change their energy-absorbing and spectrum-narrowing characteristics to optimally extend pump service life.
Note that in certain embodiments, the preload flange may comprise a substantially cylindrical periphery associated with substantially longitudinal shear. Other embodiments may comprise a non-cylindrical periphery for facilitating annular shear preload having both longitudinal and transverse components associated with viscoelastic flow past the flange. Such an invention embodiment provides for damping of transverse as well as longitudinal vibration. Transverse vibration may originate, for example, when slight valve body misalignment with a valve seat causes abrupt lateral valve body movement during valve closing.
Note also that one or more flanges may or may not be longitudinally fixed to the guide stem for achieving one or more predetermined assembly resonant frequencies.
And note further that the first predetermined assembly resonant frequency of greatest interest, of course, will typically approximate one of the natural resonances of the pump and/or pump housing. Complementary hysteresis loss and vibration spectrum narrowing may be added via a second predetermined assembly resonant frequency achieved via the viscoelastic groove element (which may comprise at least one circular tubular area containing at least one shear-thickening material). The time-varying viscosity of the shear-thickening material(s), if present, furnishes a non-linear constraint of the vibrating structure analogous in part to that provided by the adjustable preload flange. The result is a predetermined shift of the tunable check valve assembly's vibrating mode analogous to that described above.
Note that when a nonlinear system is driven by a periodic function, such as can occur with harmonic excitation, chaotic dynamic behavior is possible. Depending on the nature of the nonlinear system, as well as the frequency and amplitude of the driving force, the chaotic behavior may comprise periodic oscillations, almost periodic oscillations, and/or coexisting (multistable) periodic oscillations and nonperiodic-nonstable trajectories (see Harris , p. 4-28).
In addition to a shift in the tunable check valve assembly's vibrating mode, incorporation of at least one circular tubular area containing at least one shear-thickening material within the viscoelastic groove element increases impulse duration by slightly slowing valve closure due to reinforcement of the viscoelastic groove element. Increased impulse duration, in turn, narrows the closing energy impulse vibration spectrum. And shear-thickening material itself is effectively constrained by its circular location within the viscoelastic groove element(s).
The shear-thickening material (sometimes termed dilatant material) is relatively stiff near the time of impact and relatively fluid at other times. Since the viscoelastic groove element strikes a valve seat before the valve body, complete valve closure is slightly delayed by the shear-thickening action. The delay effectively increases the valve-closure energy impulse's duration, which means that vibration which is transmitted from the tunable check valve assembly to its (optionally tunable) valve seat and pump housing has a relatively narrower spectrum and is less likely to excite vibrations that predispose a pump housing to early fatigue failure. The degree of spectrum narrowing can be tuned to minimize excitation of known pump housing resonances by appropriate choice of the shear-thickening material. Such vibration attenuation, and the associated reductions in metal fatigue and corrosion susceptibility, are especially beneficial in cases where the fluid being pumped is corrosive.
The functions of the viscoelastic groove element, with its circular shear-thickening material, are thus seen to include those of a conventional valve seal as well as those of a tunable vibration attenuator and a tunable vibration damper. See, e.g., U.S. Pat. No. 6,026,776, incorporated by reference. Further, the viscoelastic reservoir element, functioning with a predetermined annular shear preload provided via an adjustable preload flange, can dissipate an additional portion of valve-closure impulse energy as heat while also attenuating and damping vibration. And viscoelastic fenestration elements, when present, may contribute further to hysteresis loss as they elastically retain the groove element in the seal-retention groove via coupling to the reservoir element. Overall hysteresis loss in the viscoelastic elements combines with hysteresis loss in the valve body to selectively reduce the bandwidth, amplitude and duration of vibrations that the closing impulse energy would otherwise tend to excite in the valve and/or pump housing.
Examples of mechanisms for such selective vibration reductions are seen in the interactions of the viscoelastic reservoir element with the adjustable preload flange. The interactions contribute to hysteresis loss in a tunable check valve assembly by, for example, creating what has been termed shear damping (see, e.g., U.S. Pat. No. 5,670,006, incorporated by reference). With the preload flange adjustably fixed centrally to the check valve body (e.g., fixed to a central guide stem), valve-closure impact causes both the preload flange and guide stem to temporarily move distally with respect to the (peripheral) valve seat interface (i.e., the valve body experiences a concave-shaped flexure). The impact energy associated with valve closure causes temporary deformation of the check valve body; that is, the valve body periphery (e.g., the valve seat interface) is stopped by contact with a valve seat while the central portion of the valve body continues (under inertial forces and pumped-fluid pressure) to elastically move distally. Thus, the annular constrained area of the viscoelastic reservoir element (shown constrained by the preload flange in the schematic illustrations herein) moves substantially countercurrent (i.e., in shear) relative to the annular unconstrained area (shown radially farther from the guide stem and peripheral to the preload flange). That is, relative distal movement of the preload flange thus tends to extrude the (more peripheral) annular unconstrained area proximally. Energy lost (i.e., dissipated) in connection with the resulting shear strain in the viscoelastic element is subtracted from the total closing impulse energy otherwise available to excite destructive flow-induced vibration resonances in a valve, valve seat and/or pump housing. See, e.g., U.S. Pat. No. 5,158,162, incorporated by reference.
Note that in viscoelastic and shear-thickening materials, the relationship between stress and strain (and thus the effect of material constraint on resonant frequency) is generally time-dependent and non-linear. So a desired degree of non-linearity in “tuning” may be predetermined by appropriate choice of viscoelastic and shear-thickening materials in a tunable check valve assembly or tunable check valve.
Another aspect of the interaction of the viscoelastic reservoir element with an adjustable preload flange contributes to vibration damping and/or absorption in a tunable check valve assembly. As a result of compliance in the viscoelastic element, longitudinal movement of a guide stem and a coupled preload flange results in a phase lag as shear stress develops within the viscoelastic material. This is analogous to the phase lag seen in the outer ring movement in an automotive torsional vibration damper or the antiphase movement of small masses in an automotive pendulum vibration damper. See, e.g., the '776 patent cited above. Adjusting the shear preload flange as described above effectively changes the tunable check valve assembly's compliance and thus the degree of phase lag. One may thus, in one or more limited operational ranges, tune viscoelastic element preload to achieve effective vibration damping plus dynamic vibration absorption at specific frequencies of interest (e.g., pump housing resonant frequencies).
To achieve the desired hysteresis loss associated with attenuation and vibration damping effects described herein, different viscoelastic and/or composite elements may be constructed to have specific elastic and/or viscoelastic properties. Note that the term elastic herein implies substantial characterization by a storage modulus, whereas the term viscoelastic herein implies substantial characterization by a storage modulus and a loss modulus. See, e.g., the '006 patent cited above.
Specific desired properties for each viscoelastic element arise from a design concept requiring coordinated functions depending on the location of each element. The viscoelastic reservoir element affects hysteresis associated with longitudinal compliance of the tunable check valve assembly because it viscoelasticly accommodates longitudinal deformation of the valve body toward a concave shape. Hysteresis in the viscoelastic groove element (related, e.g., to its valve seal and vibration damping functions) and the valve body itself further reduces closing energy impulse amplitude through dissipation of portions of closing impulse energy as heat.
Elastic longitudinal compliance of a tunable check valve assembly results in part from elastic properties of the materials comprising the tunable check valve assembly. Such elastic properties may be achieved through use of composites comprising reinforcement materials as, for example, in an elastic valve body comprising steel, carbon fiber reinforced polymer, carbon nanotube/graphene reinforced polymer, and/or carbon nanotube/graphene reinforced metal matrix. The polymer may comprise a polyaryletherketone (PAEK), for example, polyetheretherketone (PEEK). See, e.g., U.S. Pat. No. 7,847,057 B2, incorporated by reference.
Note that the description herein of valve body flexure as concave-shaped refers to a view from the proximal or high-pressure side of the valve body. Such flexure is substantially elastic and may be associated with slight circular rotation (i.e., a circular rolling contact) of the valve body's valve seat interface with the valve seat itself. When the degree of rolling contact is sufficient to justify conversion of the valve seat interface from a conventional frusto-conical shape to a convex curved shape (which may include, e.g., circular, elliptic and/or parabolic portions), a curved concave tunable valve seat mating surface may be used. In such cases, the valve seat interface has correspondingly greater curvature than the concave tunable valve seat mating surface (see Detailed Description herein). Such rolling contact, when present, augments elastic formation of the concave valve body flexure on the pump pressure stroke, reversing the process on the suction stroke.
The circular rolling contact described herein may be visualized by considering the behavior of the convex valve seat interface as the valve body experiences concave flexure (i.e., the transformation from a relatively flat shape to a concave shape). During such flexure the periphery of the valve seat interface rotates slightly inwardly and translates slightly proximally (relative to the valve body's center of gravity) to become the proximal rim of the concave-shaped flexure.
While substantially elastic, each such valve body flexure is associated with energy loss from the closing energy impulse due to hysteresis in the valve body. Frictional heat loss (and any wear secondary to friction) associated with any circular rolling contact of the convex valve seat interface with the concave tunable valve seat mating surface is intentionally relatively low. Thus, the rolling action, when present, minimizes wear that might otherwise be associated with substantially sliding contact of these surfaces. Further, when rolling contact between valve body and tunable valve seat is present during both longitudinal valve body flexure and the elastic rebound which follows, trapping of particulate matter from the pumped fluid between the rolling surfaces tends to be minimized.
Since rolling contact takes place over a finite time interval, it also assists in smoothly redirecting pumped fluid momentum laterally and proximally. Forces due to oppositely directed radial components of the resultant fluid flow tend to cancel, and energy lost in pumped fluid turbulence is subtracted (as heat) from that of the valve-closure energy impulse, thus decreasing both its amplitude and the amplitude of associated vibration.
In addition to the above described energy dissipation (associated with hysteresis secondary to valve body flexure), hysteresis loss will also occur during pressure-induced movements of the viscoelastic groove element (in association with the valve seal function). Note that pumped fluid pressure acting on a valve comprising an embodiment of the invention's tunable check valve assembly may hydraulically pressurize substantially all of the viscoelastic elements in a tunable check valve assembly. Although polymers suitable for use in the viscoelastic elements generally are relatively stiff at room ambient pressures and temperatures, the higher pressures and temperatures experienced during pump pressure strokes tend to cause even relatively stiff polymers to behave like fluids which can transmit pressure hydraulically. Thus, a viscoelastic element in a peripheral seal-retention groove is periodically hydraulically pressurized, thereby increasing its sealing function during the high-pressure portion of the pump cycle. Hydraulic pressurization of the same viscoelastic element is reduced during the low-pressure portion of the pump cycle when the sealing function is not needed.
Because of the above-described energy loss and the time required for valve body longitudinal deformation to take place, with the associated dissipation of closing impulse energy described above, a valve-closure energy impulse applied to a tunable check valve assembly or tunable radial array is relatively lower in amplitude and longer in duration (e.g., secondary to having a longer rise time) than an analogous valve-closure energy impulse applied to a conventionally stiff valve body which closes on a conventional frusto-conical valve seat. The combination of lower amplitude and increased duration of the valve-closure energy impulse results in a narrowed characteristic vibration bandwidth having reduced potential for induction of damaging resonances in the valve, valve seat, and adjacent portions of the pump housing. See, e.g., the above-cited '242 patent.
Note that in describing the fluid-like behavior of certain polymers herein under elevated heat and pressure, the term “polymer” includes relatively homogenous materials (e.g., a single-species fluid polymer) as well as composites and combination materials containing one or more of such relatively homogenous materials plus finely divided particulate matter (e.g., nanoparticles) and/or other dispersed species (e.g., species in colloidal suspension, graphene) to improve heat scavenging and/or other properties. See, e.g., U.S. Pat. No. 6,432,320 B1, incorporated by reference.
In addition to heat scavenging, damping is a function of the viscoelastic elements in various embodiments of the invention. Optimal damping is associated with relatively high storage modulus and loss tangent values, and is obtained over various temperature ranges in multicomponent systems described as having macroscopically phase-separated morphology, microheterogeneous morphology, and/or at least one interpenetrating polymer network. See, e.g., the above-cited '006 patent and U.S. Pat. Nos. 5,091,455; 5,238,744; 6,331,578 B1; and 7,429,220 B2, all incorporated by reference.
Summarizing salient points of the above description, recall that vibration attenuation and damping in a tunable check valve assembly, tunable valve seat, tunable plunger seal, or tunable radial array of the invention operate via four interacting mechanisms. First, impulse amplitude is reduced by converting a portion of total closing impulse energy to heat (e.g., via hysteresis and fluid turbulence), which is then ultimately rejected to the check valve body surroundings (e.g., the pumped fluid). Each such reduction of impulse amplitude means lower amplitudes in the characteristic vibration spectrum transmitted to the pump housing.
Second, the closing energy impulse as sensed at the valve seat is reshaped in part by lengthening the rebound cycle time (estimated as the total time associated with peripheral valve seal compression, concave valve body flexure and elastic rebound). Such reshaping may in general be accomplished using mechanical/hydraulic/pneumatic analogs of electronic wave-shaping techniques. In particular, lengthened rebound cycle time is substantially influenced by the valve body's increased longitudinal compliance associated with the rolling contact/seal and concave valve body flexure described herein between valve body and valve seat. The units of lengthened cycle times are seconds, so their inverse functions have dimensions of per second (or 1/sec), the same dimensions as frequency. Thus, as noted above, the inverse function is termed herein rebound characteristic frequency.
Lowered rebound characteristic frequency (i.e., increased rebound cycle time) corresponds to slower rebound, with a corresponding reduction of the impulse's characteristic bandwidth due to loss of higher frequency content. This condition is created during impulse hammer testing by adding to hammer head inertia and by use of softer impact tips (e.g., plastic tips instead of the metal tips used when higher frequency excitation is desired). In contrast, tunable check valve assemblies and tunable radial arrays achieve bandwidth narrowing (and thus reduction of the damage potential of induced higher-frequency vibrations) at least in part through increased longitudinal compliance. In other words, bandwidth narrowing is achieved in embodiments of the invention through an increase of the effective impulse duration (as by, e.g., slowing the impulse's rise time and/or fall time as the valve assembly's components flex and relax over a finite time interval).
Third, induced vibration resonances of the tunable check valve assembly, tunable valve seat, and/or other tunable components are effectively damped by interactions generating structural hysteresis loss. Associated fluid turbulence further assists in dissipating heat energy via the pumped fluid.
And fourth, the potential for excitation of damaging resonances in pump vibration induced by a closing energy impulse is further reduced through narrowing of the impulse's characteristic vibration bandwidth by increasing the check valve body's effective inertia without increasing its actual mass. Such an increase of effective inertia is possible because a portion of pumped fluid moves with the valve body as it flexes and/or longitudinally compresses. The mass of this portion of pumped fluid is effectively added to the valve body's mass during the period of flexure/relaxation, thereby increasing the valve body's effective inertia to create a low-pass filter effect (i.e., tending to block higher frequencies in the manner of an engine mount).
To increase understanding of the invention, certain aspects of tunable components (e.g., alternate embodiments and multiple functions of structural features) are considered in greater detail. Alternate embodiments are available, for example, in guide means known to those skilled in the art for maintaining valve body alignment within a (suction or discharge) bore. Guide means thus include, e.g., a central guide stem and/or a full-open or wing-guided design (i.e., having a distal crow-foot guide).
Similarly, alteration of a viscoelastic element's vibration pattern(s) in a tunable fluid end is addressed (i.e., tuned) via adjustable and/or time-varying constraints. Magnitude and timing of the constraints are determined in part by closing-impulse-related distortions and/or the associated vibration. For example, a viscoelastic reservoir (or central) element is at least partially constrained as it is disposed in the central annular reservoir, an unconstrained area optionally being open to pumped fluid pressure. That is, the viscoelastic reservoir element is at least partially constrained by relative movement of the interior surface(s) of the (optionally annular) reservoir, and further constrained by one or more structures (e.g., flanges) coupled to such surface(s). Analogously, a viscoelastic groove (or peripheral) element is at least partially constrained by relative movement of the groove walls, and further constrained by shear-thickening material within one or more circular tubular areas of the element (any of which may comprise a plurality of lumens).
Since the magnitude and timing of closing-impulse-related distortions are directly related to each closing energy impulse, the tunable fluid end's overall response is adaptive to changing pump operating pressures and speeds on a stroke-by-stroke basis. So for each set of operating parameters (i.e., for each pressure/suction stroke cycle), one or more of the constrained viscoelastic elements has at least a first predetermined assembly resonant frequency substantially similar to an instantaneous pump resonant frequency (e.g., a resonant frequency measured or estimated proximate the suction valve seat deck). And for optimal damping, one or more of the constrained viscoelastic elements may have, for example, at least a second predetermined assembly resonant frequency similar to the first predetermined assembly resonant frequency.
Note that the adaptive behavior of viscoelastic elements is beneficially designed to complement both the time-varying behavior of valves generating vibration with each punp pressure stroke, and the time-varying response of the fluid end as a whole to that vibration.
Note also that a tunable check valve assembly and/or tunable valve seat analogous to those designed for use in a tunable suction check valve may be incorporated in a tunable discharge check valve as well. Either a tunable suction check valve or a tunable discharge check valve or both may be installed in a pump fluid end housing. Additionally, one or more other tunable components may be combined with tunable suction and/or discharge check valves. A pump housing resonant frequency may be chosen as substantially equal to a first predetermined resonant frequency of each of the tunable components installed, or of any combination of the installed tunable components. Or the predetermined component resonant frequencies may be tuned to approximate different pump housing resonant frequencies as determined for optimal vibration damping.
For increased flexibility in accomplishing the above tuning, fenestrations may be present in the groove wall to accommodate radial tension members. At least a portion of each fenestration may have a transverse area which increases with decreasing radial distance to said longitudinal axis. That is, each fenestration flares to greater transverse areas in portions closer to the longitudinal axis, relative to the transverse areas of portions of the fenestration which are more distant from the longitudinal axis. Thus, a flared fenestration is partly analogous to a conventionally flared tube, with possible differences arising from the facts that (1) fenestrations are not limited to circular cross-sections, and (2) the degree of flare may differ in different portions of a fenestration. Such flares assist in stabilizing a viscoelastic groove element via a plurality of radial tension members.
Note that in addition to the example alternate embodiments described herein, still other alternative invention embodiments exist, including valves, pump housings and pumps comprising one or more of the example embodiments or equivalents thereof. Additionally, use of a variety of fabrication techniques known to those skilled in the art may lead to embodiments differing in detail from those schematically illustrated herein. For example, internal valve body spaces may be formed during fabrication by welding (e.g., inertial welding or laser welding) valve body portions together as in the above-cited '837 patent, or by separately machining such spaces with separate coverings. Valve body fabrication may also be by rapid-prototyping (i.e., layer-wise) techniques. See, e.g., the above-cited '057 patent. Viscoelastic elements may be cast and cured separately or in place in a valve body as described herein. See, e.g., U.S. Pat. No. 7,513,483 B1, incorporated by reference.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic 3-dimensional view of a partially sectioned tunable check valve assembly/tunable radial array embodiment showing how an adjustable preload flange constrains an area of the viscoelastic reservoir element as described herein.
FIG. 2 includes a schematic 3-dimensional exploded view of the tunable check valve assembly/tunable radial array embodiment of FIG. 1 showing viscoelastic body elements, the valve body, and the adjustable preload flange.
FIG. 3 is a schematic 3-dimensional partially-sectioned view of viscoelastic reservoir, groove and fenestration elements (i.e., viscoelastic body elements) of FIGS. 1 and 2 showing the constrained area of the reservoir element where it contacts an adjustable preload flange, as well as an adjacent unconstrained area.
FIG. 4 is a schematic 3-dimensional partially-sectioned view of two check valve bodies with an adjustable preload flange located at different longitudinal positions on a central guide stem.
FIG. 5 is a schematic 3-dimensional instantaneous partially-sectioned view of shear-thickening material which would, e.g., substantially fill a circular tubular area in a viscoelastic groove element, a support circular tubular area of a tunable valve seat, a tunable plunger seal, or a tunable resilient circumferential seal.
FIG. 6 is a schematic illustration of an exploded partially-sectioned 2-dimensional view of major components of a pump fluid end subassembly, together with brief explanatory comments on component functions. The schematically-illustrated subassembly comprises a pumping chamber within a subassembly pump housing, the pumping chamber being in fluid communication with a suction bore, a discharge bore, and a piston/plunger bore. Schematic representations of a suction check valve, a discharge check valve, and a piston/plunger are shown in their respective bores, together with brief annotations and graphical aids outlining the structural relationships.
FIG. 7 is a schematic illustration of two views of an exploded partially-sectioned 3-dimensional view of a valve body and tunable valve seat embodiment. Curved longitudinal section edges of the valve body's convex valve seat interface and corresponding concave mating portions of the tunable valve seat are shown schematically in a detail breakout view to aid description herein of a rolling valve seal along a circular line. A tunable (suction or discharge) check valve embodiment of the invention may comprise a combination of a tunable check valve assembly/tunable radial array (see, e.g., FIGS. 1 and 2 ) and a tunable valve seat (see, e.g., FIGS. 7 and 8 ).
FIG. 8 is a schematic 3-dimensional exploded and partially-sectioned view of a tunable valve seat embodiment showing a concave mating surface longitudinally spaced apart from a lateral support mounting surface, and an adjustable lateral support assembly comprising first and second securable end spacers in combination with a plurality of circular viscoelastic support elements, each support element comprising a support circular tubular area.
FIG. 9 is a schematic 3-dimensional exploded view of a partially sectioned tunable check valve assembly embodiment. A dilatant (i.e., shear-thickening) liquid is schematically shown being added to a check valve body's internal cavity, the cavity being shown as enclosing a tuned vibration damper comprising discrete mechanical elements (e.g., a mass and three springs).
FIG. 10 is a schematic 3-dimensional exploded view of a tunable check valve embodiment comprising the tunable check valve assembly of FIG. 9 together with a tunable valve seat, the tunable check valve embodiment including structures to facilitate a rolling seal along a circular line between the valve body's valve seat interface and the tunable valve seat's mating surface. Note that the (convex) valve seat interface has correspondingly greater curvature than the (concave) mating surface, and the mating surface has correspondingly less curvature than the valve seat interface.
FIG. 11 is a schematic 3-dimensional exploded view of an alternate tunable check valve embodiment comprising the tunable check valve assembly of FIG. 9 together with a tunable valve seat, the tunable check valve embodiment including structures to facilitate a rolling seal along a circular line between the check valve body's peripheral valve seat interface and the tunable valve seat's mating surface. An adjustable lateral support assembly is shown with the tunable valve seat, the assembly comprising first and second securable end spacers in combination with a plurality of circular viscoelastic support elements, each support element shown in a detail breakout view as comprising a support circular tubular area.
FIG. 12 illustrates two schematic 3-dimensional views of an alternate tunable check valve assembly embodiment comprising a plurality of radially-spaced vibration dampers disposed in a valve body having a peripheral seal. Each vibration damper comprises a circular tubular area, and at least one vibration damper is tunable via a fluid medium (shown schematically being added) in a tubular area.
FIG. 13 is a schematic 3-dimensional exploded view of the alternate tunable check valve assembly embodiment of FIG. 12 . Detail breakout views include the peripheral seal's medial flange and the flange body's corresponding flange channel. An instantaneous schematic view of the fluid medium in the peripheral seal's circular tubular area is shown separately.
FIG. 14 illustrates a partial schematic 3-dimensional view of an alternate tunable check valve embodiment comprising the valve body of FIGS. 12 and 13 , together with a tunable valve seat. A detail breakout view shows that the valve seat interface has correspondingly greater curvature than the mating surface. The mating surface has correspondingly less curvature than the valve seat interface to facilitate a rolling seal along a circular line between the valve body's valve seat interface and the tunable valve seat's mating surface.
FIG. 15 illustrates a partial schematic 3-dimensional view of a tunable hydraulic stimulator embodiment comprising a driver element and a hammer element in a hollow cylindrical housing, one end of the housing being closed by a fluid interface, and the fluid interface comprising a MEMS accelerometer.
FIG. 16 illustrates a partial schematic 3-dimensional exploded view of the tunable hydraulic stimulator embodiment of FIG. 15 , a first electrical cable being shown to schematically indicate a feedback path (for an accelerometer signal) from the accelerometer to the driver element. A second electrical cable is shown to schematically indicate an interconnection path for, e.g., communication with one or more additional stimulators and/or associated equipment.
DETAILED DESCRIPTION
Tunable equipment associated with high-pressure well-stimulation systems comprises a first family of tunable hydraulic stimulators (plus associated controllers, power supplies, etc.), together with a second family comprising a plurality of fluid end embodiments. Each such embodiment has at least one installed tunable component chosen from: tunable check valve assemblies, tunable valve seats, tunable radial arrays and/or tunable plunger seals.
The above two tunable equipment families have strikingly different operational characteristics. In the first family, tunable hydraulic stimulators operate down-hole, generating and transmitting vibration tailored to enhance stimulation of geologic materials for higher hydrocarbon yields. In contrast, fluid ends of the second family have one or more installed tunable components which facilitate selective attenuation of valve-generated vibration at or near its source to reduce fluid end fatigue failures. Structures related to the two families are shown in FIGS. 1-16 and described below.
FIGS. 1-14 relate generally to the above second tunable equipment family. They schematically illustrate how adding tunable valve seats, tunable radial arrays and/or plunger seals to tunable check valve assemblies in a fluid end further facilitates optimal damping and/or selective attenuation of vibration at one or more predetermined (and frequently-localized) fluid end resonant frequencies. Optimized vibration attenuation (via, e.g., optimized fluid end damping) is provided by altering resonant frequencies in each tunable component in relation to one or more (measured or estimated) fluid end resonant frequencies and/or tunable component resonant frequencies.
A tunable (suction or discharge) check valve of the invention may comprise, for example, a combination of a tunable check valve assembly/tunable radial array 99 (see, e.g., FIG. 1 ) and a tunable valve seat 20 or a tunable valve seat 389 (see, e.g., FIGS. 7 and 11 ). Details of the structure and functions of each component are provided herein both separately and as combined with other components to obtain synergistic benefits contributing to longer pump service life.
FIGS. 1 and 2 schematically illustrate an invention embodiment of a tunable check valve assembly/tunable radial array 99 substantially symmetrical about a longitudinal axis. Illustrated components include a valve body 10 , an adjustable preload flange 30 , and a plurality of viscoelastic body elements 50 . Check valve body 10 , in turn, comprises a peripheral groove 12 (see FIG. 2 ) spaced apart by an annular (central) reservoir 16 from a longitudinal guide stem 14 , groove 12 being responsive to longitudinal compressive force. A plurality of viscoelastic body elements 50 comprises an annular (central) reservoir element 52 coupled to a (peripheral) groove element 54 by a plurality of (optional) radial fenestration elements 56 (in fenestrations 18 ) to form a tunable radial array. Groove element 54 functions as a vibration damper and valve seal, comprising at least one circular tubular area 58 .
Responsiveness of groove 12 to longitudinal compressive force is characterized in part by damping of groove wall 11 / 13 / 15 vibrations. Such damping is due in part to out-of-phase vibrations in proximal groove wall 13 and distal groove wall 11 which are induced by longitudinal compressive force. Such out-of-phase vibrations will cause various groove-related dimensions to vary with longitudinal compressive force, thereby indicating the responsiveness of groove 12 to such force (see, for example, the dimension labeled A in FIG. 2 ). Each phase shift, in turn, is associated with differences in the coupling of proximal groove wall 13 to guide stem 14 (indirectly via longitudinal groove wall 15 and radial reservoir floor 19 ) and the coupling of distal groove wall 11 to guide stem 14 (directly via radial reservoir floor 19 ). Note that longitudinal groove wall 15 may comprise fenestrations 18 , thereby increasing the responsiveness of groove 12 to longitudinal compressive force on tunable check valve assembly 99 .
Referring to FIGS. 1-3 , adjustable preload flange 30 extends radially from guide stem 14 (toward peripheral reservoir wall 17 ) over, for example, about 20% to about 80% of viscoelastic reservoir element 52 (see FIG. 3 ). Adjustable preload flange 30 thus imposes an adjustable annular shear preload over an annular constrained area 62 of viscoelastic reservoir element 52 to achieve at least a first predetermined assembly resonant frequency substantially replicating a (similar) measured or estimated resonant frequency (e.g., a pump housing resonant frequency). Note that an adjacent annular unconstrained area 60 of viscoelastic reservoir element 52 remains open to pumped fluid pressure. Note also that adjustable preload flange 30 may be adjusted in effective radial extent and/or longitudinal position.
Note further that annular constrained area 62 and annular unconstrained area 60 are substantially concentric and adjacent. Thus, for a tunable suction valve subject to longitudinal (i.e., distally-directed) compressive constraint applied via preload flange 30 to annular constrained area 62 , annular unconstrained area 60 will tend to move (i.e., extrude) proximally relative to area 62 . The oppositely-directed (i.e., countercurrent) movements of constrained and unconstrained annular areas of viscoelastic reservoir element 52 create a substantially annular area of shear stress.
Finally, each circular tubular area 58 is substantially filled with at least one shear-thickening material 80 (see FIG. 5 ) chosen to achieve at least a second predetermined assembly resonant frequency similar, for example, to the first predetermined assembly resonant frequency). Note that FIG. 5 schematically represents a partially-sectioned view of an instantaneous configuration of the shear-thickening material 80 within circular tubular area 58 .
Referring to FIGS. 1 and 2 in greater detail, a tunable check valve assembly/tunable radial array embodiment 99 comprises viscoelastic body elements 50 which comprise, in turn, reservoir (central) element 52 coupled to groove (peripheral) element 54 via radial fenestration (tension) elements 56 . Elements 52 , 54 and 56 are disposed in (i.e., integrated with and/or lie substantially in) reservoir 16 , groove 12 and fenestrations 18 respectively to provide a tuned radial array having at least a third predetermined resonant frequency. An adjustable preload flange 30 is coupled to guide stem 14 and contacts viscoelastic reservoir element 52 in reservoir 16 to impose an adjustable annular constraint on viscoelastic reservoir element 52 for achieving at least a first predetermined assembly resonant frequency substantially similar to, for example, a measured resonant frequency (e.g., a pump housing resonant frequency). Such adjustable annular constraint imposes an adjustable shear preload between constrained annular area 62 and unconstrained annular area 60 . Tunable check valve assembly 99 may additionally comprise at least one circular tubular area 58 in groove element 54 residing in groove 12 , each tubular area 58 being substantially filled with at least one shear-thickening material 80 chosen to achieve at least a second predetermined assembly resonant frequency similar, for example, to the first predetermined assembly resonant frequency).
The above embodiment may be installed in a pump housing having a measured housing resonant frequency; the measured housing resonant frequency may then be substantially replicated in the (similar) first predetermined resonant frequency of the tunable check valve assembly. Such a combination would be an application of an alternate embodiment. An analogous tuning procedure may be followed if the tunable check valve assembly of the second embodiment is installed in a pump having a (similar or different) resonant frequency substantially equal to the second predetermined resonant frequency. This synergistic combination would broaden the scope of the valve assembly's beneficial effects, being yet another application of the invention's alternate embodiment.
Note that preload flange 30 may have a non-cylindrical periphery 32 for imposing on viscoelastic reservoir element 52 an adjustable annular shear preload having both longitudinal and transverse components.
Note further that the periphery of adjustable preload flange 30 , if cylindrical, predisposes a tunable check valve assembly to substantially longitudinal shear damping with each longitudinal distortion of check valve body 10 associated with valve closure. The character of such shear damping depends, in part, on the longitudinal position of the preload flange. Examples of different longitudinal positions are seen in FIG. 4 , which schematically illustrates the flange 30 ′ longitudinally displaced from flange 30 ″. Further, as shown in FIG. 4 , the convex periphery of a longitudinally adjusted preload flange 30 ′ or 30 ″ may introduce shear damping of variable magnitude and having both longitudinal and transverse components. Such damping may be beneficial in cases where significant transverse valve-generated vibration occurs.
To clarify the placement of viscoelastic body elements 50 , labels indicating the portions are placed on a sectional view in FIGS. 2 and 3 . Actual placement of viscoelastic body elements 50 in valve body 10 (see FIG. 1 ) may be by, for example, casting viscoelastic body elements 50 in place, or placing viscoelastic body elements 50 (which have been precast) in place during layer-built or welded fabrication. The tunable check valve assembly embodiment of the invention is intended to represent check valve body 10 and viscoelastic body elements 50 as complementary components at any stage of manufacture leading to functional integration of the two components.
To enhance scavenging of heat due to friction loss and/or hysteresis loss, shear-thickening material 80 and/or viscoelastic body elements 50 may comprise one or more polymers which have been augmented with nanoparticles and/or graphene 82 (see, e.g., FIG. 5 ). Nanoparticles and/or graphene may be invisible to the eye as they are typically dispersed in a colloidal suspension. Hence, they are schematically represented by cross-hatching 82 in FIG. 5 . Nanoparticles may comprise, for example, carbon forms (e.g., graphene) and/or metallic materials such as copper, beryllium, titanium, nickel, iron, alloys or blends thereof. The term nanoparticle may conveniently be defined as including particles having an average size of up to about 2000 nm. See, e.g., the '320 patent.
FIG. 6 is a schematic illustration of an exploded partially-sectioned 2-dimensional view of major components of a pump fluid end subassembly 88 , together with graphical aids and brief explanatory comments on component functions. The schematically-illustrated subassembly 88 comprises a pumping chamber 74 within a subassembly (pump) housing 78 , the pumping chamber 74 being in fluid communication with a suction bore 76 , a discharge bore 72 , and a piston/plunger bore 70 . Note that piston/plunger bore 70 comprises at least one recess (analogous to that labeled “packing box” in FIG. 6 ) in which at least one lateral support assembly 130 (see FIG. 8 ) may be sealingly positionable along the plunger as part of a tunable plunger seal embodiment. Schematic representations of a tunable suction valve 95 (illustrated for simplicity as a hinged check valve), a tunable discharge valve 97 (also illustrated for simplicity as a hinged check valve), and a piston/plunger 93 (illustrated for simplicity as a plunger) are shown in their respective bores. Note that longitudinally-moving valve bodies in check valve embodiments schematically illustrated herein (e.g., valve body 10 ) are associated with certain operational phenomena analogous to phenomena seen in hinged check valves (including, e.g., structural compliance secondary to closing energy impulses).
Regarding the graphical aids of FIG. 6 , the double-ended arrows that signify fluid communication between the bores (suction, discharge and piston/plunger) and the pumping chamber are double-ended to represent the fluid flow reversals that occur in each bore during each transition between pressure stroke and suction stroke of the piston/plunger. The large single-ended arrow within the pumping chamber is intended to represent the periodic and relatively large, substantially unidirectional fluid flow from suction bore through discharge bore during pump operation.
Further regarding the graphical aids of FIG. 6 , tunable suction (check) valve 95 and tunable discharge (check) valve 97 are shown schematically as hinged check valves in FIG. 6 because of the relative complexity of check valve embodiments having longitudinally-moving valve bodies. More detailed schematics of several check valve assemblies and elements are shown in FIGS. 1-11 , certain tunable check valve embodiments comprising a tunable check valve assembly and a tunable valve seat. In general, the tunable check valve assemblies/tunable radial arrays of tunable suction and discharge valves will typically be tuned to different assembly resonant frequencies because of their different positions in a subassembly housing 78 (and thus in a pump housing as described herein). Pump housing resonant frequencies that are measured proximate the tunable suction and discharge valves will differ in general, depending on the overall pump housing design. In each case they serve to guide the choices of the respective assembly resonant frequencies for the valves.
Note that the combination of major components labeled in FIG. 6 as a pump fluid end subassembly 88 is so labeled (i.e., is labeled as a subassembly) because typical fluid end configurations comprise a plurality of such subassemblies combined in a single machined block. Thus, in such typical (multi-subassembly) pump fluid end designs, as well as in less-common single-subassembly pump fluid end configurations, the housing is simply termed a “pump housing” rather than the “subassembly housing 78 ” terminology of FIG. 6 .
Further as schematically-illustrated and described herein for clarity, each pump fluid end subassembly 88 comprises only major components: a pumping chamber 74 , with its associated tunable suction valve 95 , tunable discharge valve 97 , and piston/plunger 93 in their respective bores 76 , 72 and 70 of subassembly housing 78 . For greater clarity of description, common fluid end features well-known to those skilled in the art (such as access bores, plugs, seals, and miscellaneous fixtures) are not shown. Similarly, a common suction manifold through which incoming pumped fluid is distributed to each suction bore 76 , and a common discharge manifold for collecting and combining discharged pumped fluid from each discharge bore 72 , are also well-known to those skilled in the art and thus are not shown.
Note that the desired check-valve function of tunable check valves 95 and 97 schematically-illustrated in FIG. 6 requires interaction of the respective tunable check valve assemblies (see, e.g., FIGS. 1-5 ) with a corresponding (schematically-illustrated) tunable valve seat (see, e.g., FIGS. 7 , 8 , 10 and 11 ). The schematic illustrations of FIG. 6 are only intended to convey general ideas of relationships and functions of the major components of a pump fluid end subassembly. Structural details of the tunable check valve assemblies that are in turn part of tunable check valves 95 and 97 of the invention (including their respective tunable valve seats) are illustrated in greater detail in other figures as noted above. Such structural details facilitate a plurality of complementary functions that are best understood through reference to FIGS. 1-5 and 7 - 11 .
The above complementary functions of tunable check valves include, but are not limited to, closing energy conversion to heat via structural compliance, energy redistribution through rejection of heat to the pumped fluid and pump housing, vibration damping and/or selective vibration spectrum narrowing through changes in tunable check valve assembly compliance, vibration frequency down-shifting (via decrease in rebound characteristic frequency) through increase of rebound cycle time, and selective vibration attenuation through energy dissipation (i.e., via redistribution) at predetermined assembly resonant frequencies.
FIG. 7 is a schematic illustration of two views of an exploded partially-sectioned 3-dimensional view including a check valve body 10 and its convex valve seat interface 22 , together with concave mating surface 24 of tunable valve seat 20 . Mating surface 24 is longitudinally spaced apart from a pump housing interface surface 21 . A curved longitudinal section edge 28 of the tunable valve seat's mating surface 24 , together with a correspondingly greater curved longitudinal section edge 26 of the valve body's valve seat interface 22 , are shown schematically in detail view A to aid description herein of a rolling valve seal.
The correspondingly greater curvature of valve seat interface 22 , as compared to the curvature of mating surface 24 , effectively provides a rolling seal against fluid leakage which reduces wear on the surfaces in contact. The rolling seal also increases longitudinal compliance of a tunable suction or discharge valve of the invention, with the added benefit of increasing the rise and fall times of the closing energy impulse (thus narrowing the associated vibration spectrum). Widening the closing energy impulse increases rebound cycle time and correspondingly decreases rebound characteristic frequency.
Further regarding the terms “correspondingly greater curvature” or “correspondingly less curvature” as used herein, note that the curvatures of the schematically illustrated longitudinal section edges (i.e., 26 and 28 ) and the surfaces of which they are a part (i.e., valve seat interface 22 and mating surface 24 respectively) are chosen so that the degree of longitudinal curvature of valve seat interface 22 (including edge 26 ) exceeds that of (i.e., has correspondingly greater curvature than) mating surface 24 (including edge 28 ) at any point of rolling contact. In other words, mating surface 24 (including edge 28 ) has correspondingly less curvature than valve seat interface 22 (including edge 26 ). Hence, rolling contact (i.e., a rolling valve seal) between valve seat interface 22 and mating surface 24 is along a substantially circular line (i.e., mating surface 24 is a curved mating surface for providing decreased contract area along the circular line). The plane of the circular line is generally transverse to the (substantially coaxial) longitudinal axes of valve body 10 and tunable valve seat 20 . And the decreased contract area along the circular line is so described because it is small relative to the nominal contact area otherwise provided by conventional (frusto-conical) valve seat interfaces and valve seat mating surfaces.
Note that the nominal frusto-conical contact area mentioned above is customarily shown in engineering drawings as broad and smooth. But the actual contact area is subject to unpredictable variation in practice due to uneven distortions (e.g., wrinkling) of the respective closely-aligned frusto-conical surfaces under longitudinal forces that may exceed 250,000 pounds. An advantage of the rolling valve seal along a substantially circular line as described herein is minimization of the unpredictable effects of such uneven distortions of valve seat interfaces and their corresponding mating surfaces.
Note also that although valve seat interface 22 and mating surface 24 (and other valve seat interface/mating surface combinations described herein) are schematically illustrated as curved, either may be frusto-conical (at least in part) in certain tuned component embodiments. Such frusto-conical embodiments may have lower fabrication costs and may exhibit suboptimal distortion, down-shifting performance and/or wear characteristics. They may be employed in relatively lower-pressure applications where other tunable component characteristics provide sufficient operational advantages in vibration control.
The above discussion of rolling contact applies to the alternate tunable valve seat 20 ′ of FIG. 8 , as it does to the tunable valve seat 20 of FIG. 7 . FIG. 8 schematically illustrates a 3-dimensional exploded and partially-sectioned view of a tunable valve seat showing a mating surface (analogous to mating surface 24 of FIG. 7 ) longitudinally spaced apart from a lateral support mounting surface 21 ′. But the lateral support mounting surface 21 ′ in FIG. 8 differs from pump housing interface surface 21 of FIG. 7 in that it facilitates adjustably securing a lateral support assembly 130 to alternate tunable valve seat 20 ′. Lateral support assembly 130 comprises first and second securable end spacers ( 110 and 124 respectively) in combination with a plurality of circular viscoelastic support elements ( 114 , 118 and 122 ), each support element comprising a support circular tubular area (see areas 112 , 116 and 120 respectively). Shear-thickening material in each support circular tubular area 112 , 116 and 120 is chosen so each lateral support assembly 130 has at least one predetermined resonant frequency. Lateral support assemblies thus configured may be part of each tunable valve seat and each tunable plunger seal. When part of a tunable plunger seal, one or more lateral support assemblies 130 reside in at least one recess analogous to the packing box schematically illustrated adjacent to piston/plunger 93 (i.e., as a portion of piston/plunger bore 70 ) in FIG. 6 .
Note also that in general, a tunable (suction or discharge) check valve of the invention may comprise a combination of a tunable check valve assembly 99 (see, e.g., FIG. 1 ) and a tunable valve seat 20 (see, e.g., FIG. 7 ) or a tunable valve seat 20 ′ (see, e.g., FIG. 8 ). Referring more specifically to FIG. 6 , tunable suction check valve 95 is distinguished from tunable discharge check valve 97 by one or more factors, including each measured resonant frequency to which each tunable check valve is tuned so as to optimize the overall effectiveness of valve-generated vibration attenuation in the associated pump housing 78 .
FIGS. 9-11 show schematic exploded views of a nonlinear spring-mass damper 227 / 228 / 229 / 230 , which may be incorporated in a tunable check valve assembly embodiment 210 . FIGS. 9-11 can each be understood as schematically illustrating a tunable check valve assembly with or without a peripheral groove viscoelastic element. That is, each figure may also be understood to additionally comprise a viscoelastic groove element analogous to groove element 54 (see FIG. 2 ) residing in groove 218 ′/ 218 ″ (see FIG. 9 )—this groove element is not shown in exploded FIGS. 9-11 for clarity, but may be considered to comprise at least one circular tubular area analogous to tubular area 58 in groove element 54 (see FIG. 2 ), each tubular area 58 being substantially filled with at least one shear-thickening material 80 chosen to achieve at least one predetermined assembly resonant frequency.
Referring to FIG. 9 , Belleville springs 227 / 228 / 229 are nonlinear, and they couple mass 230 to the valve body base plate 216 and the proximal valve body portion 214 . Additionally, dilatant liquid 242 is optionally added (via sealable ports 222 and/or 220 ) to central internal cavity 224 to immerse nonlinear spring-mass damper 227 / 228 / 229 / 230 . The nonlinear behavior of dilatant liquid 242 in shear (as, e.g., between Belleville springs 227 and 228 ) expands the range of tuning the nonlinear spring-mass damper 227 / 228 / 229 / 230 to a larger plurality of predetermined frequencies to reduce “ringing” of valve body 214 / 216 in response to a closing energy impulse.
To clarify the function of nonlinear spring-mass damper 227 / 228 / 229 / 230 , mass 230 is shown perforated centrally to form a washer shape and thus provide a passage for flow of dilatant liquid 242 during longitudinal movement of mass 230 . This passage is analogous to that provided by each of the Belleville springs 227 / 228 / 229 by reason of their washer-like shape.
FIG. 10 shows an exploded view of an alternate embodiment of a tunable check valve comprising the tunable check valve assembly 210 of FIG. 9 , plus a tunable valve seat 250 . FIGS. 10 and 11 schematically illustrate two views of an exploded partially-sectioned 3-dimensional view including a valve body 214 / 216 and its valve seat interface 234 , together with mating surface 254 of tunable valve seats 250 and 250 ′. Mating surface 254 is longitudinally spaced apart from pump housing interface surface 252 in FIG. 10 , and from lateral support mounting surface 252 ′ in FIG. 11 . In FIG. 10 , a curved longitudinal section edge 256 of the tunable valve seat's mating surface 254 , together with a correspondingly greater curved longitudinal section edge 236 of valve seat interface 234 , are shown schematically to aid description herein of a rolling valve seal along a substantially circular line.
Note that valve body 214 / 216 may be fabricated by several methods, including that schematically illustrated in FIGS. 9-11 . For example, circular boss 215 on proximal valve body portion 214 may be inertia welded or otherwise joined to circular groove 217 on valve body base plate 216 . Such joining results in the creation of peripheral seal-retention groove 218 ′/ 218 ″ having proximal groove wall 218 ′ and distal groove wall 218 ″.
To enhance scavenging of heat due to friction loss and/or hysteresis loss, liquid polymer(s) 242 may be augmented by adding nanoparticles which are generally invisible to the eye as they are typically dispersed in a colloidal suspension. Nanoparticles comprise, for example, carbon and/or metallic materials such as copper, beryllium, titanium, nickel, iron, alloys or blends thereof. The term nanoparticle may conveniently be defined as including particles having an average size of up to about 2000 nm. See, e.g., the '320 patent.
The correspondingly greater curvature of valve seat interface 234 , as compared to the curvature of mating surface 254 , effectively provides a rolling seal against fluid leakage which reduces frictional wear on the surfaces in contact. The rolling seal also increases longitudinal compliance of a tunable suction or discharge valve of the invention, with the added benefit of increasing the rise and fall times of the closing energy impulse (thus narrowing the associated vibration spectrum).
Further regarding the term “correspondingly greater curvature” as used herein, note that the curvatures of the schematically illustrated longitudinal section edges (i.e., 236 and 256 ) and the surfaces of which they are a part (i.e., valve seat interface 234 and mating surface 254 respectively) are chosen so that the degree of longitudinal curvature of valve seat interface 234 (including edge 236 ) exceeds that of (i.e., has correspondingly greater curvature than) mating surface 254 (including edge 256 ) at any point of rolling contact. Hence, rolling contact between valve seat interface 234 and mating surface 254 is always along a substantially circular line that decreases contact area relative to the (potentially variable) contact area of a (potentially distorted) conventional frusto-conical valve body/valve seat interface (see discussion above). The plane of the circular line is generally transverse to the (substantially coaxial) longitudinal axes of valve body 214 / 216 and tunable valve seat 250 . (See notes above re frusto-conical valve seat interface shapes and mating surfaces).
The above discussion of rolling contact applies to the alternate tunable valve seat 250 ′ of FIG. 11 , as it does to the tunable valve seat 250 of FIG. 10 . But the lateral support mounting surface 252 ′ in tunable check valve 399 of FIG. 11 differs from pump housing interface surface 252 of FIG. 10 in that it facilitates adjustably securing a lateral support assembly 330 to alternate tunable valve seat 250 ′ to form tunable valve seat 389 . Lateral support assembly 330 comprises first and second securable end spacers ( 310 and 324 respectively) in combination with a plurality of circular viscoelastic support elements ( 314 , 318 and 322 ), each support element comprising a support circular tubular area ( 312 , 316 and 320 respectively).
Note that in general, a tunable (suction or discharge) check valve of the invention may comprise a combination of a tunable check valve assembly 210 (see, e.g., FIG. 9 ) and a tunable valve seat 250 (see, e.g., FIG. 10 ) or a tunable valve seat 250 ′ (see, e.g., FIG. 11 ). Referring more specifically to FIG. 6 , tunable suction valve 95 is distinguished from tunable discharge check valve 97 by one or more factors, including each measured or estimated resonant frequency to which each tunable check valve is tuned so as to optimize the overall effectiveness of valve-generated vibration attenuation in the associated pump housing 78 .
FIG. 12 illustrates two schematic 3-dimensional views of an alternate tunable check valve assembly embodiment 410 / 470 / 480 (see exploded view in FIG. 13 ) which is symmetrical about a longitudinal axis and comprises a plurality of radially-spaced vibration dampers. One such damper is in the peripheral seal 470 with its peripheral circular tubular area 472 and enclosed fluid tuning medium 482 , tubular area 472 being responsive to longitudinal compression of the assembly. A second damper is in valve body 410 with enclosed spaces 460 / 464 in fluid communication with central circular tubular area 462 via fluid flow restrictors 466 / 468 in the presence of fluid tuning medium 442 . Tubular area 462 and fluid flow restrictors 466 / 468 are also responsive to longitudinal to compression of the assembly, thereby prompting fluid flow through the flow restrictors in association with valve closure shock and/or vibration.
Thus, each vibration damper comprises a circular tubular area ( 462 / 472 ), and at least one vibration damper is tunable to a predetermined frequency (e.g., a resonant frequency of a fluid end in which the assembly is installed). The tuning mechanisms may differ: e.g., via a fluid medium 442 (shown schematically being added in FIG. 12 via a sealable port 422 in valve body 410 ) in a tubular area 462 and/or via a fluid medium 482 (shown as an instantaneous shape 480 ) within tubular area 472 . Control of variable fluid flow resistance and/or fluid stiffness (in the case of shear-thickening fluids) facilitates predetermination of resonant frequency or frequencies in the central and peripheral dampers.
In either case, tuning is function of responsiveness of the respective dampers to vibration secondary to valve closure impact (see above discussion of such impact and vibration). For example, longitudinal force on the closed valve will tend to reduce the distance between opposing fluid flow restrictors 466 / 468 , simultaneously prompting flow of fluid tuning medium 442 from circular tubular area 462 to areas 464 and/or 460 ( 460 acting as a surge chamber). Flow resistance will be a function of fluid flow restrictors 466 / 468 and the fluid viscosity. Note that viscosity may vary with time in a shear-thickening liquid 442 , thereby introducing nonlinearity for predictably altering center frequency and/or Q of the damper. Analogous predetermined viscosity variation in fluid tuning medium 482 is available for predictably altering the center frequency and/or Q (i.e., altering the tuning) of the peripheral damper 470 / 472 / 482 as the seal 470 distorts under the longitudinal load of valve closure.
Note that the peripheral seal vibration damper 470 / 472 / 482 comprises a medial flange 479 sized to closely fit within flange channel 419 of valve body 410 , and medial flange 419 partially surrounds circular tubular area 472 within said seal 470 . Those skilled in the art know that conventional peripheral seals tend to rotate within their retaining groove. The illustrated seal embodiment herein shows that such rotation will tend to be resisted by the combined action of medial flange 479 and flange channel 419 . Further, the portion of circular tubular area 472 partially surrounded by medial flange 419 will tend to stiffen medial flange 479 in a nonlinear manner when circular tubular area 472 contains a shear-thickening fluid tuning medium.
FIG. 14 illustrates a partial schematic 3-dimensional view of an alternate tunable check valve embodiment comprising the valve body 410 of FIG. 13 , together with a tunable valve seat 452 . A detail breakout view shows that the valve seat interface has correspondingly greater curvature than the mating surface to facilitate a rolling valve seal along a substantially circular line, the seal having predetermined rebound cycle time and rebound characteristic frequency as described above.
FIGS. 15 and 16 illustrate partial schematic 3-dimensional views of a tunable hydraulic stimulator embodiment 599 , FIG. 16 being an exploded view. Numerical labels may appear in only one view. A hollow cylindrical housing 590 has a longitudinal axis, a first end 594 , and a second end 592 . First end 594 is closed by fluid interface 520 for transmitting and receiving vibration. Fluid interface 520 comprises at least one accelerometer 518 for producing an accelerometer signal (i.e., an accelerometer-generated feedback signal) representing vibration transmitted and received by fluid interface 520 .
Driver element 560 (comprising electromagnet/controller 564 / 562 ) reversibly seals second end 592 , and hammer element 540 is longitudinally movable within housing 590 between driver element 560 and fluid interface 520 . In some embodiments, hammer element 540 may be analogous in part to the armature of a linear electric motor, as in a railgun. (See, e.g., U.S. Pat. Nos. 8,371,205 B2 and 8,677,877 B2, both incorporated by reference). Note that the above accelerometer-generated feedback signal may be augmented by, or replaced by, sensorless control means (e.g., using operating parameters of electromagnet 564 ) in free piston embodiments of the tunable hydraulic stimulator. (See, e.g., U.S. Pat. No. 6,883,333 B2, incorporated by reference).
Thus, hammer element 540 is responsive to driver element 560 for striking, and rebounding from, fluid interface 520 . The duration of each such striking and rebounding cycle (termed herein the “hammer rebound cycle time”) has the dimension of seconds. And the inverse of this duration has the dimension of frequency. Hence, the term herein “hammer rebound characteristic frequency” is the inverse of a hammer rebound cycle time, and the hammer rebound cycle time itself is inversely proportional to the bandwidth of transmitted vibration spectra resulting from each hammer strike and rebound from fluid interface 520 .
Fluid interface 520 transmits vibration spectra generated by hammer impacts on fluid interface 520 as well as receiving backscattered vibration from geologic formations excited by stimulator 599 . Fluid interface 520 comprises, for example, a MEMS accelerometer 518 for producing an accelerometer signal representing vibration transmitted and received by fluid interface 520 . (See MicroElectro-Mechanical Systems in Harris , pp. 10-26, 10-27).
Hammer element 540 comprises a striking face 542 (see FIG. 16 ) which has a predetermined modulus of elasticity (e.g., that of mild steel, about 29,000,000 psi) which can interact with the modulus of elasticity of fluid interface 520 (again, e.g., that of mild steel). In a practical example, interaction of the two suggested moduli of elasticity predetermines a relatively short rebound cycle time for hammer element 540 , which is associated with a corresponding relatively broad-spectrum of vibration to be transmitted by fluid interface 520 . In other words, striking face 542 strikes fluid interface 520 and rebounds to produce a relatively short-duration, high-amplitude mechanical shock. (See, e.g., Harris p. 10.31).
Both FIGS. 15 and 16 schematically illustrate a tunable resilient circumferential seal 580 for sealing housing 590 within a wellbore, thus partially isolating vibration transmitted by fluid interface 520 within the wellbore. Seal 580 comprises at least one circular tubular area 582 which may contain at least one shear-thickening fluid 80 (see FIG. 5 ) which is useful in part for tuning purposes. And fluid 80 may comprise nanoparticles 82 for, e.g., facilitating heat scavenging. FIG. 16 also schematically illustrates a first electrical cable 516 for carrying accelerometer signals (schematically representing vibration transmitted by and/or received by fluid interface 520 ) from accelerometer 518 to driver element 560 . A second electrical cable 514 also connects to driver element 560 of each tunable hydraulic stimulator to schematically represent interconnection of two or more such stimulators (in a tunable hydraulic stimulator array) and/or for connecting one or more down-hole tunable hydraulic stimulators to related equipment (e.g., programmable microprocessors and/or controllers, not shown) proximal in a wellbore and/or adjacent to the wellhead. Accelerometer signals provide feedback on transmitted vibration and also on received backscattered vibration to driver element 560 .
While accelerometer-mediated feedback may be desired for tailoring stimulation to specific geologic formations and/or to progress in producing desired degrees for fracture within a geologic formation, predetermined stimulation protocols may be used instead to simplify operations and/or lower costs.
In certain embodiments, software and data to implement sensorless control via operating parameters of electromagnet 564 , or to implement feedback control incorporating accelerometer 518 , are conveniently stored and executed in a microprocessor (located, e.g., in controller 562 ). (See, e.g., U.S. Pat. No. 8,386,040 B2, incorporated by reference). See FIGS. 5 and 6 of the '040 patent reference, for example, with their accompanying specification.
Note, however, that while certain of the electrodynamic control characteristics of a tunable hydraulic stimulator may be represented in earlier devices, the tunable hydraulic stimulator's reliance on mechanical shock (i.e., generated by hammer strike and rebound) to generate tuned vibration (i.e., specified via magnitude and/or frequency) imposes unique requirements indicated by the dynamic responsiveness of certain stimulator elements to other stimulator elements as described herein. Further, the power/data cable 514 , or an analogous communication medium, (see FIG. 16 ) may extend to other hydraulic stimulators and/or to wellhead or other auxiliary equipment (not shown) that may 1) power the hydraulic stimulator, 2) receive and transmit stimulation-related data, 3) coordinate stimulator operation (e.g. vibration phase, frequency and/or amplitude) with related equipment, and/or 4) modify driver-related software programs affecting tunable hydraulic stimulator operations.
Note also that in addition to individual applications of a tunable hydraulic stimulator, two or more such stimulators may operate in a combined tunable hydraulic stimulator array during a given stage of fracking (e.g., in a temporarily isolated section of horizontal wellbore). Section isolation in a wellbore may be accomplished with swell packers, which may function interchangeably in part as the tunable resilient circumferential seals described herein. A single tunable hydraulic stimulator or an interconnected tunable hydraulic stimulator array may be programmed in near-real time to alter stimulation parameters in response to changing conditions in geologic materials adjacent to a wellbore. A record of such changes, together with results, guides future changes to increase stimulation efficiency.
In summary, the responsiveness of certain elements of a tunable hydraulic stimulator to other elements and/or to parameter relationships facilitates operational advantages in various alternative stimulator embodiments. Examples involving such responsiveness and/or parameter relationships include, but are not limited to: 1) driver element 560 comprises an electromagnet/controller 564 / 562 having cyclical magnetic polarity reversal characterized by a variable polarity reversal frequency; 2) longitudinal movement of hammer element 540 is responsive to the driver cyclical magnetic polarity reversal; 3) longitudinal movement of hammer element 540 striking, and rebounding from, fluid interface 520 may be substantially in phase with the polarity reversal frequency to generate vibration transmitted by fluid interface 520 ; 4) the driver element polarity reversal frequency may be responsive to the accelerometer signal; 5) longitudinal movement of hammer element 540 may be substantially in phase with the polarity reversal frequency; 6) longitudinal movement of hammer element 540 striking, and rebounding from, fluid interface 520 has a hammer rebound characteristic frequency which is the inverse of the hammer rebound cycle time; and 7) the hammer rebound characteristic frequency may be similar to the polarity reversal frequency. | Selected designs for reciprocating pumps and down-hole well-stimulation equipment reflect disparate applications of identical technical principles (relating to, e.g., the vibration spectrum of an impulse). In certain of these designs, the vibration spectrum is controlled, suppressed and/or damped using tunable components to limit destructive excitation of resonances; in others the vibration spectrum is tuned at its source for maximum resonance excitation. For example, tunable fluid ends control valve-generated vibration to increase fluid-end reliability. By down-shifting the frequency domain of each valve-closing impulse shock, initial excitation of fluid end resonances is minimized. Subsequent damping and/or selective attenuation of vibration likely to excite one or more predetermined (and frequently localized) fluid end resonances represents further optimal use of fluid end vibration-control resources. Vibration generation in stimulators, in contrast, includes techniques for production of desired frequency bands (vibration spectra) and amplitudes (vibration energy) near explosively-formed perforations in a wellbore. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Application No. 60/945,979, filed Jun. 25, 2007, the disclosure of which is incorporated herein by reference.
BACKGROUND
[0002] 1. Field
[0003] The present invention relates generally to reflector shapes for light emitting devices and specifically to shapes designed to directly generate vertically emitted polarized light.
[0004] 2. Description of the Related Art
[0005] High efficiency and power, long lifetime, small size, and the wide range of wavelengths available are reasons why light-emitting diodes (LEDs) are becoming increasingly important in areas such as sensing and imaging, general illumination and liquid crystal display (LCD) backlighting. A key benefit provided by LEDs is the ability to tune properties such as wavelength or color temperature to meet the needs of specific applications. However, the control of one property in particular—the optical polarization—has remained elusive. Polarized LEDs would be extremely useful particularly for LCD backlighting but also for imaging and communications. Accordingly, there is a need for a polarized LED source, which is enabled by a polarization-enhancing reflector design matched to the emission characteristics of GaInN LEDs so that light incident upon the reflector is redirected, and through selective polarization rotation by the reflector exhibits an enhanced polarization ratio.
[0006] Previously it has been reported that the light emitted in certain directions by 20 GaInN LEDs epitaxially grown on (0001) oriented sapphire substrates shows some degree of polarization. Polarization effects have also been demonstrated with LEDs grown on non-polar or semi-polar substrates. Studies of GaInN LEDs on sapphire substrates with multiple quantum well (MQW) active regions emitting at 460 nm revealed that light emitted from the side facets of the LED chips is dominantly polarized in the plane of the quantum wells, with values as high as 7:1 for the ratio of in-plane polarized light to normal-to-plane polarized light's. However, despite the measured polarization characteristics of unpackaged chips, conventional packaged LEDs were found to be completely unpolarized. This is attributed to the use of reflectors which do not preserve the inherent polarization properties of the LED chips. These reflectors typically exhibit continuous rotational symmetry and simply take the rays emitted in different directions and reflect them upwards. When two orthogonally polarized beams of equal intensity are combined, the result is unpolarized light.
SUMMARY
[0007] A light-emitting device including a light source that exhibits polarization anisotropy and a reflector that is shaped so that for light emitted in at least two directions from the light source, the angle between the dominant polarization directions after reflecting from the reflector is smaller than the angle between the dominant polarization directions before reflecting from the reflector.
[0008] In the light-emitting device the light source may be a light-emitting diode chip.
[0009] In the light-emitting device the light source may be one of a plurality of light sources.
[0010] The reflector shape exploits the polarization characteristics of light emitted from the side facets of GaInN LEDs in order to directly generate vertically emitted (i.e. normal to the plane of the LED chip) polarized light. This reflector design varies the optical path based upon the direction of light emission in that all light emitted by the LED that is incident on the reflector is directed upwards. However, depending upon the direction of the emitted light, the polarization may also be rotated by some angle. This concept is illustrated in FIG. 1 . Through the selective polarization rotation, all side emitted light—which is initially polarized in the plane of the quantum wells—is polarized along a single direction when it leaves the reflector.
[0011] Additional aspects and/or advantages will be set forth in part in the description which follows and, in part, will be apparent from the description, or may be learned by practice of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] These and/or other aspects and advantages will become apparent and more readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
[0013] FIG. 1 is a perspective view of the polarization-enhancing reflector concept according to the present invention;
[0014] FIG. 2 is a wireframe view of the polarization-enhancing reflector concept according to the present invention;
[0015] FIG. 3 is a photographic view of the polarization-enhancing reflector concept according to the present invention;
[0016] FIG. 4 is a graph showing the measured intensity for x-polarized and y-polarized light both with and without the reflector of the present invention;
[0017] FIG. 5 is a graph showing the measured intensity for x-polarized and y-polarized light as a function of position; and
[0018] FIG. 6 is a graph showing the ratio of x-polarized to y-polarized light as a function of position.
DETAILED DESCRIPTION OF EMBODIMENTS
[0019] In the following detailed description of various embodiments, reference is made to the accompanying drawings that form a part hereof, and in which are shown by way of illustration, and not of limitation, specific embodiments in which the subject matter may be practiced, The embodiments illustrated are described in sufficient detail to enable those skilled in the art to practice the teachings disclosed herein. Other embodiments may be utilized and derived therefrom, such that compositional, structural, and logical substitutions and changes may be made without departing from the scope of this disclosure. Examples and embodiments merely typify possible variations. Individual components and functions are optional unless explicitly required, and the sequence of operations may vary. Portions and features of some embodiments may be included in or substituted for those of others. The following description is, therefore, not to be taken in a limiting sense.
[0020] The reflector shape is determined using the following algorithm. In calculations the light source is assumed to be located at the origin and emit light polarized in the quantum well plane. The reflector shape is defined in terms of a rectangular grid of points in spherical coordinates in which the azimuthal angle Θ and zenith angle φ for each point are fixed and spaced at regular intervals. The radial coordinate r for each point on the grid is initially unknown. By grouping three points on the grid, a triangle is formed. The r-values for these three points are then optimized in order to maximize the figure of merit, which is chosen to be the product of (1) transmission through a linear polarizer lying in the xy-plane above the reflector which allows x-polarized light to pass and (2)|cos(φ final )|, where φ final is the zenith angle of the propagation direction for a beam after reflection. This figure of merit ensures that the light which leaves the reflector has the desired polarization and travels in a close-to-vertical direction. It would be possible to change the figure of merit in order to tailor the far-field emission pattern of the final device. Once one triangle has been found, it is possible to form a new triangle by selecting a single new point, which is again optimized. This process is continued until the entire reflector shape is determined. The optimized reflector shape was calculated for beams that are emitted with zenith angles between φ=72° and Θ=126°. For φ greater than 126°, the reflector shape is linearly extrapolated from calculated points; for φ less than 72°, light rays do not strike the reflector. The reflector is fabricated from aluminum by a computer controlled milling machine and then extensively polished by hand to give the surface a specular optical finish. A slot is machined in the center at the bottom in order to facilitate mounting of the LED chip. A wireframe view and photograph of the reflector are shown in FIG. 2 and FIG. 3 , respectively.
[0021] The GaInN LED used to test the reflector emits at 460 nm and is 200×450 μm 2 in size. The chip is mounted on the tip of a pin which has been flattened to make a level surface for mounting and is held in place with a small amount of adhesive. The flattened pin tip is circular in shape and approximately 180 μm in diameter, which allows the edges of the chip to overhang. The pin which serves as the LED chip holder is held fixed in place and the reflector cup is positioned on a 3-axis stage so the pin protrudes through the slot in the base of the reflector. The position of the reflector with respect to the LED chip is optimized using a large-area (25 mm diameter) photodetector and polarizer located approximately 40 mm above the top of the reflector. This detector position allows the capture of nearly all light emitted in vertical and close-to-vertical directions. The reflector position is adjusted in order to maximize the polarization ratio, defined as the ratio of intensity with the polarizer aligned in the x-direction to the intensity with the polarizer aligned in the y-direction. The intensity of x-polarized and y-polarized light is also measured in the absence of the reflector in order to determine the polarization ratio for only that light which strikes the reflector. The measurement results are shown in FIG. 4 . The total polarization ratio, which combines reflected and directly emitted (i.e. light not striking the reflector) light, is measured to be 1.9:1, while ratio for reflected light only is 2.5:1. Due to the detector position and its large area, this may be considered the average polarization ratio for light traveling in the vertical direction. By comparison, an unpackaged or conventionally packaged LED has a ratio of 1:1 for vertically emitted light.
[0022] Measurements of the x- and y-polarization intensities as a function of position above the reflector are also performed. A detector with a 2.5 mm aperture is scanned over a 22.5×40 mm 2 area in the xy-plane above the reflector. This measurement reveals the farfield emission pattern of the LED with reflector. FIG. 5 shows the measured intensity as a function of detector position for both polarizations. FIG. 6 shows the ratio of the two polarizations. The peak ratio observed is approximately 3.5:1 and there are several points which have ratios above 3:1. FIGS. 5 and 6 reveal an asymmetry in both the intensity and ratio as a function of position; this difference is likely due to an asymmetry in the reflector itself. The fabrication method used relies heavily on work done by hand and does not produce a perfect result. When the reflector is examined, the surface does appear specular in general, but close inspection reveals some non-specular regions where the finish is compromised by small scratches as well as regions where the reflector shape deviates from the intended shape. This indicates that the performance would be further increased through the use of improved methods in the manufacture and polishing of the reflector. It would also be possible to increase performance by designing a deeper reflector that reflects light with φ<72°, which would allow the capture of more highly-polarized side emission. As a result, the maximum values measured for the polarization ratio should be taken as an indicator of the performance potential of the reflector. The combination of side-emitting LEDs and the polarization-enhancing reflector together with optimized encapsulant shapes could lead to highly polarized and highly efficient light sources useful for LCD backlighting and other applications.
[0023] In conclusion, the design of a reflector structure which takes advantage of the polarized emission characteristics of GaInN LEDs provides a light source that emits predominantly linearly polarized light. Measurements show that reflected light traveling in close-to-vertical directions has an intensity ratio of desired polarization to undesired polarization of 2.5:1, while the combination of reflected and directly emitted light is polarized with an average ratio of 1.9:1. In addition, a scan of the farfield emission pattern shows local polarization ratios as high as 3.5:1. The reflector design and the concept of providing a different optical path dependent upon the direction and polarization of light through selective polarization rotation are both highly promising for the development of polarized light sources individually tailored for specific applications, such as LCD backlighting.
[0024] An aspect of the present invention further provides that the LED structure is grown by metal-organic chemical vapor deposition on oriented sapphire substrates and consists of a 2 pm thick undoped GaN buffer layer, an n-type GaN lower cladding layer, a GaInN/GaN multiple quantum well active region, a p-type GaN upper cladding, and a highly doped p-type GaN contact layer. LED mesa structures are obtained by standard photolithographic patterning followed by chemically-assisted ion-beam etching using C12 and Ar to expose the n-type cladding layer. The ohmic contact for n-type GaN is Ti/Al/Ti/Au annealed at 650° C. for 1 min. Then, AgCu alloy (2 nm)/ITO (200 nm) is deposited on p-type GaN by electron-beam evaporation and 10 annealed at 500° C. under 02 ambient to form transparent ohmic contact to p-type GaN. After processing the sapphire substrate is thinned to approximately 80 pm thickness and then diced into individual LED chips.
[0025] Although a few embodiments have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents. | A light-emitting device including a light source that exhibits polarization anisotropy and a reflector that is shaped so that for light emitted in at least two directions from the light source, the angle between the dominant polarization directions after reflecting from the reflector is smaller than the angle between the dominant polarization directions before reflecting from the reflector. In the light-emitting device the light source may be a light-emitting diode chip or one of a plurality of light sources. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims the benefit of the priority filing date of international application no. PCT/EP2009/059855, and Italian application no. MI2009A000615 filed on Apr. 16, 2009.
FEDERALLY SPONSORED RESEARCH
[0002] Not Applicable
SEQUENCE LISTING OR PROGRAM
[0003] Not Applicable
STATEMENT REGARDING COPYRIGHTED MATERIAL
[0004] Portions of the disclosure of this patent document contain material that is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure as it appears in the Patent and Trademark Office file or records, but otherwise reserves all copyright rights whatsoever.
BACKGROUND
[0005] The present invention relates to a submerged pump with electrical cables outside a cylindrical lateral wall, in which protection means conformed to receive the cables are arranged as to be restrained to the body of the pump by means of quick fixing devices, which may be associated with bayonet sliding triggers to activate closing and opening connections easily executable by means of pushes, click-lifting by simple radial pressure, or simple shift restraining between the parts.
[0006] Pumping members, such as submerged pumps, are known, and are generally used for domestic, civil and industrial purposes for emptying sump pits, underground rooms, tanks or similar vessels. Known submerged pumps generally include a delivery body, within which an impeller communicates with the external environment, and a generally cylindrical driving body adapted to receive a driving member.
[0007] An example of a known submerged pump is disclosed in patent U.S. Pat. No. 5,207,562. The described submerged pump is provided with a particular handle adapted to incorporate a passage channel for the electrical supply cables of the driving member therein, as well as a port for introducing lubrication and cooling oil into the driving body.
[0008] U.S. Pat. No. 2,701,529 discloses in turn a submerged pump comprising a casing provided with a cylindrical lateral wall, a bottom wall and an upper lid for closing the open top of the pump. Such a lid has a single opening for passing both the supply cable of the actuating motor of the pump impeller and a pair of electrical cables connected to the motor itself and intended to be externally connected to liquid level control means. For connecting and fixing these control means, the lid laterally has a pair of lateral supports, in which the respective electrical cables are adapted to be inserted and appropriately connected. Thus, the need to ensure reliable electrical connection under all conditions of use is known in submerged pumps.
[0009] In order to satisfy this need, appropriate electrical cable protection means are used, which form a channel outside the body of the pump, for receiving and passing the cables. These protection means have become more widespread, and usually consist of a profiled element coupled to the body of the pump by means of an appropriate connection means, e.g. screw. However, these protection devices do not fully meet the requirements of the concerned field. These systems, while effectively protecting the electrical cables, are indeed not very practical in application. Assembling the cable protection means is slow and difficult, generally requiring coupling by means of screws. In particular, it has been observed that rapid assembly is an essential feature for handheld submerged pumps, which require easy transportation and installation for effective use under emergency conditions.
[0010] It is the task of the present invention to solve the mentioned problems by providing a submerged pump with a simple electrical cable protection device which can quickly be assembled. In the scope of this task, it is a further object of the present invention to provide a safe and reliable electrical cable protection device for all conditions of use.
[0011] Another object of the present invention is to provide an electrical cable protection device that is both effective and simple to use.
[0012] Another object of the present invention is to provide an electrical cable protection device of simple construction, versatile, and relatively low in cost.
[0013] The basic embodiment of the invention thus comprises an electrical cable protection means restrained externally to the body of the pump which totally eliminates drawbacks and disadvantages related to the known art.
[0014] Furthermore, the achievement of said objects, and others, is ensured in accordance with the above, in that the present invention relates to a submerged pump having electrical cable protection means restrained outside the body of the pump by means of quick fixing devices, which activate closing and opening connections easily, and are executable by means of pushes or click-lifting by simple radial pressure. Said devices are associable with bayonet sliding triggers for quick and stable blocking and releasing between said protection means and the lateral wall of the pump.
SUMMARY
[0015] The present invention relates to a submerged pump having electrical cable protection means restrained outside the body of the pump by means of quick fixing devices, which activate closing and opening connections and are easily executable by means of pushes or click lifting by simple radial pressure. Said devices are associable with bayonet sliding triggers for quick and stable blocking and releasing between said protection means and the lateral wall of the pump.
[0016] According to one embodiment, the quick fixing devices are receptacles conformed with resilient tails which engage notches positioned along the protection means and said receptacles are preferably soldered to the cylindrical lateral wall of the submerged pump body.
[0017] According to a further embodiment, the quick fixing devices are substantially conformed as an arc of a circle for a surface contact to the lateral cylindrical wall and are provided with inwardly shaped resilient tails, suitable to elastically deform upon simple joining pressure to receive and hold the protection means by at least one notch positioned along the longitudinal development of the protection means.
[0018] According to a further embodiment, the bayonet sliding triggers comprise a lantern-sleeve applied inferiorly to the body of the pump and which has a shaped seat predisposed to receive by plugging the terminal inferior portion of the protection means. Said shaped seat has a cavity positioned radially in the lantern-sleeve, partially externally contained by two appendices.
[0019] According to a further embodiment, the protection means consist of a longitudinal raceway element having a “U” profile-like section, provided with edges which extend towards the outside for a surface support contact with the cylindrical external wall of the body of the pump. Said protection means also have a longitudinally flaring profile at an inferior terminal protection, suitable to ease the coupling of the protection means to the shaped seat for a quick bayonet fixing.
[0020] According to a further embodiment, the quick fixing means are small disks or blocks, similar to a snap fastener, positioned along the edges of the protection means and on the cylindrical wall of the pump to click join or divide the cylindrical body of the pump and the protection of the electrical cables (juxtaposed in the scope of their functionality) by simple pressure.
DRAWINGS
[0021] The invention is described in detail below on the basis of the embodiment diagrammatically illustrated in the accompanying drawings, which outline the features of the invention; it should be noted that all the accompanying drawings, as well as the description of the drawings themselves, correspond to a preferred embodiment to better understand the implementation thereof; however, possible variations of reciprocal positions of the members, as well as the consequent simplifications, which could derive therefrom, and all the constructional variants included in the general idea are comprised within the requested scope of protection, which is presented in the accompanying drawings.
[0022] FIG. 1 is a frontal view of a submerged pump according to the present invention;
[0023] FIG. 2 is a side view of the same submerged pump;
[0024] FIG. 3 is an axonometric view of the submerged pump;
[0025] FIG. 4 is a plan view of the submerged pump;
[0026] FIG. 5 is an axonometric view of the upper closing assembly of the submerged pump of the present invention;
[0027] FIG. 6 is an axonometric view of the bayonet fixing means of the electrical cable protection means of the pump;
[0028] FIG. 7 is an axonometric view of said electrical cable protection means of the pump;
[0029] FIG. 8 is an axonometric view of the quick fixing means of said electrical cable protection means;
[0030] FIG. 9 is an axonometric view of a resilient protection band of the pump which serves as a filter for the suction openings.
[0031] In the figures, corresponding parts or parts with like functions are provided with the same reference characters for simplicity purposes. Similarly, in the figures, for clarity purposes of the whole, the operation of the operative members of the pump, consisting of a pumping assembly and a motor assembly of the electric type with the motor axis and the mechanism and circuit element sets, is not illustrated because they are already known, and also because they are not required for a proper understanding of the present invention.
DESCRIPTION
[0032] With particular reference to these figures, numeral 1 indicates as a whole a pump 10 of the submerged type according to the invention. The pump 1 comprises an essentially cylindrical central body, which receives impellers, of the known type, intended to transfer a liquid in which the pump 1 is at least partially submerged. The central body is laterally closed by a cylindrical wall 20 , and is closed at its top by a closing assembly 21 , usually provided with handles or other known gripping means. The closing assembly 21 includes one or more outlet holes for delivery pipes of the processed liquid. The central body is inferiorly closed by a base, which has appropriate openings for introducing fluid to be processed and for a mechanical connection to a driving member of known type (not shown).
[0033] The lower base of the central body is inferiorly and coaxially connected to an essentially cylindrical lantern-sleeve 6 . The lantern-sleeve 6 is, in turn, inferiorly connected to the driving member for operating the pump.
[0034] The lantern-sleeve 6 has a plurality of openings positioned in the lateral surface, adapted to allow the introduction of liquid to be processed. The lantern-sleeve 6 further has a cavity 7 radially positioned in the lateral surface, partially externally enclosed by a pair of teeth 10 a , 10 b . The cavity 7 is inferiorly open to allow the electrical supply cables of the driving member underneath to pass outwards.
[0035] The lantern-sleeve 6 is partially lined with a resilient protection band 12 , appropriately provided with a plurality of through holes, adapted to allow the passage of the liquid to be processed, thus preventing the introduction of possible foreign bodies. The band 12 is wound about the lantern-sleeve 6 and is press fitted at the cavity 7 , thus remaining locked in place by virtue of the teeth 10 a , 10 b which are inserted into respective notches 14 a , 14 b positioned on the lower edge of the band 12 .
[0036] The pump 1 comprises protection means 2 of the electrical supply cables of the driving member, externally restrained to the body of pump 1 , so as to form a raceway for receiving the cables themselves. The protection means 2 preferably consist of a profiled element having an essentially U-shaped section, longitudinally provided with a pair of edges 11 a , 11 b which protrude outwards, adapted to be put in contact with the lateral wall 20 of the pump 1 .
[0037] The profiled element 2 is inferiorly restrained to the pump 1 by means of first bayonet fixing means 5 , essentially consisting of the cavity 7 of the lantern-sleeve 6 and the respective teeth 10 a , 10 b . In particular, the lower terminal portion 8 of the profiled element 2 is adapted to be inserted with a bayonet fitting into the cavity 7 , and locked in position by the contrast action exerted by the walls of the cavity 7 and by the teeth 10 a , 10 b . For this purpose, in order to facilitate the fitting of the profile 2 , the terminal portion 8 advantageously has a longitudinally flared profile.
[0038] The profiled element 2 is further superiorly restrained to the lateral wall 20 of the pump 1 by means of quick fitting means 4 , restrained to the body of pump 1 and adapted to be elastically deformed to receive and hold the upper portion of the profiled element 2 . In particular, the second quick fitting means 4 preferably consist of U-shaped receptacles with resilient tails 13 a and 13 b which engage in notches 9 positioned along the protection means 2 . Said essentially U-shaped section receptacles 4 are either riveted or preferably spot soldered 14 or joined with adhesives to the cylindrical lateral wall 20 of the body of the pump 1 . Said resilient tails 13 a and 13 b are inwardly shaped, adapted to elastically deform to receive and hold the profiled element 2 at the notch 9 positioned along the upper longitudinal edge of the profiled element 2 .
[0039] The use of the submerged pump according to the invention, and in particular of the electric cable protection system, may easily be inferred from the above description.
[0040] In order to rapidly assemble the cable protection system once the pump has been installed, it is sufficient to bayonet fit the terminal part 8 of the profiled element 2 into the cavity 7 , and then lock the upper part of the element 2 against the lateral wall of the pump 1 by exerting a pressure in the radial direction at the grooved seat 9 .
[0041] The submerged pump according to the invention thus achieves the object of providing a quick fitting, electric cable protection device. In particular, such a result is obtained by virtue of the presence of the quick fitting means 4 , adapted to elastically deform to receive and hold the electrical cable protection means 2 .
[0042] An advantage of the invention is that the described cable protection device reduces the time to assemble and set-up the pump, a feature which is particularly useful and appreciated in the case of movable submerged pumps, which require easy and rapid transportation and installation to allow an effective use thereof under emergency conditions.
[0043] Another advantage of the cable protection device according to the invention resides is the low construction cost. In the practical embodiment of the invention, the materials employed, as well as the shape and size thereof, may be varied according to needs. Where the technical features mentioned in each claim are followed by reference signs, these reference signs are included for the sole purpose of improving the understanding of the claims and, therefore, they have no restrictive value on the aim of each element identified by way of example by these reference signs. The invention here suggested by an original solution, is not obviously restricted to the only embodiment for the protection of electrical cables outside the submerged pump, which was described above by way of example; on the contrary, it includes all variants thereof deriving from the same principle and which may differ in various constructional forms, and it is apparent that all the technically equivalent solutions are within the scope of the present invention. | The present invention concerns a submerged pump with electrical cables external of the cylindrical lateral wall wherein the protection means, conformed for the lodging of said cables, are predisposed to be restrained to the pump body by means of quick fixing devices associable to bayonet sliding triggers for quick and stable locking and releasing, between said means of protection and the lateral wall of the pump, with possibly interposed fixed lantern elements and a resilient protection band as a suction filter. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the formation of investment casting molds by the lost wax process and, more particularly, to a method and apparatus for drying layers of ceramic slurry on a pattern of the article to be cast.
2. Description of the Prior Art
The lost wax process for forming investment casting molds in well known in the prior art and involves dipping an expendable pattern of the article to be cast into a slurry of ceramic particles, drying the layer of slurry on the pattern and repeating the sequence until the desired thickness for a mold wall is obtained. Oftentimes, dry particulate ceramic material is applied to the wet layer of slurry before it is dried to effect more rapid buildup of the wall. After the desired wall thickness is obtained, the pattern is removed and the ceramic layers are heated for consolidation into a strong mold to be used in casting.
Drying of the layers of ceramic slurry is one of the most critical steps in the process and is one of the most troublesome. Mold defects, such as cracking, flaking, bulging and the like, are frequently encountered and result in high mold rejection rates. The most common cause of such defects is the premature drying and consequent harmful overheating and expansion of those portions of the pattern which are easiest to dry. For example, in drying a layer of ceramic slurry on a wax pattern of a gas turbine blade or vane, it has been observed that the airfoil portion of the pattern dries much faster than the root or shroud portions and that the airfoil portion is more prone to overheating. Further, if the part is to be cast by directional solidification techniques, such as described in U.S. Pat. No. 3,260,505, wherein the mold is provided with an integral base, it has been observed that the base is one of the most difficult to dry areas of the assembly as a result of gravitational migration of moisture from the upper pattern surfaces to the base. In this case, the layer of slurry on the pattern may be adequately dried long before that on the base.
Attempts by prior art workers to limit the frequency of mold defects which originate during the drying step are exemplified by U.S. Pat. Nos. 2,932,864, 3,191,250 and 3,850,224. The drying process and apparatus of the last-cited patent appear to have been the most successful and involve conveying patterns coated with a layer of ceramic slurry through a U-shaped tunnel having two leg sections connected at one end by an impact drying section and open at the other end to a work room. High velocity drying air is directed laterally over the patterns in the impact drying section and then travels down each tunnel leg to effect further drying of the patterns therein. Drying is achieved by controlling the temperature and humidity of the air entering the impact drying section such that the wet bulb temperature is equal to the initial pattern temperature and is at least 10° F. below the dry bulb temperature. Each layer of ceramic slurry is dried in a separate tunnel, the wet bulb temperature of the drying air being held substantially constant from tunnel to tunnel while the dry bulb temperature is progressively increased. Although the process and apparatus of U.S. Pat. No. 3,850,224 and the other cited patents are improvements over the prior art, they nevertheless suffer from numerous disadvantages.
First, the drying air circulating through the tunnel is conditioned and controlled only at the entrance to the impact drying section. There is no provision for varying the temperature, humidity or velocity of the drying air after it enters the system in response to changes in the drying kinetics of the slurry layer. Also, there is no provision for ensuring that the humidity of the drying air in each section of the tunnel is uniform. As the coated patterns in the leg and impact drying sections dry and release moisture, it is possible to have drying air of different humidity in different sections of the tunnel. This lack of uniformity makes precise control over the drying process extremely difficult to achieve. Second, large patterns or clusters of multiple patterns tend to shield one another from the longitudinal airflow in the tunnel legs. This shielding inhibits even and complete drying of the patterns. Third, the exact drying time which is best for each layer of ceramic slurry cannot be achieved because all the tunnels are of the same length and the conveyor speed at each tunnel is the same. Fourth, there is no provision for adjusting the drying parameters to particular pattern shapes and sizes. Large patterns requiring long drying times and small patterns requiring much less drying time are subjected to similar drying schedules. In addition, all patterns, regardless of size and shape, are subjected to the same airflow distribution in the tunnel. No provision is made for adjusting the direction of airflow to concentrate airflow differently on different pattern shapes. These, as well as other, disadvantages severely limit the effectiveness of the prior art systems in reducing the incidence of mold defects originating during the drying step of the mold formation process.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide an improved method and apparatus for drying the layers of ceramic slurry applied over patterns in the formation of investment casting molds.
It is another object of the invention to significantly reduce the incidence of cracking, flaking, bulging and other mold defects which originate during the drying step of the mold formation process.
It is another object of the invention to provide means for drying coated patterns more uniformly than has heretofore been possible.
It is still another object of the invention to improve the quality of investment casting molds while at the same time improving production rate.
The present invention may be characterized as possessing several important features, one of which is related to the discovery that, during drying, the rate of moisture removal from the slurry layer on easy to dry areas of the pattern is initially very rapid but in a short time decreases to considerably lower levels and that harmful increases in pattern temperature at these areas correspond generally with this reduction in moisture removal kinetics. One feature of the present invention is a drying process in which harmful increases in pattern temperature resulting from such a reduction in moisture removal rate are prevented by providing drying air of different quality during the different stages of moisture removal from the slurry layer. In the preferred practice of the invention, drying air having a wet bulb temperature, dry bulb temperature and velocity specially suited for rapid moisture removal from the slurry layer is initially employed in the drying process. However, after drying has progressed to the stage where harmful increases in pattern temperature are likely to occur as a result of reduced moisture removal kinetics, drying air of a different quality is employed. Generally, the drying air employed in the latter stage of the drying process will have, singly or in combination, a reduced wet bulb temperature, a reduced dry bulb temperature and increased velocity, as compared to the drying air utilized in the rapid moisture removal stage.
Another feature of the present invention is a drying system having means to optimize the time that each layer of ceramic slurry and each size and shape of pattern is dried. Still another feature of the invention is a drying system in which each coated pattern is dried with drying air whose quality and flow are unaffected by other patterns being dried in proximity thereto. A further feature of the invention is a drying system having means for concentrating flow of the drying air differently on different pattern shapes.
In a typical embodiment of the invention, patterns having a layer of ceramic slurry thereon are conveyed through a tunnel having an alternating series of individual drying and exhaust stations therein. At each drying station, drying air of controlled wet bulb and dry bulb temperatures and velocity is directed over the coated patterns transverse to their direction of advancement in the tunnel. Adjustable louvers are provided at each drying station to concentrate the flow of the drying air on those portions of the particular pattern which are most difficult to dry. After the drying air passes over the coated patterns, it is removed through the exhaust stations before it can adversely influence other drying stations in the tunnel. In accordance with the invention, drying air of a different quality is supplied to those drying stations where harmful increases in pattern temperature are likely to occur as a result of reduced moisture removal kinetics of the slurry layer. Optimum drying time for each layer of ceramic slurry is provided by proper selection of the time during which the coated patterns are progressively dried at each drying station and the number of drying stations to which the patterns are exposed.
In this and other embodiments of the invention, it may be desirable and preferred to provide means for rotating the coated patterns with their major axis in a substantially horizontal plane during progression through the tunnel. Horizontal rotation of the coated patterns greatly reduces gravitational migration of moisture on the pattern surfaces and thus improves drying uniformity and the quality of the molds produced.
Other objects, uses and advantages of the present invention will become apparent to those skilled in the art from the following drawings, description and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a top view of the preferred drying apparatus partly broken away and partly in section to reveal the internal structure.
FIG. 2 is a perspective view of the incoming leg and a portion of the turnaround section of the preferred drying apparatus, partly broken away and partly in section to reveal the internal structure.
FIG. 3 is a vertical sectional view taken along line 3--3 in FIG. 1.
FIG. 4 is a fragmentary prespective view of the drying tunnel showing individual drying stations and exhaust stations.
FIG. 5 is a fragmentary view of the conveyor and associated carrier for vertical drying.
FIG. 6 is a fragmentary view of the conveyor and associated carrier for horizontal drying.
FIG. 7 is a graph of water weight loss from the slurry layer versus drying time for a conventional drying process.
FIG. 8 is a graph of pattern temperature versus drying time for a conventional drying process.
FIG. 9 is a top view of a drying apparatus especially adapted for horizontal drying.
FIG. 10 is a sectional view taken along line 10--10 in FIG. 9.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A preferred apparatus for practicing the present invention is illustrated in FIGS. 1 through 5. The drying apparatus, as shown, may be used to dry one or more of the layers of ceramic slurry which are applied over the patterns during the mold formation process. Those skilled in the art will recognize that a plurality of such apparatus would normally be utilized in the mass production of investment molds, one such apparatus being employed to dry each layer of ceramic slurry applied to the patterns. Although not shown in the drawings, a dip tank containing ceramic slurry and a dusting device containing dry particulate ceramic material are generally associated with each drying apparatus.
FIG. 1 is a top view of the preferred drying apparatus with a portion broken away to reveal the internal structure. Generally, the drying apparatus comprises a U-shaped tunnel 1, an endless overhead conveyor (not shown) to transport the patterns through the tunnel and two air conditioning units 2a and 2b. The tunnel has incoming and outgoing legs 4 and 6 which open at one end to a work room where the patterns are dipped in slurry and dusted with dry ceramic particulate and which are connected at the other end by turnaround section 8. In each tunnel leg are an alternating series of drying and exhaust stations A and B which are connected to air conditioning units 2a and 2b by air supply and return conduits disposed on each side of and beneath each leg of the tunnel. The number of drying stations provided in each leg will depend on the type of patterns being dried, type of slurry applied thereto, and other factors and may be selected as desired. As the coated patterns are conveyed through the tunnel, they are progressively dried at each drying station where drying air of controlled wet bulb and dry bulb temperatures and velocity is directed over the patterns transverse to their direction of advancement in the tunnel. After the air passes over the patterns, it is removed from the tunnel by the exhaust stations disposed adjacent each of the drying stations. As shown in FIG. 1 drying air of controlled wet and dry bulb temperatures and initially controlled velocity is supplied to those drying stations in leg 4 by air conditioning unit 2a and to those in leg 6 by air conditioning unit 2b. Separate air conditioning units are utilized so that the drying air passing over the coated patterns in leg 4 can have different wet and dry bulb temperatures and velocity than that in leg 6 in accordance with the method of the invention.
In the preferred practice of the invention, the patterns 10 of the article to be cast are incorporated into plastic frames 11, such as shown in FIGS. 3 and 5 and described in more detail in copending U.S. application Ser. No. 646,804, now U.S. Pat. No. 4,062,396 entitled "Method of Making a Unitary Pattern Assembly", and assigned to the assignee of the present invention. The resulting pattern assembly 12 is dipped in a tank containing ceramic slurry, dusted with dry ceramic particulate and then suspended from the endless overhead conveyor for transportation through leg 4, turnaround section 8 and leg 6 of the tunnel. Representative sections of the endless overhead conveyor are shown in FIGS. 3 and 5 as comprising a hollow metal tube 14 of rectangular cross section, the tube having longitudinal slots in the top and bottom surfaces. The tube is supported by brackets 16 from structural framework 18. Inside the tube is drive chain 20 having pairs of vertical rollers and horizontal rollers rotatably attached thereon and cog members 22 fixedly attached thereon. The vertical rollers ride on the inside bottom surface of tube 14 while horizontal rollers travel in spaced relationship in the longitudinal slots. Attached to each cog member is vertical tube 24 which is adapted to rotatably receive shaft 26. Shaft 26 extends vertically downward to carrier 28 to which it is fixedly attached. Carrier 28 is C-shaped and has base plate 30 having a slot, notch or the like suitably located therein to receive flanged handle 32 of the pattern assembly, as shown in FIG. 5. If it is desired to rotate the pattern assembly at each drying station, shaft 26 may be provided with circular member 34, which member may be rotated by suitable means, not shown, such as a moving belt or the like. By utilizing such an arrangement, the patterns may be rotated at each drying station independently of conveyor movement. The pattern assembly is moved through the U-shaped tunnel by providing suitable means, such as hydraulic ram 38, for imparting translational motion to cog members 22. The frequency with which cog members are translated will determine the time during which the pattern assemblies are dried at each drying station. This frequency may be varied as desired to suit the particular size and shape of pattern being dried. Alternatively, continuous conveyor means, which are well known in the art, may be provided to advance the pattern assemblies continuously through the tunnel at a desired speed.
As shown most clearly in FIG. 1, each tunnel leg and air conditioning unit are of the same construction. Tunnel leg 4 and air conditioning unit 2a are illustrated in more detail in FIGS. 2 and 3. The tunnel leg is shown as having an alternating series of drying and exhaust stations A and B which are connected to air conditioning unit 2a by air supply conduits 40, 42, 44, 46 and air return conduits 50 and 52 disposed on each side of and beneath the leg. The lower half of the drying tunnel is formed by walls 56 of air supply conduits 40, walls 58 and 60 of air return conduits 50 and wall 62 of air supply conduit 46. The upper half includes upper wall 64, inclined sidewalls 66 and vertical side walls 68, vertical side walls 68 being connected to the top walls of air supply conduits 40 by flanges 70. Upper wall 64 is provided with longitudinal slot 72 of sufficient width to accommodate shaft 26 of the conveyor and allow movement thereof through the U-shaped tunnel.
In operation, blower 74 forces air upwardly through vertical conduit 76 of rectangular cross section which communicates with the bottom wall of horizontal conduit 78. Horizontal conduit 78 has velocity damper 80 and humidification means 82 therein, the velocity damper being adjustable to provide initial control of the drying air velocity and the humidification means providing drying air of controlled humidity (or wet bulb temperature). The partially conditioned air then flows down vertical conduit 84 of rectangular cross section across heater 86 which heats the drying air to the desired dry bulb temperature. As seen most clearly in FIG. 1, the drying air is then split into three segments upon leaving conduit 84. One segment flows into short, vertical conduit 88 which communicates with the top wall of horizontal supply header conduit 46. The entrance to conduit 88 is provided with volume damper 89 to regulate the proportion of the air in conduit 84 which flows therein. Supply header conduit 46 is of rectangular cross section and extends under turnaround section 8 and longitudinally beneath tunnel leg 4, being centrally disposed thereunder as shown in FIG. 3. The other segments of the drying air in conduit 84 flow downwardly into vertical conduits 90 wherein deflection means (not shown) direct the air outwardly into horizontal supply conduits 44. Supply conduits 44 are located on each side of supply header conduit 46 and extend to short, vertical supply conduits 42 of rectangular cross section. The drying air flows horizontally through conduits 44 and into horizontal supply header conduits 40 which are disposed on each side of leg 4 as shown in FIG. 3. Supply header conduits 40 extend parallel to leg 4 a sufficient distance to distribute drying air to all the drying stations therein.
The drying air in header conduits 40 is then directed through the drying stations and over the coated pattern in tunnel leg 4, removed through the exhaust stations and collected in return header conduits 50 of rectangular cross section. Return header conduits 50 are positioned below supply header conduits 40 as shown in FIGS. 2 and 3 and direct the moisture-laden air to horizontal return conduits 52. Horizontal return conduits extend longitudinally beneath supply conduits 44 and direct the return air into plenums 92 as shown most clearly in FIG. 2. Make-up air, used to lower the relative humidity of the return air if dehumidification means are not provided in the air conditioning units, is directed into plenums 92 by vertical conduits 94 which have openings 100 to the outside atmosphere. Control dampers 102 and 104 are suitably positioned in return conduits 52 and make-up conduits 94 to regulate the proportion of return air and make-up air supplied to the plenums such that the total air supply remains essentially constant regardless of the percent make-up air added. Control dampers 102 and 104 are connected by inclined linkages 106 and horizontal linkages (not shown) so that they may be operated simultaneously to achieve proportional flow control. If make-up air is to be added to the plenums, control dampers 102 are closed and control dampers 104 are opened simultaneously by actuating linkage 106 with a conventional pneumatic damper operator, excess return air being exhausted from the tunnel through slot 72 in upper wall 64. Plenums 92 communicate with blower 74 and supply the desired mixture of return air and make-up air to each side of the blower.
As mentioned above, the drying air in supply header conduits 40 is directed over the coated patterns at each drying station. FIGS. 3 and 4 illustrate that each drying station is comprised of two horizontal conduits 110 positioned on opposite sides of the tunnel leg in an opposed relationship. The conduits 110 are defined by parallel vertical walls 112, upper horizontal wall 114 and lower horizontal wall 58 and communicate with the tunnel at the outlet end and with supply headers 40 at the inlet end. The opening into supply header 40 is covered by a velocity baffle, such as fixed, vertical plate 120 and a slidable, vertical plate 122, both of which have openings, such as spaced, parallel slots 124, therein. Plate 122 is rigidly attached to control rod 126 having handle 128. By turning handle 128, plate 122 may be moved vertically up or down relative to plate 120 to vary the slot opening and thereby provide final control of the velocity of the air in conduits 110. The velocity of the air at each drying station may be independently controlled in this manner. The combined action of plates 120 and 122 and velocity damper 80 in horizontal conduit 78 of the air conditioning unit permits the velocity of the drying air in conduits 110 to be controlled over a wide range; for example, up to about 2500 feet per minute. Preferably, the velocity of the drying air through conduits 110 is approximately twice that in supply header conduits 40 to achieve equal airflow through each drying station. If desired, airflow into a drying station may be stopped altogether by suitable movement of plate 122. In this way, the number of drying stations to which the patterns are exposed in the tunnel legs may be varied as desired. Optimum drying time for each layer of ceramic slurry and each size and shape of pattern can be provided by controlling the number of drying stations to which the patterns are exposed and the time during which the patterns are dried at each station. As shown in the figures, the conduits 110 have opposed outlet ends opening into the drying tunnel. The outlet ends are provided with a plurality of parallel adjustable louvers 130 spaced horizontally thereacross. All the adjustable louvers at a given level in the drying stations are rigidly attached to common control rods 132 which are rotatably mounted on flanges attached to walls 112. Rods 132 extend horizontally through the drying and exhaust stations and are provided with handles 134 where they protrude from the end walls of each tunnel leg as shown in FIG. 1. The angular position of the louvers can be varied from about 0° to 90° relative to vertical by turning handles 134. In the drying process, the angular position of the louvers is adjusted for each pattern shape to concentrate flow of the drying air on those portions of the pattern which are most difficult to dry. In this way, impingement of the drying air on the coated patterns can be controlled to achieve optimum moisture removal and more uniform drying of the patterns.
As explained hereinbefore, vertical conduit 88 directs air into horizontal supply header conduit 46 which extends longitudinally and centrally disposed beneath each tunnel leg, as shown most clearly in FIGS. 3 and 4. In the preferred drying apparatus of the invention, supply header 46 is provided with openings in its upper horizontal wall 62. These openings are located between the opposed outlet ends of conduits 110 and are covered by baffle plates 136 and 138, both of which have spaced, parallel slots 140 therein for controlling the velocity of the air passing therethrough. Plate 136 is fixedly attached to wall 62 of the header conduit while plate 138 is slidably mounted a short distance above plate 136. Slidable plate 138 is attached rigidly to control arm 142 having handle 144. Although not essential to the present invention, supply header conduit 46, plates 136 and 138 and their related components are desirable in the mass production of investment molds to direct air vertically against the bottom of the pattern assembly at each drying station. This insures that the slurry layer on the bottom of pattern assembly is dried and thereby prevents slurry from one dip tank from being carried into other dip tanks. If the bottom of the pattern assembly is not to be dried, the supply header conduit and associated velocity baffle plates may be removed and replaced by a flat plate to enclose the bottom of the tunnel leg between return conduits 50.
After the drying air passes over the coated patterns at each station, it is exhausted from the tunnel leg through the exhaust stations disposed adjacent the drying stations. The exhaust stations are seen most clearly in FIGS. 3 and 4 wherein it is shown that each exhaust station comprises an opening 146 of rectangular cross section disposed adjacent each of conduits 110 of each drying station, the openings being covered by damper means, such as doors 148. As illustrated in FIG. 4, the openings are located in horizontal wall 58 which forms a portion of the tunnel bottom and the doors 148 are rotatably mounted on flanges attached to said wall. The doors of each exhaust station are attached by linkages 150 to common control arm 152 having handle 154. By manipulating the handle, the doors 148 of each exhaust station may be opened to connect the interior of the tunnel to return header conduits 50. The pressure in the tunnel may be adjusted as desired by varying the extent to which the doors are open. Usually, a slight positive air pressure is maintained in the tunnel to prevent infiltration of outside air through slot 72 in upper wall 64 and through the entrance and exit ends of the tunnel. After the drying air passes over the patterns at each drying station, it is quickly exhausted from the tunnel leg through the openings 146 and collected in return header conduits 50. In this way, moisture-laden air from one drying station is prevented from interfering with the drying air of controlled quality at other stations in proximity thereto.
In the preferred apparatus illustrated herein, the blower size and configuration of the tunnel and conduits are selected such that a maximum air velocity across the patterns of about 2000 feet per minute can be attained, the velocity damper 80, plates 120 and 122 and plates 136 and 138 being in the full open position. As mentioned, under normal operating conditions, the drying air in the tunnel will have a slight positive pressure to preclude infiltration of outside air through the slot in the upper wall and through the entrance and exit ends of the tunnel. When make-up air is added to the system by simultaneously closing control dampers 102 and opening control dampers 104, excess pressure in the system is relieved through slot 72 in upper wall 64 of the tunnel.
The method of the present invention is a significant departure from prior art practices wherein each layer of ceramic slurry is dried in a tunnel supplied with air of one quality, i.e., air having constant wet bulb and dry bulb temperatures, during the entire drying time. In addition, in the prior art, the wet bulb temperature is maintained constant at a value equal to the initial pattern temperature. As shown in FIG. 7, under such drying conditions, the rate of moisture removal from the slurry layer on easy to dry areas of the pattern is initially very rapid but in a short time, generally 5 to 10 minutes, decreases to considerably lower levels. It has been discovered from experimental drying tests that harmful increases in pattern temperature at the easy to dry areas correspond generally with the decrease in the moisture removal kinetics of the slurry layer, as shown in FIG. 8. Of course, the exact shape of the curves in FIGS. 7 and 8 will vary with such factors as the type of slurry being dried, the type of ceramic particulate applied to the slurry layer before drying, the temperature and humidity of the drying air and the like. The present invention effectively minimizes the harmful increases in pattern temperature caused by such a reduction in moisture removal kinetics during drying.
According to the invention, the temperature of the pattern is allowed to vary within critical limits during drying. The limits will of course vary with the type of pattern material being employed but, for most pattern waxes, has been found experimentally to be from about 60° F. to about 85° F. If the temperature of the wax pattern exceeds these limits, defective investment molds will normally result. Generally, in the practice of the invention, the initial temperature of the pattern is selected to be room temperature, which is usually from 75° to 85° F. In carrying out the process of the invention with the preferred apparatus illustrated herein, the coated patterns at room temperature are conveyed through the U-shaped tunnel in which the first series of 7 drying stations in leg 4 removes moisture from the slurry with air of a quality adapted to high removal rates and the second series of 7 drying stations in leg 6 removes the remaining moisture with air of a different quality, specifically adapted to prevent harmful increases in pattern temperature due to the reduction in moisture removal rate. The time during which the coated patterns are dried at each station and the number of stations to which the patterns are exposed are selected as desired to ensure that the reduction in moisture removal rate occurs near the end of the first series of drying stations or, preferably, shortly after the patterns have been conveyed therethrough. Preferably, 95 to 100% of the so-called "easy water" (see FIG. 7) of each layer is removed in the tunnel, about 65 to 75% being removed in the first series of drying stations and the remainder being removed in the second series. Attempts to remove the so-called "residual water" (see FIG. 7), which amounts to 10 to 15% of total moisture, in relatively short times, such as 15 min. -20 min., will result in severe pattern overheating. "Residual water" is therefore not removed in the drying apparatus of the present invention.
In removing moisture from the slurry layer in the first series of drying stations in leg 4, the drying air may have a quality, including wet bulb and dry bulb temperatures and velocity, customarily employed in the prior art tunnels to dry the various layers of ceramic slurry. For example, in drying the first (prime) slurry layer, a wet bulb temperature of 75° F. and a dry bulb temperature of 90° F. could be employed in combination with an air velocity across the patterns of at least 400 feet per minute. Total drying time in leg 4 would be selected to ensure that reduced moisture removal kinetics occur near the end thereof or, preferably, after the coated patterns have been conveyed therethrough. For the second and third layers of slurry, a wet bulb temperature of 75° F. and a dry bulb temperature of 95° F. could be employed in combination with an air velocity of at least 400 feet per minute. The remaining layers of slurry could be dried similarly. It should be noted that in prior art drying tunnels, the entire drying time is spent at these air qualities; in the present invention these air qualities exist only in the first series of drying stations in leg 4 where reduced moisture removal kinetics are insignificant.
Preferably, however, the quality of the drying air supplied to the first series of drying stations is substantially different from that used in the prior art. According to the invention, the wet bulb temperature of the air in the first series of drying stations is maintained substantially below the initial pattern temperature and may be in the range from about 60° F. to 70° F. This differs radically from the prior art processes wherein the wet bulb temperature of the air is kept constant during drying at a value equal to the initial pattern temperature. The dry bulb temperature is at least 10°, preferably 20°-25°, above the wet bulb temperature and is selected to provide a relative humidity in the range from 10 to 60%, preferably 30 to 50%. The velocity of the drying air passing over the patterns is then selected in the range from about 200 to 2000 feet per minute, preferably 200 to 700 feet per minute to obtain the desired drying rate. Drying time in leg 4 is selected as described above. During such nonadiabatic drying in the first series of drying stations, the temperature of the pattern, if wax, will decrease after a few minutes, e.g. 2 to 3 minutes, and tend to approach the wet bulb temperature of the drying air as a result of the pattern giving up the latent heat of vaporization. So long as the pattern temperature does not fall below about 60° F., this decrease is harmless and is actually beneficial in that it inhibits deleterious pattern heatup during drying in the first series of stations. The rate of moisture removal is very rapid in the first series of drying stations and preferably removes from 70-75% of the "easy water" from the slurry layer. The danger of pattern heat-up is minimal since drying has not progressed to the stage where the rate of moisture removal from the slurry layer has decreased sufficiently to cause harmful increases in pattern temperature.
The partially dried coated patterns are then conveyed to the second series of drying stations in leg 6 via turnaround section 8 which serves no other purpose. At the second series of drying stations, the remaining "easy water" is removed from the coated patterns with drying air of a quality different from that supplied to the first series, the quality being specifically adapted to remove the remaining "easy water" without harmful increases in pattern temperature due to reduced moisture removal kinetics. As compared to the drying air supplied to the first series of drying stations, that supplied to the second series will have, singly or in combination, a reduced wet bulb temperature, reduced dry bulb temperature or increased velocity. By suitable adjustment of these parameters in the second series of drying stations, the harmful increase in pattern temperature evident in FIG. 8 and corresponding to the reduction in the moisture removal rate in FIG. 7 can be effectively minimized, if not eliminated. Of course, the exact wet bulb and dry bulb temperatures and velocity selected for the air supplied to the second series of drying stations will depend upon the air quality at the first series, the particular slurry layer being dried and other factors. By way of example, in drying each of the first three layers of slurry in accordance with the preferred method of the invention, the air passed over the coated patterns in the first series of drying stations would have wet bulb and dry bulb temperatures of 70° F. and 85° F., respectively, and a velocity over the patterns of about 600 feet per minute. In contrast, in the second series of drying stations, the drying air could have wet bulb and dry bulb temperatures of 62° F. and 75° F., respectively, and a velocity of about 1200 feet per minute. Generally, in the second series of stations, the wet bulb temperature will be in the range from 55° to 70° F., preferably 60° to 65° F., and the dry bulb will be maintained at least 10°, preferably 20 to 25°, above the wet bulb to provide a relative humidity from 10 to 60%, preferably 30 to 50%. Velocity of the drying air across the patterns will be from about 200 to about 2000 feet per minute, preferably 700 to 1400 feet per minute.
Conventional and well-known devices may be employed to measure the wet and dry bulb temperatures of the drying air and its velocity in each series of stations. These devices (not shown) may be conveniently located, such as in conduits 110, and may be wired to a control station to automatically control velocity damper 80, humidifier 82 and heater 86. In order to continually provide drying air of 10 to 60% relative humidity during the drying process, it may be necessary to have dehumidification means incorporated in air conditioning units 2a and 2b or in conduits 94 through which make-up air is drawn or to house the entire drying apparatus in a room having such controlled humidity.
As mentioned hereinbefore, the most common cause of mold defects is the premature drying and consequent harmful overheating of certain portions of the pattern. Premature drying may oftentimes be aggravated by the fact that the patterns are dried in the vertical position. The problem is especially acute in producing investment molds for directional solidification processes wherein the mold is provided with an integral base. During the drying of such molds, water in the slurry layer migrates under gravitational force to the mold base and other horizontal platform-like areas on the pattern. Moisture migration from one surface to another promotes nonuniform drying of the pattern and results in a greater incidence of mold defects. In a preferred embodiment of the present invention, the coated patterns are rotated with their major axis in a substantially horizontal plane after being coated with the slurry layer and during their progression through the U-shaped tunnel and drying stations. Horizontal rotation of the patterns greatly reduces gravitational moisture migration and thus improves drying uniformity and the quality of molds produced.
The preferred apparatus illustrated hereinabove may be readily adapted to effect horizontal rotation of the coated patterns as shown in FIG. 6. In this embodiment, the plastic frame 11 in which the pattern is incorporated is provided with a base 160 having a cylindrical projection 162 on the bottom thereof. The projection 162 is in axial alignment with cylindrical handle 32 and is, preferably, of the same diameter. The carrier is provided with vertical members 164 which are adapted to rotatably receive projection 162 and handle 32, as shown. A small motor 166, preferably battery powered, is located near the base plate projection and has spindle 168 adapted to engage the projection and rotate the pattern assembly in the horizontal plane. The pattern is thus held with its major axis horizontally oriented and simultaneously rotated about said axis as it progresses through the tunnel.
Alternatively, a drying apparatus especially designed for horizontal drying of the patterns in accordance with the invention may be utilized. One such embodiment is illustrated in FIGS. 9 and 10. It includes the same general components as the preferred drying apparatus described in detail above, including a U-shaped tunnel having incoming and outgoing legs 4' and 6' which are connected to air conditioning units 2a' and 2b' by air supply and return conduits. An endless conveyor is provided to convey the patterns through the tunnel while simultaneously rotating them with their major axis in the horizontal plane.
The conveyor is positioned with the "U" formed by the tunnel legs and the turnaround section. The handle 32 of the pattern assembly is gripped by a chuck 170 which is mounted on horizontal shaft 172 extending rotatably through housing 174. The end of shaft 172 opposite the chuck has roller 176 attached thereto. The roller is driven by conventional means, such as a moving belt or the like, to impart continuous horizontal rotation to the pattern. The patterns are conveyed through the tunnel by overhead conveyor 178 which is connected to the housing by arm 180. To maintain proper positioning of the housing, L-shaped bracket 182 is attached thereto, the bracket having a roller 184 positioned thereon to travel in a locating slot projecting from support structure 186.
In operation, air conditioning units 2a' and 2b' supply conditioned drying air to the drying stations in tunnel legs 4' and 6', respectively, through air supply headers 40' disposed above the tunnel. Each drying station is comprised of one vertical conduit 110' opening into the tunnel at its lower end and into air supply header 40' at the top end. The opening into the supply conduit is covered by fixed and slidable plates, both of which have spaced, parallel slots therein and the opening into the tunnel is covered by adjustable louvers, these components functioning as described above with regard to the preferred drying apparatus. The apparatus may also include air supply headers 46' and associated components for drying the bottom of the pattern assemblies as they progress from one drying station to another in the tunnel.
After the drying air passes over the patterns, it is removed from the tunnel through exhaust stations disposed in opposed relation to the drying stations. Each exhaust station includes an opening 146' connecting the tunnel leg to air return header 50', the opening being oppositely disposed from the outlet end of conduit 110'. The opening is covered by door 148' rotatably mounted on the top wall of return header 50' as shown. The moisture-laden air at the drying stations passes through the openings, is collected in the return headers and is then carried beneath the drying tunnels to a plenum in the air conditioning units, where the return air may be mixed with make-up air. The desired air mixture is then fed into the blowers and passed through the velocity dampers, humidification means and heating means as described hereinabove with reference to the preferred drying apparatus.
Of course, those skilled in the art will recognize that the present invention may be practiced in numerous other ways. For example, individual drying stations, each supplied with drying air of a different quality by individual air conditioning units is within the scope of the invention. In such an embodiment, a drying tunnel to enclose all the drying stations may not be necessary. Also, instead of being conveyed through a U-shaped tunnel, the coated patterns may be transported through one longitudinal tunnel in which several series of drying stations are disposed, each series being supplied drying air of a different quality. In addition to those disclosed, various other configurations and orientations of drying stations and exhaust stations may be utilized to practice the present invention. | The method and apparatus of the present invention substantially reduce the incidence of cracking, flaking, bulging and other mold defects which originate during the drying step of the investment mold formation process. Drying is conducted under conditions which enhance uniformity of drying and which preclude harmful increases in pattern temperature resulting from changes in the moisture removal kinetics of the slurry layer. In particular, during the drying process, drying air of different quality is provided during the different stages of moisture removal from the slurry layer. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an apparatus for controlling a compressor used in an automobile air-conditioner.
2. Description of the Prior Art
Japanese Patent Laid-open Publication No. 60-22525 exemplifies an apparatus for controlling the displacement of a variable displacement compressor incorporated in an automobile air-conditioner and driven by an engine of the automobile. The apparatus includes means for setting a target cooling power of a cooler and means for measuring the actual cooling power of the cooler. The target cooling power is determined depending on various conditions such as thermal loads in the vehicle passenger compartment, a temperature set by an occupant, etc. The displacement of the variable displacement compressor is controlled by properly adjusting a displacement adjustment signal until the actual cooling power is in equal to the target cooling power.
According to the known control apparatus, the target cooling power varies with a change thermal load having an influence on the vehicle passenger compartment temperature or with a manual setting of the temperature by the occupant. A change in target cooling power directly varies the displacement of the compressor. Consequently, if the vehicle compartment setting temperature is greatly varied by manual settings of the occupant, the displacement of the compressor changes rapidly as a consequence of a sudden change of the target cooling power. Such a rapid change of the compressor displacement may increase the engine load which will affect the drivability of the automobile or provide an unpleasant feeling due to a sudden change in temperature of the discharged air.
A modified form of the compressor control apparatus is proposed by the present assignee, wherein the operation of the compressor continues even when the cooling power of the evaporator represented in terms of the temperature of the evaporator is below a freezing initiation temperature near 0° C. This is achieved either by setting the target cooling power to an extremely low temperature such as -10° C. to supply a maximum cooling power (cool-down control) when a quick cooling of the vehicle passenger compartment is needed, or by similarly setting the target cooling power to a low temperature to improve the demist performance characteristic (low temperature demist control) when the outside air temperature is low. However, a continuing operation under such a cool-down control and low temperature demist control is likely to cause a freezing of the evaporator which makes it impossible to return to the regular control mode.
SUMMARY OF THE INVENTION
With the foregoing difficulties in view, it is an object of the present invention to provide an apparatus for controlling a variable displacement compressor of an automobile air-conditioner, which apparatus is capable of preventing a sudden change in cooling ,power of an evaporator to thereby maintain the drivability of the automobile and to provide a pleasant air-conditioned feeling in the vehicle passenger compartment even when the setting temperature is greatly varied.
Another object of the present invention is to provide a highly reliable compressor controlling apparatus which is capable of properly selecting the rate of change of the displacement of a compressor depending on the current control condition so as to prevent freezing of the evaporator.
According to a first aspect of the present invention as shown in FIG. 1, there is provided an apparatus for controlling a compressor of an automobile air-conditioner, comprising: a variable displacement compressor 18 capable of varying its displacement according to an external control signal; a mode sensor 45 for detecting the cooling power of an evaporator 8 of the automobile air-conditioner; target cooling power change means 200 for manually or automatically changing a target cooling power for the evaporator 8; target cooling power change rate adjustment means 300 for limiting the rate of change of the target cooling power to a predetermined rate after the target cooling power is changed by the target cooling power change means 200; displacement determination means 400 for determining the displacement of the variable displacement compressor 18 in such a manner as to reduce the deviation of an actual cooling temperature of the evaporator 8 from the target cooling power the evaporator 8; and drive control means 500 for controlling the operation of the variable displacement compressor 18 according to the output from the displacement determination means 400.
According to a second aspect of the present invention as shown in FIG. 2, there is provided an apparatus for controlling a compressor of an automobile air-conditioner, comprising: a variable displacement compressor 18 capable of varying its displacement according to an external control signal; a mode sensor 45 for detecting the cooling power of an evaporator 8 of the automobile air-conditioner; target cooling power change means 200 for manually or automatically changing a target cooling power for the evaporator 8; target cooling power change rate adjustment means 300 for limiting the rate of change of the target cooling power to a predetermined rate after the target cooling power is changed by the target cooling power change means 200; change rate selection means 600 for selecting the target cooling power change rate from a plurality of preset values depending on a desired control condition to which the target cooling power is to be changed; displacement determination means 400 for determining the displacement of the variable displacement compressor 18 in such a manner as to reduce the deviation of an actual cooling temperature of the evaporator from the target cooling power of the evaporator; and drive control means 500 for controlling the operation of the variable displacement compressor 18 according to the output from the displacement determination means 400.
With this construction, when the target cooling power of the evaporator is changed either automatically by a change in thermal load in the vehicle passenger compartment, or manually by an occupant of the vehicle, the target cooling power varies gently at a limited rate until the target cooling power is obtained. The displacement of the compressor changes gently, too, so that a sudden change of the discharged air temperature can be prevented. The change rate of the target cooling power is selectable, so the rate of change of the compressor displacement can be controlled so as to preferentially perform the anti-freezing operation of the evaporator.
The above and other objects features and advantages of the present invention will become manifest to those versed in the art upon making reference to the detailed description and the accompanying sheets of drawings in which a preferred structural embodiment incorporating the principles of the present invention is shown by way of illustrative example.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing the general construction of a compressor controlling apparatus according to a first embodiment of the present invention;
FIG. 2 is a block diagram showing the general construction of a compressor controlling apparatus according to a second embodiment of the present invention;
FIG. 3 is a diagrammatical view showing the general construction of an automobile air conditioner in which the compressor controlling apparatus shown in FIGS. 1 and 2 are incorporated;
FIG. 4 is a cross-sectional view of a variable displacement compressor used in the automobile air-conditioner;
FIG. 5 is a flowchart showing a first part of a control routine achieved by a microcomputer for controlling the variable displacement compressor; and
FIG. 6 is a flowchart showing a second part of the control routine shown in FIG. 5.
DETAILED DESCRIPTION
The present invention will be described hereinbelow in greater detail with reference to certain preferred embodiments shown in the accompanying drawings.
As shown in FIG. 3, an automobile air-conditioner in which principles of the present invention are embodied includes a main air-flow duct 1 having an intake door selection device 2 disposed at the upstream end of the main airflow duct 1. The intake door selection device 2 includes a selector door 5 disposed at the junction between a recirculated air inlet 3 and an outside air inlet 4 that are provided in bifurcated fashion. The selector door 5 is actuated by an actuator 6 to select the outside air or the recirculated air to be introduced into the main air-flow duct 1.
A blower 7 is disposed in the duct 1 adjacent to the air inlets 3, 4 for forcing the air to flow downstream through the main air-flow duct 1. The duct 7 also includes an evaporator 8 and a heater core g disposed downstream of the blower 7 in the order named. An air-mix door 10 is disposed in front of the heater core 9 and pivotally movable by an actuator 11 so that the ratio of the amount of air flowing directly through the heater core 9 to the amount of air bypassing the heater core 9 is adjusted depending on the opening of the air-mix door 10, thereby controlling the temperature of air blown off from the air-conditioner.
The main air-flow duct 1 has at its downstream end a defroster outlet 12, a vent outlet 13 and a heat outlet 14 that are provided in a branched fashion and all open to a vehicle compartment. Two mode doors 15a, 15b are disposed at the junction between the vent outlet 13 and heat outlet 14 and the junction between the heat outlet 14 and the defroster outlet 12. The mode doors 15a, 15b are actuated by actuators 16, 17, respectively, to set a desired discharge mode of the air-conditioner.
The evaporator 8 is in fluid communication with a variable displacement compressor 18, a condenser 19, a liquid tank 20 and an expansion valve 21 to jointly constitute a refrigeration cycle or system for cooling air passing around the evaporator 8. The variable displacement compressor 18 is of the swash plate type, for example. The swash plate type variable displacement compressor 18 includes, as shown in FIG. 4, a drive shaft 24 disposed in a compressor body 25 and coupled to an engine 22 (FIG. 3) via an electromagnetic clutch 23 (FIG. 3), and a swash plate 26 mounted on the drive shaft 24 by a hinge ball 27. The swash plate 26 thus mounted on the drive shaft 24 oscillates or swings about the hinge ball 27 within a crank chamber 28 so that at least one piston 29 connected to the swash plate 26 is reciprocated in a cylinder bore 30 in response to the oscillation of the swash plate 26. The variable displacement compressor 18 further has a pressure control valve 31 facing the crank chamber 28. The pressure control valve 31 includes a movable valve element 33 movable for adjusting the degree of communication between the crank chamber 28 and an intake chamber 32 communicating the intake side of the compressor 18, a pressure responsive member 34 responsive to the pressure in the intake chamber 32 for moving the valve element 3, and a solenoid 36 for displacing the valve element 33 according to the magnitude of an exiting current I SOL supplied to an electromagnetic coil 35. With the pressure control valve 31 thus constructed, the amount the blowby gas (leaking between the piston 29 and the cylinder bore 30) returned from the crank chamber 28 to the intake side can be adjusted by externally controlling the exciting current I SOL . The pressure control valve 31 constitutes a main part of a displacement adjustment device 37 (FIG. 3) for changing the displacement of the variable displacement compressor 18. When the exciting current I SOL flowing through the electromagnetic coil 35 is increased to enhance the magnetic force of the solenoid 36, the valve element 33 is displaced in a direction to reduce or limit the communication between the crack chamber 28 and the intake chamber 32, thereby lowering the amount of return of the blowby gas from the crank chamber 28 and the intake chamber 32. As a consequence, the : pressure in the crank chamber 28 increases, as does the force or pressure acting on the back of the piston 29. Thus, the swash plate 26 is pivoted about the pivot ball 27 in a direction to reduce it angle of oscillation, thereby reducing the stroke of the piston 29. The displacement of the compressor 18 is thus lowered.
The displacement adjustment device 37 is not limited to the pressure control valve 31 which is constructed to adjust the return of the blowby gas to the intake side as described above. It may be constructed to change the number of cylinders in the compressor, or the pulley ratio of a belt transmission mechanism coupling the compressor and the engine 22, In the case of a variable displacement compressor of the rotary vane type, the displacement adjustment device is constructed to change the number of vanes.
The actuators 6, 11, 16, 17, a motor 7a of the blower 7, the electromagnetic clutch 23 and the displacement adjustment device 37 of the variable displacement compressor 18 are controlled by output signals supplied thereto from a microcomputer 41 through corresponding drive circuits 4Oa-4Of, as shown in FIG. 3.
The microcomputer 41 is of a conventional type known per se and includes a central processing unit (CPU), a read only memory (ROM), a random access memory (RAM), an input/output port (I/O), a clock pulse generator having a quartz oscillator for generating a reference pulse, etc. (none of them shown). The microcomputer 41 is supplied with an output signal T R from a vehicle compartment temperature sensor 42 for detecting the temperature in the vehicle passenger compartment, an output signal T A from an outside air temperature sensor 43 for detecting the outside temperature, an output signal Q S from a sunlit portion temperature sensor 44 for detecting the radiation energy of the sun in the form of the temperature of a portion illuminated by the sun, and an output signal T INT from a mode sensor 45 disposed on or downstream of the evaporator 8 for detecting, as the power of the evaporator 8, the temperature of the evaporator 8 or the temperature of air passed through the evaporator 8. Before being inputted to the microcomputer 41, these output signals are selected by a multiplexer (MPX) 46 and then digitized by an A/D converter 47.
The microcomputer 41 is also supplied with output signals from an instrument panel 48. The instrument panel 48 is provided with an A/C switch 49 for starting the variable displacement compressor with all components of the air-conditioner set in an automatically controlled condition, an ECON switch 50 for economically controlling the variable displacement compressor 18 in the auto mode, an OFF switch 51 for instructing the stop mode, a REC switch 52 for selecting the intake mode between the recirculating air intake mode and the outside air intake mode, a DEF switch 53 for setting the discharge mode to the defrost mode, a temperature setter 54 for setting the temperature inside the vehicle passenger compartment, a blower power setter 55 for setting the power of the blower 7, and a discharge mode setter 56 for setting the discharge mode other than the defrost mode.
The temperature setter 54 is composed of up and down switches 54a, 54b and an indicator or display 54c for indicating a setting temperature T D . The setting temperature T D indicated on the display 54c can be varied within a predetermined range by properly actuating the up and down switches 54a, 54b. The blower power setter 55 includes a FAN switch 55a for selecting the level of rotation of the blower 7 and a level indicator 55b for indicating the current rotation level of the blower 7. By manually actuating the FAN switch 55a repeatedly, the power of the blower 7 is shifted in sequence between the stop mode (level 0), LOW mode (level 1), MID mode (level 2) and HI mode (level 3). In this instance, a word "MANUAL" is display above the indicator 55b. The mode setter 56 includes a MODE switch 56a for selectively setting the discharge mode between the vent mode, the bi-level mode and the heat mode, in sequence, and a graphic indicator 56b for indicating the current discharge mode by graphic image. When the MODE switch 56a is actuated, the direction of airflow in the selected mode is indicated on the graphic indicator 56b by at least one arrow 57a, 57b. In this instance, a word "MANUAL" is indicated above the graphic indicator 56b. The indicators 54c, 55b, 56b and the lighting are controlled by the microcomputer 41 via a display circuit 58.
FIG. 5 and 6 are is a flowchart showing a control program achieved by the microcomputer 41 for controlling the variable displacement compressor 18. The microcomputer 41 starts the program from a step 100. If steps 102, 104 and 106 judge respectively that the blower 7 is stopped, the OFF switch or the ECON switch is actuated to send an instruction to stop the variable displacement compressor 18, or the refrigerant temperature T REF is lower than a predetermined temperature, the control program advances to a step 108 to stop the variable displacement compressor 18 for preventing freezing of the compressor. If each of the steps 102, 104, 106 judges to the contrary, the control program proceeds to a step 110 which determines the condition of the outside air temperature among preset values (A, B, C or D) based on the outside air temperature T A (for example, T A >10=condition A, 5<T A 13=condition B, -5<T A <7=condition C, and -2>T A =condition D). The next step 112 judges whether the DEF switch 53 is depressed to set the discharge mode to the defrost mode. If the discharge mode is set to one other than the defrost mode, then the control program advances to a step 114. The step 114 judges whether the necessary discharge temperature XM calculated by the expression (1) before the control program routine is lower than -10° C.
X.sub.M =A·T.sub.D +B˜T.sub.R +C·T.sub.A +D·Q.sub.S +E (1)
where A, B, C, D are gains of T D , T R , T A and Q S , respectively, and E is a correction term.
If X M ≦-10 in this step 114, this means that a rapid cooling of the blow-off air is needed. Accordingly, the control program goes on to a step 116 to set a flag for executing the cool-down control. Thereafter, the control program advances to a step 118 to set the target cooling power T' INT of the evaporator 8° to -10° C. The cool-down control continues until the necessary discharge temperature X M exceeds 8° C. (step 120), or the actual cooling power of the evaporator 8 falls below 3° C. for more than 10 minutes (step 122). In the cool-down control, the displacement TINT of the variable displacement compressor 18 is controlled in a step 124 such that the deviation of T INT from T' INT is less than 1° C. If the condition of the step 120 or the step 122 is satisfied, the cool-down control is terminated in step 126. Then, a flag for a transition control is set in a step 128 to let the program return to the regular control and, thereafter, the control program proceeds to a step 130. If X M >-10 in the step 114, the control program goes on to a step 132 to determine whether the cool-down control is going on now. If yes, the control program proceeds to the step 118. If the cooling-down control is terminated, then the control program goes on to the step 130.
The step 130 makes a judgment as to whether the A/C switch 43 is depressed or not. If no, the control program advances to a step 134 to further judge whether the outside temperature is higher than the predetermined temperature. If judgment in step 134 is no, the control program moves to the step 108 to stop the variable displacement compressor 18. If the outside temperature is judged as exceeding the predetermined temperature in the step 134, then the control program advances to a step 136. The step 136 determines the target cooling power T' INT from a predetermined characteristic pattern based on X M . If the A/C switch 49 is depressed in the step 130, then steps 138, 140, 142,144 judge in succession whether the outside air temperature T A is in either condition A-D. In case of the condition D, the control program goes on to a step 150 to stop the variable displacement compressor 18. If the outside air temperature is in the condition C, or if the outside air temperature is in the condition B in the 142 and then the intake mode is set to the recirculating air intake mode (REC) in a step 144, the control program goes on to a step 146 to proceed with another control operation needed for the demist operation. In a condition other A than specified above, the target cooling power T' INT is set to 3° C. in a step 148.
If the discharge mode is set to the defrost mode in the step 112, the control program moves to a step 160 to judge whether the cool-down control is going on now. If yes, the cooling-down control is terminated in a step 162 and thereafter a flag needed for a transition control from the cool-down control to the regular control is set in a step 164. Then the control program advances to the step 138 stated above. If the cool-down control is terminated in the step 160, the control program jumps to the step 138 from which the operation continues in the manner as described above.
After the target cooling power T' INT is determined in the step 136 or the step 148, the control program advances to a step 166 to determine whether the low temperature demist control is now going on or not. If yes, this low temperature demist control is terminated in a step 168 and then a flag needed to a transition control to the regular control is set in a step 170. Thereafter, the control program proceeds to a step 172. If the low temperature demist control is terminated in the step 166, the control directly moves to the step 172. The step 172 judges whether the transition from the cool-down control to the regular control is now going on. In the next following step 174, a further judgment is achieved to determine whether the transition from the demist control to the regular control is now going on. If the transition control is not going on and the regular control is being achieved to the contrary, the control program advances to a series of following steps beginning from a step 176. In the step 176 it is judged whether the actual cooling power T INT of the evaporator 8 is greater than a predetermined temperature which is high enough to prevent freezing. If no, the control moves to a step 178 to stop the operation of the variable displacement compressor 18. If the actual cooling power T INT exceeds the predetermined temperature, the control proceeds to a step 180 to vary the target cooling power T' INT gradually toward the value determined in the step 136 or 148 with the agency of a first order lag filter having a time constant of 86 seconds. In the next following step 182, the displacement of the variable displacement compressor 18 is controlled until T INT approaches T' INT .
If the transition from the cool-down to the regular control still continues in the step 172, the control program moves to a step 184 to make a further judgment as to whether the actual cooling power T INT of the evaporator 8 is greater than 3° C. or not. In the case where the judgment in the step 174 indicates that the transition from the low temperature demist control to the regular control still continues, the control program moves to a step 186 to judge whether T INT is higher than 1° C. or not. The reference temperatures set in the steps 184, 186 indicate that the regular control can be achieved without trouble when the cooling power of the evaporator exceed these reference temperatures. If T INT exceeds the reference temperature set in the step 184 or 186, the control program goes on to a steps 188 or 190 to terminate the transition control and thereafter advances to the step 176 onward. If T INT is lower than the reference temperature set in the step 184 or 186, a step 192 varies T' INT using a first order lag filter whose time constant is smaller (40 seconds for example) than the time constant of the first order lag filter used in the step 180. The displacement of the variable displacement compressor 18 is controlled until T INT approaches to T' INT in a step 182.
Consequently, in the regular control mode, when the target cooling power T' INT of the evaporator 8 is changed either automatically by a change in thermal load in the vehicle passenger compartment, or manually by an occupant of the vehicle, the target cooling power T' INT varies gently, thereby preventing the occurrence of a sudden change of the discharged air temperature which would otherwise be caused by a rapid change in the actual cooling power T INT of the evaporator 8. In the course of the transition from the cool-down control or the low temperature demist control to the regular control, the cooling power of the evaporator is lowered as quickly as possible, in preferential to the control needed for preventing a sudden change of the discharged air temperature, until the temperature of the evaporator 8 rises to a value enabling the regular control. The freezing of the evaporator can be prevented and hence the regular control is achieved smoothly.
As described above, the target cooling power change rate is limited to a predetermined speed so as to prevent a sudden change or fluctuation of the displacement of the variable displacement compressor. As a result, the drivability is never deteriorated even when the engine load changes suddenly. The cooling power of the evaporator changes gently so that a pleasant temperature regulation in the vehicle passenger compartment can be achieved. The rate of change of the target cooling power is selectable. Accordingly, during the transition from the cool-down control or the demist control in which the evaporator operates at a temperature below the freezing temperature, a higher change rate is selected to preferentially perform the anti-freezing operation. Thus the automobile air-conditioner having the inventive compressor control apparatus is highly reliable in operation.
Obviously, various modifications and variations of the present invention are possible in the light of the above teaching. It is therefore to be understood that within the scope of the appended claims the present invention may be practiced otherwise than as specifically described. | In an apparatus for controlling a variable displacement compressor incorporated in an automobile air-conditioner, the displacement of the compressor is varied with a change in the target cooling temperature. The change rate of the target cooling temperature thus changed is limited to such an extent that a sudden change in displacement of the compressor is prevented to maintain the drivability of an automobile and to change the cooling power of the evaporator gently, thereby keeping a pleasant feeling during the temperature regulating operation. The change rate of the target cooling temperature can be selected from a plurality of predetermined values to meet a current controlling condition so that the reliability of the air-conditioner is improved. | 1 |
REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of commonly assigned and co-pending U.S. patent application Ser. No. 08/382,993, U.S. Pat. No. 5,520,627, filed Feb. 3, 1995, entitled RANGE-OF-MOTION ANKLE SPLINT, which is a continuation-in-part of commonly assigned and co-pending U.S. patent application Ser. No. 08/205,837, filed Mar. 4, 1994, U.S. Pat. No. 5,437,614 entitled RANGE-OF-MOTION SPLINT WITH ECCENTRIC SPRING, which is a continuation-in-part of commonly assigned U.S. Pat. No. 5,399,154, issued Mar. 21, 1995, entitled CONSTANT TORQUE RANGE-OF-MOTION SPLINT.
Reference is made to the following commonly assigned and co-pending application: U.S. patent application Ser. No. 08/383,063, filed Feb. 3, 1995, entitled HALO HOOKS FOR RANGE-OF-MOTION SPLINT by Andrzej Malewicz.
BACKGROUND OF THE INVENTION
The present invention relates generally to splint assemblies, and more particular to dynamic splints or braces for applying torque across joints undergoing rehabilitative therapy.
Injuries or surgery to ankles, wrists, elbows, knees and other joints often results in flexion or extension contractures. These debilitating conditions prevent the patient from fully flexing (in the case of an extension contracture) or extending (in the case of a flexion contracture) the injured joint. Range-of-motion (ROM) splints are dynamic devices commonly used during physical rehabilitative therapy to increase the range of motion over which the patient can flex or extend the joint. Splints of this type are known, and disclosed, for example, in the Mitchell et al. patent entitled DYNAMIC EXTENSION SPLINT, U.S. Pat. No. 5,036,837.
Commercially available range-of-motion splints typically include spring loaded brace sections for applying torque to the injured joint in opposition to the contracture. This force tends to gradually increase the working range or angle of joint motion. Springs, however, are passive devices and exert decreasing amounts of force as they retract. Most range-of-motion splints, therefore, require continual adjustment to maintain a constant amount of applied torque as the patient's range of joint motion increases during therapy. These torque adjusting procedures are time consuming and inconvenient.
In addition, with respect to range-of-motion splints for an ankle joint, commercially available splints do not provide for flexibility between the foot bracket positioned on the side of the foot of the user and the foot plate which supports the foot of the user. This flexibility between the two components is necessary to accommodate foot inversion, which is the twisting of the foot during flexion or extension contractures. Without compensating for foot inversion, an ankle range-of-motion splint will not provide the most beneficial rehabilitative therapy as possible.
It is evident that there is a continuing need for improved range-of-motion splints for an ankle joint. In particular, there is a need for splints capable of applying relatively constant torque over the entire working joint angle range without adjustments. The amount of torque applied by the splint should also be adjustable to suit the needs of different patients. In addition, the splint should provide for flexibility between the foot bracket positioned on the side of the foot of the user and the foot plate which supports the foot of the user to accommodate for foot inversion.
SUMMARY OF THE INVENTION
The present invention is a range-of-motion splint for providing torque to an ankle joint of a patient undergoing rehabilitative therapy. The range-of-motion splint is designed so that it accommodates foot inversion, which is the twisting of the foot during flexion contractures of the ankle joint.
The range-of-motion ankle splint includes a foot plate for supporting the foot of a patient. First and second foot brackets are connected to the foot plate via first and second fastening means, respectively. A first flexible grommet is positioned about the first fastening means to flexibly separate the foot plate from the first foot bracket, while a second flexible grommet is positioned about the second fastening means to flexibly separate the foot plate from the second foot bracket. First and second pivot means pivotally connect a first and second ankle bracket to the first and second foot brackets. First and second torque applying means are connected to the first and second foot brackets and the first and second ankle brackets, respectively. The first torque applying means applies torque between the first foot bracket and the first ankle bracket, while the second torque applying means supplies torque between the second foot bracket and the second ankle bracket.
In one preferred embodiment, the range-of-motion ankle splint further includes foot securing means connected to the foot plate for securing the foot of the patient to the foot plate. The foot securing means further comprises a pad of flexible material having hook and loop material. The splint includes a plurality of ankle straps connected to the first and second pivot means for securing the first and second foof brackets and the first and second ankle brackets to an ankle of the patient. A calf hook is also provided and is connected to the first and second ankle brackets. Calf securing means secures the calf hook to a calf of a patient.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a range-of-motion ankle splint.
FIG. 2 is a side view of a range-of-motion ankle splint.
FIG. 3 is a front view of range-of-motion ankle splint.
FIG. 4 is a sectional view of the fastening means which flexibly fastens the foot plate to the foot bracket as shown from line 4--4 of FIG. 1.
FIG. 5 is a sectional side view of the drive assembly of the present invention as shown from line 5--5 of FIG. 3.
FIG. 6 is a detailed end view of the drive assembly as shown from line 6--6 of FIG. 5, illustrating the pivot assembly.
FIG. 7 is a detailed end view of the drive assembly as shown from line 7--7 of FIG. 5, illustrating the pivot assembly.
FIG. 8 is a detailed end view of the drive assembly as shown from line 8--8 of FIG. 5, illustrating the spring and lock mechanism.
FIG. 9 is a detailed end view of the drive assembly as shown from line 9--9 of FIG. 5, illustrating the torque adjustment mechanism.
FIG. 10 is a side view of an alternate embodiment of a range-of-motion ankle splint.
FIG. 11 is an exploded view of a portion of the alternate embodiment shown in FIG. 10.
FIG. 12 is a second side view of the alternate embodiment of the range-of-motion ankle splint with portions of the splint removed for clarity.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to range-of-motion splint 10 shown in FIGS. 1-3 for applying torque to an ankle joint of a patient. FIG. 1 is a perspective view of range-of-motion splint 10. FIG. 2 is a side view and FIG. 3 is a front view of splint 10. Splint 10 includes calf hook 12, calf padding 14, calf strap 16, ankle bracket 18 comprising first telescoping bracket 20 having pin 21 and second telescoping bracket 22 having holes 23, ankle bracket 24 comprising first telescoping bracket 26 having pin 27 and second telescoping bracket 28, ankle hook 30, ankle padding 32, ankle strap 34, foot bracket 36 comprising first telescoping bracket 38 having pin 39 and second telescoping bracket 40 having holes 41, foot bracket 42 comprising first telescoping bracket 44 having pin 45 and second telescoping bracket 46, foot plate 48, foot padding 50, foot strap 52, housing 54, torque adjustment arms 56 and 57, locks 58 and 59, and housing 60 which houses a drive assembly, a pivot assembly, a lock mechanism and a torque adjustment mechanism.
In operation, a patient having an ankle joint which has undergone a flexion or extension contracture will place his foot through calf strap 16, ankle strap 34 and foot strap 52. Ankle brackets 18 and 24 can be adjusted via holes 23 and pins 21 and 27 such that calf hook 12 and ankle hook 30 are properly positioned on the patient. Likewise, foot brackets 36 and 42 can be adjusted via holes 41 and pins 39 and 45 such that foot plate 48 and foot strap 52 are properly positioned on the patient. Calf strap 16, ankle strap 34 and foot strap 52 can then be individually tightened. In one preferred embodiment, calf strap 16, ankle strap 34 and foot strap 52 are formed from hook and loop material such as material sold under the trademark VELCRO. Range-of-motion splint 10 will then be properly secured to the foot and lower leg of the patient. Calf padding 14, ankle padding 32 and foot padding 50 prevent irritation and bruising of the patient's lower leg and foot.
Ankle bracket 18 is connected to foot bracket 36 via a pivot pin (not shown in FIGS. 1-3). Housing 54 houses a torque adjustment mechanism (not shown in FIGS. 1-3) which is connected to both ankle bracket 18 and foot bracket 36 to provide torque between ankle bracket 18 and foot bracket 36. Likewise, ankle bracket 24 is connected to foot bracket 42 by a pivot pin (not shown in FIGS. 1-3). In addition, housing 60 houses a torque adjustment mechanism (not shown in FIGS. 1-3) which provides a torque between ankle bracket 24 and foot bracket 42. The torque adjustment means housed by housing 60 is independent of the torque adjustment means housed in housing 54. Thus, the torque applied to the left side of the foot and ankle joint of a patient is independent of the torque applied to the right side of the foot and ankle joint of the patient.
FIG. 4 is a sectional view of a portion of range-of-motion splint 10 as seen from line 4--4 shown in FIG. 1. As shown in FIG. 4, foot plate 48 is connected to first telescoping bracket 38 of foot bracket 36 via pin 70 and flexible grommet 72. Foot plate 48 is also connected to first telescoping bracket 44 of foot bracket 42 via a second pin and a second flexible grommet identical to that of pin 70 and flexible grommet 72.
As shown in FIG. 4, because of flexible grommet 72, foot plate 48 is capable of pivoting up and down about pin 70 within arc C. Likewise, foot plate 48 can pivot about the second pin connecting foot plate 48 to first telescoping bracket 44 of foot bracket 42 about a pivot pin within a similar arc. This design permits a "twisting" of splint 10 such that foot bracket 36 can pivot within arc A and foot bracket 42 can pivot without arc B, independent of each other.
The design shown in FIGS. 1-4 permit range-of-motion splint 10 to accommodate foot inversion, which is the twisting of the foot from left to right or right to left during flexion or extension of the ankle joint. Flexible grommet 72 and the flexible grommet which connects foot plate 48 to first telescoping bracket 44 of foot bracket 42 permits the angle between first telescoping bracket 38 of foot bracket 36 and foot plate 48 and the angle between first telescoping bracket 44 of foot bracket 42 and foot plate 48 to vary. If foot plate 48 was securely connected to foot brackets 36 and 42, the angles between foot plate 48 and foot brackets 36 and 42 would remain constant. This type of design would not accommodate foot inversion, and the rehabilitation process would be limited, as well as uncomfortable for the patient.
Pivot assembly 74, shown in FIGS. 5-9, includes ankle bracket 18, foot bracket 36 and an elongated link 75 pivotally connected at one end to ankle bracket 18 by pivot pin 98. An identical pivot assembly would be provided between ankle bracket 24 and foot bracket 42. Pivot pin 98 defines a first or primary joint pivot axis about which ankle bracket 18 and foot bracket 36 rotate. The end of bracket 36 interconnects with pivot assembly 74 and includes elongated gap 76 forming extensions 77 on opposite sides of the bracket. The ends of extensions 77 are pivotally connected to the sides of link 75 by screws 78. Screws 78 define a second or lateral joint pivot axis which is perpendicular to the primary splint pivot axis. Gap 76 is sized to receive link 75 while allowing foot bracket 36 to pivot with respect to ankle bracket 18 about the lateral joint pivot axis. Ankle bracket 18 includes extension 79 which extends beyond pivot pin 98 toward foot bracket 36 and is configured to engage pivot pin 94 of locking mechanism 120 (described below) to limit the range of rotational motion of ankle bracket 18 and foot bracket 36.
Drive assembly 80, which is housed in housings 54 and 60, is now described with reference to FIGS. 5-9. While drive assembly 80 is shown and described with reference to ankle bracket 18, foot bracket 36, and housing 54, it is understood that an identical drive assembly would be housed within housing 60. Drive assembly 80 includes drive mechanism 82, spiral spring 84 having inner end 86 and outer end 88, gear 90 having shaft 92, pivot pin 94, link 96, pivot pin 98, gear pivot pin 100, recess 102 of housing 54, and screws 104.
As shown in FIGS. 5-9, drive assembly 80 includes drive mechanism 82 mounted to ankle bracket 18 and foot bracket 36 and enclosed by housing 54. Drive mechanism 80 includes spiral spring 84 having first or inner end 86 and second or outer end 88. Inner end 86 is mounted to a slot within shaft 92 of gear 90. Outer end 88 is hooked to pivot pin 94 extending from the end of link 96 opposite pivot pin 98. Gear 90 is rotatably mounted within housing 54 by gear pivot pin 100 which extends through gear shaft 92. The end of gear pivot pin 100 adjacent gear 90 is mounted within recess 102 on the inner surface of housing 54. The end of gear pivot pin 100 adjacent shaft 92 is rotatably mounted within a recess or aperture in ankle bracket 18. Housing 54 is fastened to ankle bracket 18 by screws 104.
Spiral spring 84 is eccentrically mounted with respect to the primary splint pivot axis formed by pivot pin 98. As shown in FIGS. 6-9, the rotational axis of gear pivot pin 100 is offset or spaced from pivot pin 98. In the embodiment shown, when ankle bracket 18 and foot bracket 36 are linearly aligned, a line (not shown) extending through pins 98 and 100 form a 90 degree angle with a line (also not shown) extending through pins 94 and 98. In other words, pins 94 and 100 form a right angle with respect to pivot pin 98. The offset between gear pivot pin 100 and pin 98 is 1/4 inch (64 mm) in one embodiment.
As shown in FIGS. 5 and 9, a torque adjustment mechanism is shown which includes adjustment worm 110 having end 112, crank 114 having handle 116, and pivot 118.
As shown in FIGS. 5 and 9, adjustment worm 110 is mounted with recesses in housing 54 for engagement with gear 90 and rotation about an axis perpendicular to gear pivot pin 100. End 112 of adjustment worm 110 extends through housing 54 and is connected to crank 114 by pivot pin 118. Crank 114 is configured for pivotal movement about a retracted position adjacent housing 54 (shown in solid lines), and an extended position (shown in broken lines). When in the extended position, handle 116 of crank 114 can be actuated to rotate adjustment worm 110, thereby rotating gear 90 to wind and unwind spiral spring 84 in order to increase and decrease the amount of torque applied across ankle bracket 18 and foot bracket 36 by spring 84. Gear 90, adjustment worm 110 and crank 114 thereby function as a torque adjustment mechanism.
FIGS. 8 and 9 show locking mechanism 120 which can releasably lock ankle bracket 18 and foot bracket 36 with respect to one another. Locking mechanism 120 includes pawl 122, rack 124, lever 126 and base member 128 having handle 130. Locking mechanism 120 includes pawl 122 pivotally mounted to pivot pin 94 and rack 124 formed on interior surface of housing 54. Pawl 122 is actuated by lever 126 which includes base member 128 and handle 130. Base member 128 is mounted to pawl 122 and extends outwardly from housing 54. Handle 130 extends from base member 128 and is positioned generally adjacent to the exterior of housing 54. Handle 130 is actuated to drive pawl 122 between a position disengaged from rack 124, and an over-center position engaged with rack 124. When pawl 122 is in the disengaged position, ankle bracket 18 and foot bracket 36 can freely rotate with respect to one another. Conversely, when pawl 122 is in the engaged position, pawl 122 is biased into engagement with rack 124 by the force of spiral spring 84.
Locking mechanism 120 enables ankle bracket 18 and foot bracket 36 to be conveniently and rigidly locked with respect to one another at any desired position within the range-of-motion of splint 10. In one embodiment, the teeth forming rack 124 are symmetrical or bi-directional. Housing 54 can therefore be used on range-of-motion splint 10 configured for both flexion and extension contractures of an ankle joint.
Adjustable range-of-motion stop mechanism 140 is shown in FIGS. 5-7. Adjustable range-of-motion stop mechanism 140 includes threaded holes 142 and pins 144. Adjustable range-of-motion stop mechanism 140 enables a clinician to control the range of rotational motion between ankle bracket 18 and foot bracket 36. Stop mechanism 140 includes threaded holes 142 circumferentially arranged around pivot pin 98 on the end of ankle bracket 18 and a pair of removable pins 144 which can be threadably engaged with holes 142. Pins 144 extend from the side of ankle bracket 18 facing foot bracket 36. The range of rotational motion between ankle bracket 18 and foot bracket 36 is limited by the engagement of pins 144 with the ends of extensions 146 of foot bracket 36. A clinician can conveniently reposition one or both of pins 144 within holes 142 to adjust the range-of-motion over which splint 10 can operate as the patient's condition improves.
FIG. 10 is a side view of an alternate embodiment of the present invention. As shown in FIG. 10, several elements are identical to that disclosed in the embodiment shown in FIGS. 1-9. Thus, any like elements have been labeled as such.
As shown in FIG. 10, ankle hook 30, ankle pad 32 and ankle strap 34 have been removed. In their place is front ankle pad 100, outside ankle pad 102, front ankle strap 104, back ankle strap 106 and heel strap 108. The embodiment shown FIG. 10 provides a secure fit to the lower leg of a patient, while also providing comfort to the patient.
FIG. 11 is an exploded view of a portion of the alternate embodiment shown in FIG. 10, while FIG. 12 is a side view of the present embodiment with housing 54 removed for clarity. As shown in FIGS. 11 and 12, pin 110 can be positioned through plate 112 and fasteners 114, 116 and 118. Fasteners 114, 116 and 118 are connected to the ends of straps 104, 106 and 108 respectively. This type of connection allows straps 104, 106 and 108 to pivot about pin 110 in order to provide maximum comfort and stability. It is understood that there is an identical arrangement on the inside of the patient's foot. This view has not been shown to avoid duplicate drawings.
Range-of-motion splint 10 offers considerable advantages over prior art mechanisms. First, the use of two torque adjustment mechanisms provide for individual biasing on either side of an ankle joint. Second, the use of flexible grommets connecting the foot plate to the two foot brackets accommodates foot inversion, which is the twisting of the foot during flexion contractures of the ankle joint. Third, the flexibility of having either an ankle bracket or three straps provides maximum comfort and stability.
Although the present invention has been described with reference to preferred embodiments, workers skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the invention. | A range-of-motion splint for applying torque to an ankle joint of a patient is disclosed. The splint includes a foot plate for supporting the foot of a patient. First and second foot brackets are connected to the foot plate via first and second fastening means, respectively. First and second pivot means pivotally connect a first and a second ankle bracket to the first and second foot brackets, respectively. First and second torque applying means are connected to the first and second foot brackets and the first and second ankle brackets, respectively. The first torque applying means applies torque between the first foot bracket and the first ankle bracket, while the second torque applying means supplies torque between the second foot bracket and the second ankle bracket. Calf securing means are connected to the first and second ankle brackets for securing the first and second ankle brackets to a calf of the patient. A plurality of ankle straps are connected to the first and second pivot means for securing the first and second foot brackets and the first and second ankle brackets to an ankle of the patient. | 0 |
TECHNICAL BACKGROUND
The present invention relates generally to a system for producing a semiconductor and in particular to a method and apparatus for semiconductor filming wherein a thin film, such as an oxidation film, is deposited on a surface of a silicon wafer.
Semiconductor manufacture involves a step wherein an oxidation film is generated as an insulation film on a wafer surface, which step is carried out by means of an oxidation system. A known oxidation system will be explained hereunder with reference to FIG. 3.
Inside a reaction tube 1, there is provided a boat 3 carrying a lot of horizontally oriented wafers 2 laid in a multi-storied fashion. The boat 3 is vertically disposed, via a boat stand 5, on a furnace opening cover 4 which airtightly covers a lower end of the reaction tube 1. In a ceiling of the reaction tube 1, there are provided a plurality of gas introduction holes 6 communicating with a gas introduction pipe 7. An exhaust pipe 8 communicates with the inside of the reaction tube 1 at a lower part thereof. The gas introduction pipe 7 is connected to a source of oxygen gas not shown and has a valve 9 and a flow rate adjuster 10 thereabove.
Referring to FIG. 4, oxidation operation in the known system will now be explained.
The wafer 2 being loaded on the boat 3 is introduced into the reaction tube 1. The internal temperature of the reaction tube 1 is elevated at a rate of 5°-10°C./min to a preset temperature (900° C. in FIG. 4) and maintained at that temperature. The exhaust pipe 8 is opened to feed oxygen from the gas introduction pipe 7 into the reaction tube 1 to thereby oxidize the wafer 2 surface. Upon completion of the oxidation process, the gas is exhausted from the exhaust pipe 8.
After the oxidation process is completed, the internal temperature is lowered at a rate of 2°-5° C./min to a predetermined temperature, e.g., 800°C. and maintained at that temperature. After lapsing of a predetermined time period, the boat 3 is taken out of the reaction tube 1.
Since the exhaust gas is eventually exhausted to the atmosphere, the back pressure of the exhaust gas is greatly influenced by the atmosphere. Thus, internal pressure of the reaction tube 1 is liable to be influenced by the atmospheric pressure. Further, since the oxidation rate of the wafer depends on the absolute pressure of oxygen, a change in the atmospheric pressure leads to a change in the absolute pressure, and the oxidation rate changes as the atmospheric pressure changes. Consequently, there has been a problem that the quality of the oxidation process varies depending on the atmospheric pressure during such process and thus becomes unstable.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to maintain an absolute pressure of a reaction gas during a process such as an oxidation process to thereby achieve improved stability in product quality.
According to one aspect of the present invention, the above object is met by a method of semiconductor filming wherein a thin film is deposited on a wafer under an atmospheric pressure, the method comprising the steps of simultaneously supplying a reactive gas and an inert gas to a reaction tube and maintaining a partial pressure of the reactive gas constant.
In one particular form of the method, a flow rate of the inert gas is changed relative to a change in the atmospheric pressure and the partial pressure of the reactive gas is maintained constant.
In another particular form of the method, a flow rate of the reactive gas is changed relative to a change in the atmospheric pressure and the partial pressure of the reactive gas is maintained constant.
In a further particular form of the method, a flow rate of one of the reactive and inert gases is regularly changed relative to a change in the atmospheric pressure and a flow rate of the other one of the reactive and inert gases is changed relative to a change in the flow rate of the one of the reactive and inert gases and a change in the atmospheric pressure whilst the partial pressure of the reactive gas is maintained constant.
According to another aspect of the present invention, there is provided an apparatus for carrying out semiconductor filming, which comprises a reactive gas supply pipe for supplying a reactive gas to a reaction tube, an inert gas supply pipe for supplying an inert gas to the reaction tube, a flow rate adjuster disposed on each of the reactive gas supply pipe and the inert gas supply pipe, a barometer for measuring an atmospheric pressure, and a controller for controlling a flow rate of at least one of the flow rate adjusters based on the measurements of the barometer.
In a particular form of the apparatus, the controller includes an arithmetic means for operating the flow rates of the inert and reactive gases for maintaining a partial pressure of the reactive gas employing as variables a change in the atmospheric pressure, the flow rates of the inert and reactive gases, the partial pressure of the reactive gas and the atmospheric pressure.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic perspective view illustrating an embodiment of the present invention.
FIG. 2 is a flow chart showing the operation of the embodiment.
FIG. 3 is a schematic perspective view illustrating a known apparatus.
FIG. 4 is a graph illustrating a manner of oxidation film deposition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Preferred embodiment of the present invention will now be explained with reference to the accompanying drawings.
In FIG. 1, same reference numerals will be used for corresponding parts shown in FIG. 3.
Inside a reaction tube 1, there is provided a boat 3 carrying a plurality of horizontally oriented wafers 2 laid in a multi-storied fashion. The boat 3 is vertically disposed, via a boat stand 5, on a furnace opening cover 4 which in an airtight manner covers a lower end of the reaction tube 1. In a ceiling of the reaction tube 1, there are provided a plurality of gas introduction holes 6 communicating with a gas introduction pipe 7. An exhaust pipe 8 communicates with the inside of the reaction tube 1 at a lower part thereof. The gas introduction pipe 7 is branched to provide a reactive gas supply pipe 11 connected to an oxygen gas source as a source of reactive gas not shown and an inert gas supply pipe 12 connected to a source of inert gas not shown.
The reactive gas supply pipe 11 has a flow rate adjuster 10. Upstream and downstream of the flow rate of adjuster 10, there are provided a valve 9 and a valve 13, respectively. Similarly, the inert gas supply pipe 12 has a flow rate adjuster 14, upstream and downstream of which there are provided a valve 15 and a valve 16, respectively.
On the inventive apparatus, there is also provided a controller 17 for controlling the flow rates of the flow rate adjusters 10 and 14, in which pressures detected by a barometer 18 are input.
Operation of the apparatus will be described hereinbelow with reference to FIG. 2.
The valves 13 and 9 are opened, and the flow rate of the flow rate adjuster 10 is set by means of the controller 17, the oxygen gas at constant flow rate is supplied. Then, the valves 16 and 15 are opened to place the inert gas in condition to be supplied through the gas introduction pipe 7 to the inside of the reaction tube 1, and the flow rate of the flow rate adjuster 14 is set by means of the controller 17. The flow rate setting is performed such that the absolute pressure of the oxygen gas at a reference atmospheric pressure corresponds to a set pressure.
A value indicative of the atmospheric pressure detected by the barometer 18 is input into the controller 17. The controller 17 computes a deviation between the detected atmospheric pressure and reference atmospheric pressure. It then computes the flow rate of the inert gas at which the absolute pressure of the oxygen gas is maintained constant under such deviation and controls the flow rate adjuster 14 to allow flow of the relevant gas at the computed flow rate.
The flow rate of the inert gas may be maintained constant whilst the flow rate of the oxygen gas is varied in correspondence with a change in the atmospheric pressure, maintaining a partial pressure of the oxygen gas constant. Alternatively, the flow rate of one of the inert gas or oxygen gas may be changed regularly, that is, in accordance with a functional equation, and the flow rate of the other gas may be changed relative to that change and a change in the atmospheric pressure.
Relations between the inert gas, oxygen gas, atmospheric pressure and partial pressure of the oxygen gas are represented by Equation 1 and Equation 2, shown below, where the inert gas is x; the oxygen gas is y; the partial pressure of the oxygen gas is z; and the atmospheric pressure is w.
x=y(w/z-1) Equation 1
y=x(w/z-1) Equation 2
These operational equations 1 and 2 are input for presetting the controller 17. The controller 17 performs the required operations, and the flow rate adjusters 10 and 14 are controlled as explained hereunder.
When the flow rates of the oxygen gas and the partial pressure of the oxygen gas are maintained constant, an operation is carried out according to Equation 1, on basis of the detected atmospheric pressure and the preset partial pressure of the oxygen gas, to compute the flow rate of the inert gas. A control signal is then output to the valve 15 to control same to allow the relevant gas to flow at the computed flow rate. As the flow rates of the inert gas and the partial pressure of the oxygen gas are maintained constant, an operation is carried out according to Equation 2, based on the detected atmospheric pressure and preset partial pressure of the oxygen gas, to compute the flow rate of the oxygen gas, whereafter the flow rate adjuster 10 is controlled to allow the relevant gas to flow at the computed flow rate. Where one of the flow rates of the inert and oxygen gases is to be changed regularly, an operation is performed according to either Equation 1 or Equation 2 to obtain a variable for maintaining the partial pressure of the oxygen gas constant.
Table 1 below shows an implementation where the flow rate of the oxygen gas is maintained constant and the partial pressure of oxygen is maintained constant at 900 hpa. The values shown in Table 1 are obtained by Equation 1 above.
TABLE 1______________________________________ OXYGENATMOSPHERIC OXYGEN INERT GAS PARTIALPRESSURE FLOW RATE FLOW RATE PRESSURE hpa! SLM! SLM! hpa!______________________________________1 1,000 9 1 9002 980 9 0.8 9003 950 9 0.5 900______________________________________
As is now apparent, notwithstanding occurrence of a change in the atmospheric pressure, it is possible to maintain the partial pressure of the oxygen gas constant by changing the flow rate of the inert gas. Further, since the pressure inside the reaction tube is kept substantially equal to the atmospheric Pressure, existing oxidation furnaces can also be used as they are.
Next, in a first way of controlling the inventive apparatus, the atmospheric pressure is firstly detected by the barometer 18 prior to treatment of the wafer 2 or during a predetermined time period of wafer insertion and completion of the temperature rise. Then, the flow rates of the inert and oxygen gases being processed for maintaining the partial pressure of the oxygen gas at the preset value are computed, the flow rates being maintained constant during the process.
In a second way of controlling the apparatus, additionally to the first way, a value detected by the barometer 18 may be input to adjust the flow rates at least once during the wafer treatment. In a third way of controlling the apparatus, the flow rates may be adjusted intermittently by inputting values detected by the barometer 18 at predetermined time intervals. Alternatively, the flow rates may be adjusted continuously by continuously inputting values detected by the barometer 18. Selection of these ways of controlling the apparatus depends on factory locations. For example, in districts experiencing a diversity of weather changes, the third way of controlling the apparatus may be desirable as the atmospheric pressure is likely to change. The first and second ways of controlling the apparatus may be suited to districts with little atmospheric pressure changes.
With the inventive system thus arranged, it is possible not only to avoid discrepancies between or errors in treatment conditions due to regional differences, e.g., altitudinal differences of factory locations but also to avoid errors in batches of treatment, apparatuses and factories whilst achieving compatibility of treatment data.
As it may readily be appreciated by those of ordinary skill in the art, the present invention should not be limited to use on an oxidation apparatus but it may also be applied to a phosphorus diffusion apparatus, a PYRO oxidation (hydrogen gas burning oxidation) apparatus, a hydrogen chloride oxidation apparatus, etc. when an inert gas is additionally used and a reactive gas and a partial pressure of an oxidation gas are controlled, thus achieving stability in product quality.
Since, as thus far explained, the absolute pressure of a reactive gas can be maintained constant in the apparatus according to the present invention, it achieves deposition of thin films of uniform film thickness and quality and hence provides products of improved quality and improved reproductiveness. Further, since the internal pressure of a reaction chamber may be kept substantially equal to an atmospheric pressure, existing oxidation furnaces may be used as they now stand, without making any alterations thereto. | A method of semiconductor filming wherein a thin film is deposited on a wafer under an atmospheric pressure, which comprises the steps of simultaneously supplying a reactive gas and an inert gas to a reaction tube and maintaining a partial pressure of the reactive gas constant by adjusting the flow rates of those gases, whereby stability in film quality is improved. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a recording apparatus for recording an information signal on a record bearing medium.
2. Description of the Prior Art
Known recording and/or reproducing apparatuses of the above-stated kind include video tape recorders (hereinafter referred to as VTR's) of a rotary two-head type which is arranged, for example, to perform the so-called four-frequency pilot type tracking control. In the following description, the VTR of this kind is taken up by way of example.
In carrying out the so-called jointed recording in which a new video signal is continuously recorded on a magnetic tape without leaving any blank part after the end of a previously recorded video signal, the VTR's of this kind have employed the following method: First, when an instruction for a halt is issued, the magnetic tape is immediately wound backward to a predetermined extent (or for a given period of time "to"). Then, the tape comes to a stop. After that, when the tape is released from the stopping action, it is allowed to travel at a normal speed with the VTR shifted to a reproducing mode under tracking control. Then, after the tape is allowed to travel forward to an extent a little shorter than the above-stated backward winding extent, i.e. after the lapse of a period of time "t1" which is shorter than the period "t0", a new video signal is recorded from a part at which a recording track begins in synchronism with a head switch-over signal.
However, the conventional VTR which is arranged to be capable of performing the jointed recording in the above-stated manner has presented the following problems: First, during a period of time corresponding to a difference between the periods "t0" and "t1", there remains a portion of the previously recorded signal. Therefore, the new signal comes to be overlapped or superimposed on this portion of the previous record. As a result, the quality of a reproduced picture deteriorates in this part. Next, since the VTR of the kind performing four-frequency type tracking control is generally arranged to perform so-called azimuth overlapped writing, the locus of tracing performed by a head at the time of reproduction deviates from that of tracing performed by a head in recording. Therefore, with the tape wound backward after the halt as mentioned above, the arrangement to record a new video signal with tracking made in the same manner as the reproduction tracking made at the time of the halt would result in the irregular width of tracks formed in the joint part. Therefore, when the jointed record is played back across the jointed part, tracking cannot be stably accomplished at that part.
To solve these problems, there have been contrived various methods. In one of such methods, a VTR is arranged to lessen the overlapped recording part. In another, a VTR is arranged to compensate for the deviation of the tracing locus of the head. These methods, however, necessitate additional arrangement of high precision control means. Therefore, each of these methods has resulted in a complex circuitry, which has hindered reduction in size and cost of the apparatus.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a recording apparatus which is capable of indicating the end part of a record on a record bearing medium without necessitating any complex arrangement for that purpose.
It is another object of this invention to provide a recording apparatus which is capable of indicating a stopped part of a recording operation on a record bearing medium without producing any additional signal for indicating.
It is a further object of this invention to provide a recording apparatus which is capable of detecting a part at which a recording operation is stopped on a record bearing medium and to automatically switch one operating mode over to another without necessitating any complex arrangement.
It is a still further object of this invention to provide a recording apparatus which is capable of stopping a recording operation after a predetermined number of recording tracks are formed on a record bearing medium without necessitating any complex arrangement for that purpose.
Under these objects, a recording apparatus arranged according to this invention to record an information signal on a record bearing medium comprises: recording means for recording the information signal on the medium; instruction means for producing an instruction to stop a recording operation; stopping means for causing, in response to the instruction of the instruction means, the recording means to stop recording; pilot signal generating means for generating pilot signals having different frequencies from each other in a first generating pattern; control means for controlling the pilot signal generating means to generate the pilot signals in a second generating pattern in response to the instruction of the instruction means; and superimposing means for superimposing upon the information signal the pilot signals generated by the pilot signal generating means.
The above and other related objects and features of this invention will become apparent from the following detailed description of embodiments thereof taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an illustration of magnetized recording tracks formed by a VTR of the type performing tracking control by the four-frequency pilot method.
FIG. 2 is a block diagram showing the essential parts of a reproduction circuit arranged to obtain a tracking error signal.
FIGS. 3A, 3B and 3C are illustrations showing the shortcoming of the jointed recording performed by the conventional VTR.
FIG. 4 is a diagram showing the arrangement of essential parts of a VTR embodying this invention as an ebodiment thereof.
FIGS. 5A to 5E are illustrations showing the operation of the VTR of FIG. 4.
FIG. 6 is a timing chart showing the wave forms of signals produced from various parts of the VTR shown in FIG. 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The details of this invention will be understood from the following description of a preferred embodiment thereof: First, let us briefly describe the manner in which a tracking control signal is obtained by the four-frequency pilot method. FIG. 1 of the accompanying drawings shows the magnetized recording tracks formed by a VTR of the kind performing tracking control in accordance with the four-frequency pilot method. FIG. 2 is a block diagram showing the essential parts of a reproduction circuit arranged to obtain the tracking error signal.
Referring to FIG. 1, the illustration includes a magnetic tape 1 and an arrow 2 which indicates the travelling direction of the tape 1. Recording tracks A1, B1, A2, B2, . . . are formed with recording performed by heads A and B which have different predetermined azimuth angles. An arrow 3 indicates a direction in which scanning is performed by these heads. In each of recording tracks 4, one of pilot signals having four different frequencies f1 to f4 is recorded along with a video signal. The pilot signals are thus superimposed on a video signal one after another for every field portion of the record (one in every track). The recording sequence of these pilot signals is, for example, as follows as shown in FIG. 1: The track A1 has the pilot signal of the frequency f1 which is, for example, 102.5 KHz≈6.5 fH (fH representing the frequency of a horizontal synchronizing signal). The track B1 has the pilot signal of the frequency f2 which is, for example, 118.9 KHz≈7.5 fH. The track A2 has the pilot signal of the frequency f4 which is, for example, 165.2 KHz≈10.5 fH. The track B2 has the pilot signal of the frequency f3 which is, for example, 148.7 KHz≈9.5 fH. The frequency difference between the pilot signals recorded in adjacent recording tracks is arranged to be either fH or 3 fH as shown in FIG. 1. Further, when the head is scanning a track Ai (i: 1, 2, 3, . . . ), the frequency difference between the pilot signal of the track and that of another track which is located next on the right-hand side of the track Ai as viewed on the drawing is always fH while the frequency difference between the pilot signal of the track Ai and that of another track on the left-hand side thereof is always 3 fH. When the head is scanning a track Bi (i: 1, 2, 3, . . . ) on the other hand, the frequency difference between the pilot signal of the track and that of another track on the right-hand side is always 3 fH while the frequency difference between the pilot signal of the track Bi and that of another track on the left-hand side is always fH.
Further, since the pilot signals of the frequencies f1 to f4 are relatively low frequency signals, the head can reproduce the pilot signals of the adjacent tracks as cross-talks in addition to that of the track being mainly scanned even in the case of azimuth recording arrangement. In other words, assuming that the head is mainly scanning the track A2, a composite signal including components of frequencies f4, f2 and f3 is detected as the pilot signal. In case that the center of the tracing locus of the head accurately coincides with the center line of the mainly scanned track, i.e. in the case of an on-track condition, the reproduced level of the pilot signal of frequency f2 and that of the pilot signal of frequency f3 are equal to each other. The letter becomes higher than the former when the position of the head deviates from the track A2 slightly toward the track B2. The former becomes higher than the latter when the head deviates slightly toward the track B1.
To obtain the direction and the degree of deviation of the head from the mainly scanned track, difference signals of fH and 3 fH representing the frequency difference between the pilot signal of the main track and that of each of the two adjacent tracks are separated and taken out; and then the levels of the two difference signals are compared with each other.
FIG. 2 is a circuit block diagram showing the arrangement of a circuit operating in accordance with the four-frequency pilot method described above. Referring to FIG. 2, a terminal is arranged to receive an incoming reproduced signal having the pilot signals superimposed on a video signal. The reproduced signal is applied to a low-pass filter (hereinafter referred to as LPF) 6 to have the pilot signal component separated alone. A multiplier 8 is arranged to perform a multiplying operation on the separated pilot signal component and a local pilot signal generated by a local pilot signal generating circuit 7. The local pilot signal is arranged to have the same frequency as that of the pilot signal recorded in the mainly scanned track. As mentioned in the foregoing with reference to FIG. 1, in case that the track A2 is being mainly scanned, the output of the LPF 6 includes components of frequencies f2, f4 and f3. Then, the frequency of the local pilot signal in this instance is f4. Accordingly, the multiplier 8 produces a signal having a frequency of a sum of and difference frequencies f2, f4 and f3 and the frequency f4 in this instance. A band-pass filter (hereinafter referred to as BPF) 9 is arranged to take out the frequency component fH from the sum and difference signal. Another BPF 10 is arranged to take out the frequency component 3 fH from the signal. The outputs of the BPF's are supplied to detection circuits 11 and 12 for detection and rectification.
Following this, the signal components fH and 3 fH are supplied to a level comparator 13. The circuit 13 then produces a signal corresponding to the level difference between these signal components. More specifically, when the reproduced level of the signal component fH is higher than that of the signal component 3 fH, a positive potential corresponding to the level difference is taken out. In the event of a converse relation, a negative potential is taken out. This arrangement thus gives a signal indicative of both the degree and the direction of the deviation of the head from the track. Therefore, this signal is usable as a tracking error signal.
Then, since the relation of the deviating direction of the head to the tracking error signal for the track Ai conversely takes place in the case of the track Bi as described in the foregoing, a switching circuit 16 is arranged to selectively allow the output of the comparison circuit 13 to pass through an inverting amplifier 14 in response to a head switch-over signal 15.
FIGS. 3A, 3B and 3C show the shortcoming of the conventional jointed recording arrangement. Assuming that a halt or stop instruction is produced to temporarily stop recording when either the head A or the head B (or a head 100) is recording halfway for one field portion of the signal as shown in FIG. 3A, the tape is then wound backward to a predetermined extent "t0" and the head 100 comes back to a point 101.
After that, there obtains a reproducing mode with the halt mode cancelled. Then, the tape is allowed to travel at a normal speed under tracking control. There obtains a recording mode in synchronism with a head switch-over signal produced after the lapse of a period of time t1 (shorter than the period of time t0). The head then records a new signal at a point 102 indicated in FIG. 3B. Before arrival at this point 102, the head has traced the tape across three tracks under tracking control. Therefore, if the recording mode obtains immediately under that condition, there would be formed a recording track of width T1 which is narrower than the width T0 of other recording tracks as shown in FIG. 3C. This has been the shortcoming of the conventional arrangement for jointed recording.
A VTR which is arranged according to this invention as an embodiment thereof is arranged as shown in FIG. 4 in a circuit diagram. FIGS. 5A to 5E show the operation of this embodiment. FIG. 6 shows the wave forms of signals obtained at various parts of the circuit arrangement of FIG. 4. The details of this embodiment will be described below with reference to these drawings:
Referring to FIG. 4, an oscillator 20 produces a reference signal, which is then frequency divided by 1/n1, 1/n2, 1/n3 and 1/n4 by means of frequency dividers 21, 22, 23 and 24. These frequency dividers 21, 22, 23 and 24 then produces signals of frequencies f1, f2, f4 and f3. One of these signals of frequencies f1, f2, f4 and f3 is selectively supplied to a multiplier 29 with one of switches 25, 26, 27 and 28 turned on. Meanwhile, a rectangular wave signal generating circuit 30 is arranged to produce a rectangular wave signal which is as shown at a part (a) in FIG. 6. This rectangular wave signal (a) alternately becomes high and low levels at every one-field period (at intervals of 1/60 sec) according to the rotation phase of a rotary drum 32 detected by a detector 31. This signal is arranged to be used also as a head switch-over signal HSW and is thus supplied to a head switch-over circuit 33. The magnetic head operation is thus switched over between heads 34a and 34b. The inversion period of this signal HSW corresponds to a period of time during which the magnetic head 34a or 34b traces one recording track on the magnetic tape 35.
The signal HSW or (a) is frequency divided by 1/2 by a 1/2 frequency divider 36 to obtain a signal (b) as shown at a part (b) in FIG. 6. As a result of this, each of AND gates 37 and 38 and NOR gates 39 and 40 produces a high level signal one after another at every one-field period (a period of time during which each of the magnetic heads 34a and 34b traces one recording track).
Meanwhile, as will be described in detail later, the output level of an OR gate 41 becomes low for normal recording and high for normal reproduction. When the output of this OR gate 41 is at a high level, the connecting positions of switches 42 and 43 are on their sides P. They are on the other sides R when the output of the OR gate 41 is at a low level. During normal recording, therefore, one of pilot signals of the frequencies f1, f2, f3 and f4 is supplied to a mixer 44 at every one-field period in a sequence of rotation of f1, f2, f4 and f3. The mixer mixes the pilot signal with an incoming video signal. The output of the mixer 44 is recorded on a magnetic tape 35 by the magnetic heads 34a and 34b. Further, during normal reproduction, signals of frequencies f1, f2, f3 and f4 are supplied one after another in rotation to a multiplier 29 in the sequence of f1, f3, f4 and f2 as local pilot signals. Then, a reproduced signal obtained from the magnetic heads 34a and 34b is supplied to the multiplier 29 via the head switch-over circuit 33 and a low-pass filter 78. The reproduced signal and the local pilot signal are subjected to a multiplying operation performed by the multiplier 29.
In case that a normal reproducing operation is designated at an operation part 52 and a reproducing instruction signal of a high level is supplied to the OR gate 41 from a system controller 53, if the frequencies of the pilot signals recorded in the main tracks are in the sequence of f1, f2, f4 and f3, the frequencies of the local pilot signals supplied to the multiplier 29 are in the sequence of f1, f3, f4 and f2. Therefore, in this instance, the frequency difference between each of the local pilot signals and the pilot signal recorded in the track preceding the main track is always 3 fH while the frequency difference between the local pilot signal and the pilot signal of the track succeeding the main track is always fH. These frequency components fH and 3 fH are separated by means of band-pass filters 45 and 46 and the detection circuits 47 and 48. Then, a comparison circuit 49 produces a signal corresponding to a difference between the outputs of the detection circuits 47 and 48. The signal from the comparison circuit 49 is employed as a tracking error signal as it is and is supplied to a capstan control circuit 50. The oscillator 20, frequency dividers 21, 22, 23 and 24, the AND gates 37 and 38, the NOR gates 39 and 40, the 1/2 frequency divider 36 and the inverter 51 jointly form the local pilot signal generating circuit 7 shown in FIG. 2.
In the event of jointed recording, the embodiment operates as follows: When a normal recording operation is designated at the operation part 52, a recording instruction signal which is at a low level is supplied from the system controller 53 to the OR gate 41. The switches 42 and 43 are connected to their sides R. Under that condition, a stop or halt is designated at the operation part 52. The system controller 53 then produces a halt instruction signal which remains at a high level while recording is brought to a stop as shown at a part (c) of FIG. 6. This signal is supplied to an OR gate 68 via a delay inversion circuit 54, an AND gate 55 and an inverter 67. The delay inversion circuit 54 and the AND gate 55 are provided for the purpose of detecting the rising edge of the recording stop instruction signal (c). An edge signal (d) which is thus obtained triggers a monostable multivibrator 56. The output of the monostable multivibrator 56 becomes a signal which remains at a high level between two fields in a manner as shown at a part (e) of FIG. 6.
Meanwhile, edge parts of the signal HSW or (a) are detected by inverters 51 and 57 and an exclusive OR circuit 58. Further, an inverter 59 and a NOR gate 60 detect only the fall edge of the signal. As a result, one edge of the signal is gated by an AND gate 61 as a pulse signal (f). This pulse signal (f) comes to set a flip-flop 62. The flip-flop 62 is reset by a next rise edge (h) of the signal HSW or (a) which is detected via AND gates 63 and 64. The flip-flop 62 then produces a signal (g) as the Q output thereof as shown at a part (g) in FIG. 6. The level of the signal (g) is at a high level for a one-field period during which the pilot signal of the frequency f2 or f3 is recorded for the first time after the recording stop instruction is produced. During that period, the level of the output (l) of the OR gate 41 is also high as shown at a part (l) in FIG. 6. Then, if the track is to be recorded with the pilot signal of the frequency f2 or f3, the frequency of the pilot signal to be recorded becomes f3 or f2.
Let us assume that a recording stop instruction is produced under a condition as represented by FIG. 5A. In other words, the recording stop instruction is produced while a head HA is in the process of tracing a track 106. In such a case, the recording operation cannot be immediately brought to a halt at that point of time (i.e. a point of time T1 shown in FIG. 6), because: an instruction signal (j) applied to the system controller 53 during the recording operation is kept at a high level with a flip-flop 65 having been set. Besides, a video signal recording instruction (k) also remains at a high level as a flip-flop 66 is not triggered.
Referring to FIG. 5B, when the head HA traces a track 107, the level of the output (l) of the OR gate 41 becomes high. Therefore, both the switches 42 and 43 are connected to their sides P. Then, in place of the pilot signal of the frequency f2 which is to be recorded, the pilot signal of the frequency f3 is recorded. The recording operation then comes to a stop when the head HA comes to a position as indicated in FIG. 5B.
At this point of time (T2 in FIG. 6), the flip-flop 62 is reset. The reset pulse (h) also resets the flip-flop 65 and sets a flip-flop 66. A monostable multivibrator 69 is triggered. Then, a capstan reverse rotating instruction signal (i) which is supplied from this monostable multivibrator to the system controller 53 becomes a high level. This high level signal (i) is supplied via the system controller 53 to a capstan control circuit 50. Upon receipt of this signal, the capstan control circuit 50 controls a capstan motor 71 which is arranged to drive a capstan 70. The capstan 70 is then driven to begin to rewind (or wind backward) the magnetic tape 35. This tape rewinding action comes to a stop after the lapse of a predetermined period of time as indicated at "t2" in FIG. 6. The magnetic tape comes to a stop accordingly.
In case that the recording is to be resumed with the recording stop instruction cancelled, the embodiment operates as follows: Assuming that a recording resuming instruction is produced at a point of time T3 as shown in FIG. 6, the level of the recording stop instruction signal (c) becomes a low level. The fall edge of the signal (c) is detected by a NOR gate 72 as shown at a part (m) in FIG. 6. A flip-flop 73 is set by this. The level of the Q output (n) of the flip-flop 73 becomes high. The high level signal (n) is then supplied to the system controller 53 as a reproducing instruction signal. Further, the level of the output (l) of the OR gate 41 also becomes high. As a result, the frequency rotation sequence of the local pilot signals becomes f1, f3, f4 and f2. Then, a reproducing operation begins on the rewound (or wound back) portion of the magnetic tape. Referring now to FIG. 5C, in the record part mentioned above, the frequency component of 3 fH is obtained from a preceding track and the frequency component of fH from a succeeding track until the head comes to trace a track 106 which is located in the third place counting from the last recording track. The head HA then comes to be in an on-track state at that point of time. Referring to FIG. 5D, when the head HB traces a track 108 located second from the last track, the tracking error signal is obtained in the following manner: In this instance, frequency components of 3 fH are obtained as cross-talk components from the pilot signals recorded in both the tracks preceding and succeeding the mainly traced track. Therefore, when the head HB begins to trace the track 108, the level of the tracking error signal produced from the comparison circuit 49 of FIG. 4 suddenly rises. This urges the travelling speed of the magnetic tape to be increased to shift the position of the head HB in the direction of arrow 109 as indicated in FIG. 5D. Following this, when the head HA comes to begin to trace the last track 107, the position of one end of the head HA approximately coincides with the border line between the tracks 107 and 108.
While the head HB is mainly tracing the track 108, any abnormality of the tracking error signal is detected with the signal compared by a hysteresis comparator 74 with a reference voltage produced from a reference voltage generating circuit 75. Further, in the event of detection of any abnormality during this period, an abnormality detection signal (o) is obtained in a manner as shown at a part (o) in FIG. 6. The fall edge of this signal (o), that is, a point of time T4 (see FIG. 6) at which the tracing action on the track 108 by the head HB comes to an end is detected by an AND gate 77 which receives a signal obtained by slightly delaying the abnormality detection signal (o) via a delay circuit 76 and an edge of the signal HSW or (a) as shown at part (p) in FIG. 6.
The timing pulse (p) which is thus obtained resets the flip-flop 66 and another flip-flop 73. With these flip-flops reset, recording is resumed by bringing the reproduction of a vide signal to a stop. Since the level of the Q output (n) of the flip-flop 73 changes to a low level, the level of the output (l) of the OR gate 41 also becomes low. As a result the rotation sequence of frequencies of the pilot signals comes back to the sequence of f1→f2→f4→f3. Then, in the track 107, recording is performed with the pilot signal of the frequency f2 superimposed upon a video signal.
As obvious from the description given above, the overlapped writing part which is obtained by the VTR according to this invention is limited to only one-field portion of the video signal (one track). Besides, the width of tracks in the jointed part of the signal is unvarying. Therefore, the embodiment is capable of carrying out a continuous reproducing operation without deterioration of picture quality and unstable travel of the magnetic tape. It is another advantage of the embodiment that the above-stated advantages are attainable by just generating pilot signals in frequency rotation in the same sequence as in normal recording and reproduction. The invented arrangement thus dispenses with such arrangements as a time counting circuit and a last track detection signal generating circuit that have been indispensable for jointed recording by the conventional VTR's. | A recording apparatus for recording an information signal on a record bearing medium comprises recording means for recording the information signal on the record bearing medium, instruction means for producing an instruction to stop a recording operation, stopping means for bringing the recording operation to a stop in response to the instruction of the instruction means, pilot signal generating means for generating pilot signals of frequencies differing from each other in a first generating pattern one after another, control means for controlling the pilot signal generating means to generate the pilot signals in a second generating pattern in response to the instruction of the instruction means, and superimposing means for superimposing upon the information signal the pilot signals generated by the pilot signal generating means. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a method for bead seating a tubeless tire onto a rim and an apparatus for the same.
2. Description of the Related Art
While tubeless tires provide significant advantages over the tube-type, it is extremely difficult to seat the bead of the tire on the rim. This difficulty creates a special problem when trying to change a tire on the road, far from the customary equipment used to seat the tire.
One solution to the problem had been the introduction of ether inside the tire. The ether is the ignited and the resulting explosion often will seat the bead of the tire on the rim of the tire. Of course, determining the precise amount of ether necessary to seat the tire without potential injury to the operator is often difficult to determine. Factors such as the volume of the tire, the relative humidity in the air, ambient breeze, volume of ether are virtually impossible for the operator to calculate in order to be reasonably certain that sufficient ether is being used. However, if too much ether, again virtually impossible to consistently determine, is used, then a dangerous explosion is possible. Although extremely dangerous and despite the warning by every tire manufacturer that this procedure should not be used, this method is still being employed even though a number of deaths and serious injury result each year.
Another solution, which is best described as mechanical, although it may include some pneumatic elements, relies on the use of flexible straps or segmented hoops which squeeze along the circumference of the tire and thereby force the bead upward toward the bead seating surface. These mechanical devices are not conducive to being portable and require a substantial amount of time in the preparation of the equipment prior to the inflation process.
Still another solution is a class of pneumatic tools, which utilize a source of compressed air to impart momentum to the bead and inject air into the tire, thereby initiating a progressive bead seating process. While these tools are substantial improvement over the above-described apparatus, this type of design still presents problems and, as yet, no pneumatic tool has been universally adopted or totally eliminated the practice of using ether.
U.S. Pat. No. 3,866,654, issued to Duquesne on Feb. 18, 1975, discloses a portable device for inflating tubeless tires that utilizes a source of compressed air stored within a tank which directly supplies an injection nozzle through a long flexible hose. A complicated valve is used for releasing the air stored within a portable tank to control the airflow. The device is expensive to construct, especially due to its complicated valve assembly and cannot release enough air in a sufficiently short period of time so that the bead of the tire will be forced against the rim to properly seat the bead. The inadequacy of this device to meet tire bead seating requirements is primarily due to its cumbersome valve as well as the use of a relatively long flexible standard compressed air hose.
U.S. Pat. No. 5,042,547, issued to Van De Sype on Aug. 27, 1991, discloses a tire bead seating device having multiple air injection nozzles. Four are depicted which direct air from a portable tank. Van De Sype recognized the need for using a simple valve, a ball valve, that permits faster release of the air than was achievable with Duquesne's disclosed valve. However, Van De Sype defeated any advantage gained by the use of the ball valve by requiring multiple flexible long flexible lines having small nozzles. This arrangement substantially increases the airflow resistance downstream of the ball valve, thus correspondingly slowing the rise time of the air released against the bead of the tire and subsequently, reducing the impact on the bead of the tire.
U.S. Pat. No. 5,072,764, issued to Ochoa on Dec. 17, 1991, discloses, as did Van De Sype, a bead seating apparatus that utilizes a hand-operated valve, preferably a ball-type valve, to release a charge of air from a portable storage tank. However, Ochoa, while recognizing the need for a very fast discharge of air from the storage tank, failed to recognize that his nozzle is unnecessarily restricting airflow. Ochoa teaches the use of a nozzle having a discharge area that is less than the cross-sectional area of the discharge barrel. Ochoa also teaches away from the use of large diameter discharge barrels, that is, discharge barrels having an opening larger than 20.4 square centimeters. Ochoa incorrectly states that larger dimensions of discharge barrels tend to cause the discharge impulse of air to impart an undesirably large quantity of momentum to the sidewall of the tire, thereby introducing undesired components into the motion of the bead of the tire. Consequently, much of the advantage gained by the use of a short, rigid, discharge short discharge barrel is lost. Ochoa failed to recognized that the time its takes for the ball valve to be moved from the fully closed to the fully opened position retards the rise time of the pulse of air, thus reducing the effectiveness of the apparatus.
An improvement on the Ochoa device is a tire bead seating apparatus that was manufactured by the BEAD SEATER Corporation. This device also featured a portable tank, a ball-type valve as taught by Van De Sype, Ochoa and a short, rigid discharge barrel as disclosed by Ochoa. However, the BEAD SEATER apparatus provided a unique fan-shaped nozzle having a radius that was dimensioned to correspond to the rim of the tire and had a discharge area that was always greater than cross-sectional area of the discharge barrel. While the nozzle as well as the use of discharge barrel larger than taught by Ochoa resulted in substantially improves performance over its predecessors. However, this device was still limited by the use of the ball-type valve.
U.S. Pat. No. 5,456,302, issued to Demers on Oct. 10, 1995, discloses a tire bead seating apparatus that eliminates the use of discharge barrel and its corresponding valve. This results in the pulse of air having a substantially faster pressure rise time than is found with above-referenced devices. This device makes use of piston that is releasably sealed against the outlet of the portable tank such that the piston is held against the tank outlet by having an air pressure that is higher on the side away from the outlet than is found on the side adjacent to the outlet. Once the air is released on the side of the piston away from the outlet via a quick release valve, the piston moves away from the outlet of the tank, allowing the air inside the tank to be released. The air flows from the tank and is immediately discharged out the discharge nozzle.
This device is substantially more effective than previous attempts due to the substantial faster response time and the further reduction in airflow resistance. However, the design suffers from having a higher cost of manufacture than the Ochoa or BEAD SEATER devices. By having an integral nozzle, this device exhibits an appreciable kickback, especially if the tank is filled to a higher pressure such as 100 lbs/in 2 . Further, the device is particularly sensitive to even small leaks since the volume of air on side of the piston away from tank outlet is very small compared to the volume of air in the tank. Once a small amount of air leaks, the pressure differential across the piston can easily be lost, thus preventing the piston from releasing sufficiently quickly to produce the desired very fast pressure rise time of air that is necessary to efficiently seat the bead of the tire.
A device that is inexpensive to produce, relatively insensitive to leaks, substantially reduces or eliminates kickback, and still provides the extremely fast release of air from the reservoir tank is not found in the prior art.
SUMMARY OF THE INVENTION
It is an aspect of the invention to provide a tire bead seating apparatus that has the least restrictive passage-way for the air charge stored within a tank to proceed to the tire that is to be seated.
It is another aspect of the invention to provide a tire bead seating apparatus that can be activated without the use of a ball-type valve or gate valve and without the use of a conduit or discharge barrel.
It is another aspect of the invention to provide a tire bead seating apparatus that is adaptable to a wide range of truck tire sizes and manufacturers, including those having the most difficult tire beads to seat.
It is still another aspect of the invention to provide a tire bead seating apparatus which is portable and can be easily stowed.
Another aspect of the invention is to provide a tire bead seating apparatus that can be manufactured inexpensively from readily available parts.
Still another aspect of the invention is to provide a tire bead seating apparatus that is insensitive to leaks so that high tolerances between parts are unnecessary.
It is another aspect of the invention to provide a tire bead seating apparatus that substantially eliminates or reduces kickback by using a specially designed nozzle that corresponds to the air releasing assembly of the invention.
Finally, it is an aspect of the invention to provide a tire bead seating apparatus that can be activated by a push button so that the operator can easily activate the device with one hand.
The invention is an apparatus for seating the bead of a tubeless tire on rim. A charging reservoir having a predetermined cross-sectional area is provided. Said charging reservoir is also provided with a fill/quick-release port, an inlet and an outlet. An inflation tank having a predetermined volume and an inlet/outlet is provided, wherein the inlet/outlet of said inflation tank is connected to the inlet of said charging reservoir. Moveably disposed within said charging reservoir is a piston. When said charging reservoir and said inflation tank is pressurized with air via the fill/quick-release port of said charging reservoir, said piston is moveably urged against the outlet of said charging reservoir. Once in this position, the pressurized air in said charging reservoir and said inflation tank is substantially prevented from exiting the outlet of the charging reservoir. When the pressurized air within said charging reservoir is quickly released via the fill/quick-release port of said charging reservoir, said piston substantially instantaneously moves away from the outlet of said charging reservoir. Then, the pressurized air stored in said inflation tank is explosively released through the outlet of said charging reservoir.
A nozzle having an inlet and an outlet is provided. The inlet of said nozzle is connected to the outlet of said charging reservoir. The cross-sectional area of the outlet of said nozzle corresponds to the inlet of said nozzle as well as the outlet of charging reservoir. When the pressurized air from said inflation tank is released, the air passes into the inlet of said nozzle and exits the outlet of said nozzle so that the airflow is directed between the bead of the tire and the rim, thereby seating the tire on the rim.
The above and further objects and advantages of the present invention will become apparent from the description contained hereinafter in combination with the accompanying illustrative figures.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial cut-away side view of the apparatus for seating the bead of a tubeless tire in accordance with the invention.
FIG. 2 is a top view of the nozzle.
FIG. 3 is a front end view of the nozzle.
FIG. 4 is rear view of the charging reservoir head plate.
FIG. 5 is a top detailed view of the preferred embodiment of the charging reservoir head plate.
FIG. 6 is a side view of an alternative embodiment of the piston.
FIG. 7 is an end view of the charging reservoir flange.
FIG. 8 is a side view of an alternative embodiment for controlling the outlet.
FIG. 9 is a cross-sectional view of another alternative embodiment of the piston.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a partial cut-away side view of invention 10 . An inflation tank 12 is preferably a pressure vessel having a capacity of at least 1500 cubic inches and a capability of storing air at pressures of at least 125 lb/in. While ASME approved tanks should be used wherever possible, non-rated tanks which meet the specifications provided herein are also acceptable for use as inflation tank 12 . The actual size and pressure rating of inflation tank 12 will vary according to the size of the tire to be sealed and to the pressure of the air stored therein. The preferred size of tank 12 specified will enable the user to seat the beads of most standard truck tire sizes.
The parts and specifications cited for the preferred embodiment disclosed herein are dimensioned to accommodate typical truck tubeless tires. Substantially smaller tires could obviously be seated with the preferred size specified, however, dimensions and sizes of the parts could be reduced accordingly to meet smaller tire requirements. Substantially larger tires may also be seated with specified apparatus, however, the air pressure within the unit may have to be adjusted accordingly as long as safe limits were not exceeded. The dimensions and parts of the apparatus could be scaled upward to meet the requirements of tires substantially larger than typical truck tires if so desired.
Invention 10 is easily maneuvered and transported by a handle (not shown) attached to the exterior of inflation tank. Another handle 84 is attached to charging head plate 34 which is shown in detail in FIGS. 4 and 5.
Attached to inflation tank 12 is relief assembly 13 , including a pressure gauge 14 which is provided to display the internal air pressure of inflation tank 12 . A pressure relief valve (not shown) that is well known in the art, preferably rated 150 psi, is provided to prevent over-inflation and to release the excess pressure within inflation tank 12 . Relief assembly 14 is connected to inflation tank 12 via nipple 16 . Relief assembly 13 is shown for the sake of clarity opposite to fill/quick-release assembly 51 . However, relief assembly 14 is preferably placed on inflation tank 12 under fill/quick-release assembly 51 so that both structures may be protected from damage during use by handle 84 .
As shown in FIG. 1, fill/quick-release assembly 51 is attached to invention 10 by way of a threaded on end (TOE) nipple 52 which is connected to the charging head plate 34 . Nipple 52 is preferably ⅜ inch sized fitting. Attached to nipple 52 is quick release valve 50 such as manufactured by Deltrol of Bellwood, Ill., model EV 24 A2. However, any type of valve which permits the air to be very rapidly exhausted from charging reservoir 22 could be also be used. Further, the inventor has found that a ⅜ inch or larger ball-type of valve could be substituted for quick release valve 50 . However, the performance of invention 10 will be degraded somewhat due to the slower rise time found with this type of design as discussed above.
Exhaust port 54 is left open so that exiting air is not restricted when valve 50 is actuated. Attached to the other port of quick release valve 50 is a ⅜ inch by ¼ inch bushing 55 . Attached to bushing 55 is ¼ inch close nipple 53 . A “T” 48 , also ¼ inch, is then attached to nipple 53 . Attached to one port of“T” 48 is discharge trigger 49 such as sold by TRAMEC, part number 35000. Attached to the remaining port of“T” 48 is ¼ inch street elbow 60 . Note that elbow 60 is not shown turned at a 90 degree angle for the sake of clarity. Attached to elbow 60 is ¼ ball valve 46 . Assembly 51 is completed by attaching air coupler 44 to ball valve 46 .
FNPT Spud 76 is sized to accommodate nipple 18 and is welded to inflation tank 12 as shown. Inflation assembly 11 is then attached inflation tank 12 via 2 inch TOE nipple 18 which is screwed into spud 76 . The other end of nipple 18 is then welded to outlet section 87 of charging reservoir 22 via welds 20 . Nipple 18 is preferably about five inches long.
Inflation assembly 11 comprises charging reservoir 22 , outlet nipple 38 , and piston 36 . The wall thicknesses and materials for the parts described below are not critical provided the parts are able to withstand the pressures that will be experienced and meet government safety requirements. Also, the dimensions specified can be scaled upwardly or downwardly to correspond to the sizes of tires that are to be seated.
The end of outlet section 87 of charging reservoir 22 is closed off via end plate 57 which is fitted with an opening so that outlet nipple 38 is within the outlet section 87 of charging reservoir 22 . While outlet nipple 38 is shown substantially axially centered within end plate 57 and charging reservoir 22 , nipple 38 could also be offset within charging reservoir 22 . Nipple 38 is welded via welds 20 to end plate 57 and end plate 57 is, in turn, welded to one end of charging reservoir 22 to complete the closure at that end. Note that outlet nipple 38 is also positioned with the threaded end 40 outside of assembly 11 and so that end 42 of nipple 38 is about ¼ inch beyond the opening provided by nipple 18 . In this manner, when piston 36 is urged against end 42 of nipple 38 , piston 36 substantially closes off the control section 89 from the outlet section 87 of charging reservoir 22 thus positioning piston 36 away from the opening provided by nipple 18 which is connected to the outlet section 87 .
In order that a tight seal is provided when piston 36 is urged against end 42 of nipple 38 , end 42 is smoothed by any suitable method such as machining, sanding, etc. Both nipples 38 and 18 are preferably made of steel and about 5 inches long with a wall thickness of approximately {fraction (3/16)} inches.
Attached to threads 40 of nipple 38 is nozzle 66 . Referring now to FIGS. 2 and 3 as well as FIG. 1, nozzle 66 is shown in detail. The inventor has discovered that if invention 10 is discharged without nozzle 66 in position, then the apparatus exhibits substantial kickback as if the user were discharging a firearm. However, the use of nozzle 66 substantially reduces if not eliminates kickback so that the apparatus can held comfortably.
Nozzle 66 is preferably fabricated from sheet steel by folding and spot welding at welds 20 . A 2 inch half-coupling 64 with internal threads 40 is provided so that nozzle 66 can be screwed onto external threads 40 of nipple 38 . Nozzle 66 is designed so that discharge opening 70 has a cross-sectional area that is preferably greater than or equal to the cross-sectional area of nipple 38 . If discharge opening 70 is approximately ¾ inches wide and 6 inches long, this will meet that requirement. However, smaller sized openings for discharge opening 70 can be used as long as the decrease in performance is acceptable. However, the cross-sectional area of discharge opening 70 should always be greater than or equal to 70% of the cross-sectional area of the outlet opening 97 of charging reservoir 22 .
If the preferred dimensions are utilized, nozzle 66 will not present any impediment to the charge of air as it exits through opening. Nozzle 66 is completed by welding a u-shaped rim guide 68 to the top of nozzle 66 via welds 20 . Rim guide 68 serves to position discharge opening 70 between the bead of the tire and rim of the wheel so that bead of the tire can be seated. Also, since nozzle 66 is threaded onto is nipple 38 , nozzle 38 may be turned as desired by a user to facilitate seating the bead of tire when the tire is placed in different positions relative to the user. The other end of charging reservoir 22 is closed via flange 24 which is welded to that end of charging reservoir 22 via welds 20 . As shown in FIG. 7, flange 24 is provided with circumferential holes 26 which serve to bolt via bolts 28 and nuts 30 , head plate 34 onto charging reservoir 22 . Gasket 32 is placed between flange 24 and head plate 34 to seal against leaks. Eight holes 26 are shown, however, more or less could be used as long as charging reservoir 22 is reasonably sealed.
Note that small leaks at this juncture or any other place in the unit are not critical since pressurized air is meant to be stored in inflation tank 12 for only a short period of time, generally, minutes. As noted above, it is an aspect of the invention to be relatively insensitive to air leaks over the short time. Since the preferred embodiment of piston 36 permits air flow to leak past the piston 36 in either direction, any small amount of air which might leak from control area 89 will be replenished from outlet area 87 and storage tank 12 . In this manner, essentially the same pressure will be kept within the control area 89 , outlet area 87 and storage tank 12 so that the release performance of piston 36 will not be degraded over the short term.
In fact, it is preferable not to have invention 10 sealed too tightly, since the unit might be stored in a charged condition which is undesirable for safety considerations. Therefore, it is preferable to have one or more small leaks so that the unit will discharge completely within an hour or so, to prevent storage of the apparatus with a pressurized tank of air.
As shown in FIGS. 4 and 5, head plate 34 provides matching holes 26 so that head plate 34 may be bolted onto flange 24 . Ears 80 extend beyond head plate to serve to provide a point of attachment for handle 84 . Ears 80 are preferably fabricated as part of head plate 34 but ears 80 could also be attached separately. Flange 82 is bent upward from ears 80 which provides two holes through handle 84 may be bolted via bolts 86 . Only one bolt 86 on each side of ears 80 is fastened during shipping the apparatus so that handle 84 may be easily folded to fit within a smaller profile shipping carton. As noted above, once both bolts 86 are in place, handle 84 serves also to protect inflation assembly 11 and relief assembly 13 from being damaged during use.
Referring again to FIG. 1, charging reservoir 22 is preferably a piece of steel pipe about 5 ¼ inches long and 3 ¾ inches OD. This provides an ID measurement for charging reservoir 22 of about 3.510 inches. Corresponding to the dimension of charging reservoir 22 , piston 36 should be 3 ½ inches in diameter. This provides clearance 72 of approximately 10 thousandths. This clearance is sufficient to enable the pressurized air that is introduced via nipple 52 to charging reservoir 22 to fill inflation tank 12 and the outlet section 87 of charging reservoir 22 by leaking past piston 36 through clearance 72 . However, since this opening is so small compared to the two inch opening provided by nipple 18 when piston 36 moves away from end 42 of outlet nipple 38 , substantially all of the air in inflation tank 12 is released through outlet nipple 38 and only a very small amount back through clearance 72 . Of course, if piston 36 configured to permit air to flow in only one direction, no air would flow back into control section 89 once piston 36 is propelled away from end 42 of nipple 38 .
While charging reservoir 22 , nipple 38 , and piston 36 are shown as having a circular cross-section, this is not critical. Other shapes, such as square or rectangular, oval, etc. could be substituted. As shown in FIG. 8, the use of rectangular shape would enable the use of a control member 111 hinged on one side via hinge 112 rather than using a piston to close off the end 42 of outlet nipple 38 . Hinge 112 is preferable any of the various “piano-type” hinges, well known in the art. The use of gasket 90 and hole 94 as shown in FIG. 6 could also be used in this alternative embodiment.
However, a cylinder is the preferred shape since this type of structure is readily available on the market in various sizes and wall thicknesses and thus keeps the cost of manufacture minimized.
As shown in FIG. 6, other options exist for piston 36 . The inventor has found that a disk of DELRIN plastic approximately 3.500 inches in diameter and ¾ inches thick is preferable. The use of this material and size for piston 36 enables the apparatus to be constructed inexpensively without compromising performance. The alternative embodiment for piston 36 shown in FIG. 6 features an aluminum disk, again about ¾ inches thick so that piston 36 will not wobble or bind when piston 36 slides inside of charging reservoir 22 .
As noted above, air is able to leak past piston 36 in either direction using the preferred embodiment. However, piston 36 could also be configured as a one-way (check) valve by the addition of gasket 90 which is attached to piston 90 via flat washer 92 and bolt 88 . A plurality of holes 94 could also be provided in piston 36 to help facilitate airflow in direction 96 but not in the reverse path.
The inventor has discovered that the use of a piston cup, such as manufactured by McMaster Carr of New Brunswick, N.J. 08903, model no. 9411 K27, could be used in place of gasket 90 . A piston cup serves to make piston 36 function even more efficiently as a one-way valve in situations where such precision may be desirable.
The resistance of the airflow path from the inflation tank 12 into end 42 must be very small compared to the resistance through the clearance 72 . Therefore, piston 36 preferably must be permitted to slide far enough away from end 42 in control section 89 to provide a cross-sectional piston discharge area that is greater than or equal to cross-sectional area of end 42 . The inventor has discovered that stroke dimension 78 should be preferably ½ to 1 inch. The minimum stroke dimension 78 that will provide a piston discharge area greater than the cross-sectional area of end 42 of the nipple 38 is easily calculated by dividing the radius of end 42 of nipple 38 squared divided by the diameter of end 42 of nipple 38 . As before, if decreased performance is acceptable, then stroke dimension 78 can be reduced accordingly but should be sufficiently long so that the air passageway between piston 36 and end 42 is at least 70% of the cross-sectional open area of end 42 .
The inventor has discovered that an essential aspect for successful seating a bead of a tire using this type of apparatus is releasing the stored air as quickly as possible between the rim and the bead of the tire. Therefore, the airflow must not be subjected to unnecessary resistance which will restrict the flow along the path from the air storage tank to the tire. As shown in FIG. 6 of the inventor's U.S. Pat. No. 5,456,302, incorporated herein by reference, the faster the response curve, the more effective the apparatus will be in seating the bead of a tire.
As noted above, the preferable OD dimension for charging reservoir 22 is 3 ¾ inches steel cylinder having a wall thickness of approximately ⅛ inch. This provides an ID of approximately 3.510 inches. However, a smaller ID pipe for charging reservoir 22 could also be used.
A pipe having a two-inch diameter ID such as outlet nipple 38 has a cross-sectional area of approximately 3.14 square inches. Therefore, to prevent the air flow path from having an air flow resistance greater than that of nipple 38 , the cross-sectional area of the ID of charging reservoir 22 less the area occupied by the OD of nipple 38 is preferably greater than or equal to 3.14 square inches. Using the ID dimension of charging reservoir 22 and the OD dimension of nipple 38 , this yields a cross-sectional area of about 5.24 square inches between the inner wall of charging reservoir 22 and the outer wall of nipple 38 , that is, outlet section 87 . This is calculated by finding the cross-sectional area of the ID of charging reservoir 22 , which is 9.67 square inches and subtracting the cross-sectional area of OD of nipple 38 which is 4.43 square inches, thus yielding 5.24 square inches for outlet section 87 .
Clearly, the airflow through this section of the unit has a resistance that is substantially less than that provided by the opening 97 in nipple 38 . The ID of charging reservoir 22 could be reduced without detrimentally increasing the resistance of outlet section 87 of charging reservoir 22 as long as the cross-sectional area of charging reservoir 22 was not less than 7.57 square inches. This results in an ID of approximately 3 ⅛ inches for charging reservoir 22 . If reduced performance is acceptable, even smaller ID charging reservoirs could be used. However, the cross-sectional area of outlet section 87 should be at least 70% of the cross-sectional area of opening 97 of the charging reservoir 22 .
Also, note that the difference between the cross-sectional area of piston 36 and nipple 38 determines the force that holds piston 36 against end 42 of nipple 38 . For example, assume that invention 10 is charged with air at a pressure of 100 psi. The force against the control section 89 side of piston 36 is 100 times 9.62 square inches or approximately 960 pounds of force. The force pushing against the outlet section 89 side of piston 36 is 100 times 4.43 square inches (provided by area 75 which was shown above to be the cross-sectional area of the charging reservoir 22 less that cross-sectional area of the OD of nipple 38 ) plus 14.7 times 3.14 square inches (the cross-sectional area of the ID of outlet nipple 38 which is at atmospheric pressure) or approximately 489 pounds. Therefore, a net force (pressure differential) of approximately 470 pounds is forcing piston 36 against end 42 of nipple 38 .
This also explains why invention 10 provides such a fast response time. By rapidly reducing the pressure in control section 89 using quick-release valve 50 , the pressure on the outlet section 87 side still remains at approximately 489 pounds thus forcing piston 36 away from end 42 . As soon as piston 36 is just slightly away from end 42 , the force pushing piston 36 changes to 100 psi over the entire outlet section 87 side of piston 36 or approximately 960. Thus, piston 36 is propelled toward the head plate 34 of charging reservoir 22 permitting the air held within inflation tank 12 to exit explosively via outlet nipple 38 through nozzle 66 and out discharge port 70 (FIG. 3 ).
To use invention 10 , an air hose (not shown) is attached to air coupler 44 and ball valve 46 is opened. Air enters through nipple 52 into charging reservoir 22 . Air is entering faster in control section 89 than can leak through clearance 72 . Therefore, piston 36 is forced against end 42 . Air pressure continues to build up in charging reservoir 22 and continues to leak through clearance 72 causing outlet section 87 of charging reservoir 22 and inflation tank 12 to fill. Once pressure gauge 14 reaches the desired pressure, ball valve 46 is closed and outlet section 87 , control section 89 of charging reservoir 22 , and inflation tank 12 are substantially at the same pressure. Then, the nozzle 66 of invention 10 is positioned between the bead of a tire and the rim as shown in the referenced FIG. 5 of the '302 patent. Trigger 49 is depressed which causes the air within the control section 89 of charging reservoir 22 to be released from port 54 of quick release valve 50 . Piston 36 is then violently propelled toward head plate flange 24 , explosively releasing the air in inflation tank 12 into outlet section 87 to exit through nipple 38 and, finally, through nozzle 66 to seat the bead of the tire onto the rim.
While there have been described what are at present considered to be the preferred embodiments of this invention, it will be obvious to those skilled in the art that various changes and modifications may be made therein without departing from the invention and it is, therefore, aimed to cover all such changes and modifications as fall within the true spirit and scope of the invention. | A method and apparatus for bead seating a tubeless tire onto a rim. Air stored in a portable tank is released as a single pneumatic pulse having an extremely fast rise time. This is accomplished using a charging reservoir having a fill/quick-release port, an inlet and an outlet. A piston divides the charging reservoir into two sections, a control section containing the fill/quick-release port and an outlet section containing the inlet and the outlet. The portable tank is connected to the inlet of the outlet section. Air that is introduced into the fill/quick-release port fills the control section of the charging reservoir. Since the piston is a loose fit, air is able to slowly leak past the piston and fill the outlet section of the charging reservoir and the portable tank that is connected to the inlet. The pressure differential across the piston keeps the piston tightly against the outlet, holding the pressurized air in the outlet section and the portable tank. Once the pressurized air in the quick-release section is released, the pressure differential is reversed and the piston is propelled away from the outlet, thereby explosively releasing the air from outlet section and the connected portable tank as a single pneumatic pulse. The pneumatic pulse is directed between the rim of the wheel and the bead of the tire by a unique nozzle to seat the bead of the tire. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a pleated car curtain, particularly to a pleated car curtain which is easily hung on a car window.
2. Description of Related Art
Current sun-protective shields used in cars basically are of one of two types: curtains fixed on car windows and shields that are movable. A fixed curtain for covering a car window mostly is made of pleated sun-protective material with upper and lower edges. Guiding cords run along the upper and lower edges and across the car window, with ends fixed on the car window, guiding the curtain, such that the curtain stays parallel to the car window when opened or closed. This arrangement provides effective protection from the sun, with the curtain stably held.
A fixed curtain, however, is normally fixed on the rear end of the car window and therefore not easily dismounted. When not in use, the curtain is therefore just folded. With the car in motion, no unhindered view out of the car is possible, a remaining dead angle adds to driving risks.
A movable shield has no guiding cords and during use has to be fixed by other means. As shown in FIG. 8, a conventional board-like movable sun-protective shield 1 for covering a car window 2 has a board with upper and lower edges that can be doubled on itself. During use, the board is opened, the lower edge thereof is laid on a dashboard 8 , and the upper edge thereof is held by a rear-view mirror 3 and sun visors 4 . Only then the upper edge of the sun-protective shield 1 is prevented from coming down, making use of the sun-protective shield 1 inconvenient.
Furthermore, as shown in FIG. 8A, the sun-protective shield 1 has a considerable thickness and takes up a relatively large volume when folded, such that storage in a car is not convenient, as well.
Referring to FIG. 9, a soft movable sun-protective shield 5 has a suction cup 6 in a central position. The sun-protective shield 5 is made of a flexible board with a reinforcing rim 7 . Being soft, the sun-protective shield 5 has only a limited area, and covering a large car window requires using several sun-protective shield 5 . When the sun-protective shield 5 is not used, the suction cup 6 is pulled away from the car window 2 , and the reinforcing rim 7 is bent into small curves to allow the sun-protective shield 5 to be stored in a small volume. This, however, is a difficult and awkward procedure.
The sun-protective shield 5 is also made without the suction cup 6 . As shown in FIG. 9A, the rear-view mirror 3 and the sun visors 4 have to be employed to hold the sun-protective shield 5 , which is rather inconvenient.
SUMMARY OF THE INVENTION
The main object of the present invention is to provide a pleated car curtain of simple structure and little weight.
Another object of the present invention is to provide a pleated car curtain which can be fixed on a car window and provides effective protection from the sun.
The present invention can be more fully understood by reference to the following description and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the structural parts of the present invention.
FIG. 2 is a front view of the pleated car curtain of the present invention when mounted in a car window.
FIG. 2A is a side view of the fixing element of the present invention, the fixing element glued to the car window.
FIG. 2B is a side view of the fixing element of the present invention, the fixing element attached to the car window by suction.
FIG. 2C is a side view of one the ears of the present invention, attached to the car window by suction.
FIG. 2D is a side view of one of the ears of the present invention, attached to the car window by Velcro latches.
FIG. 3 is an enlarged top view of the curtain of the present invention.
FIG. 4 is an enlarged top view of the curtain of the present invention when unfolded.
FIG. 5 is a perspective view of the pleated car curtain of the present invention in the second embodiment.
FIG. 5A is an enlarged schematic illustration of the pleated car curtain of the present invention in the second embodiment.
FIG. 6 is a perspective view of the pleated car curtain of the present invention in the third embodiment.
FIG. 7 is a perspective view of the pleated car curtain of the present invention in the fourth embodiment.
FIG. 8 (prior art) is a schematic illustration of a conventional board-like movable sun-protective car shield when used.
FIG. 8A (prior art) is a schematic illustration of a conventional board-like movable sun-protective car shield when folded.
FIG. 9 (prior art) is a schematic illustration of a conventional soft movable sun-protective car shield with suction cup when used.
FIG. 9A (prior art) is a schematic illustration of a conventional soft movable sun-protective car shield without suction cup when used.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is used to cover a car window 2 of a car.
As shown in FIG. 1, the pleated car curtain of the present invention in a first embodiment mainly comprises: a curtain 10 , made of sun-protective, thin material and pleated and having a width, a height, a left end and a right end; two reinforcing strips 20 on the left and right ends of the curtain 10 , reinforcing the left and right ends of the curtain 10 to maintain a straight form when the curtain 10 is unfolded; and two fixing elements 30 for fixing the left and right ends of the curtain 10 during use thereof. Two ears 11 are attached to the reinforcing strips 20 . During use of the present invention, the ears 11 are hung over the fixing elements 30 , so that the curtain 10 covers the car window 2 and has a protective effect. When the car is started, the ears 11 are removed from the fixing elements 30 , and the curtain 10 is stored away, not hindering sight from inside the car.
Referring to FIGS. 1 and 2, the fixing elements 30 are attached to the car window 2 on opposite lateral ends thereof. Each of the fixing elements 30 has a hook 31 . Each of the ears 11 has a hole 12 . The holes 12 of the ears 11 are respectively hung over the hooks 31 to fix the left and right ends of the curtain 10 on the car window 2 .
Each of the fixing elements 30 is attached to the car window alternatively by one of various ways. As shown in FIG. 2A, a glue layer 30 a lies between each of the fixing elements 30 and the car window 2 , holding together the fixing elements 30 and the car window 2 . Alternatively, as shown in FIG. 2B, each of the fixing elements 30 has a suction cup 30 b, held on the car window 2 by suction.
As a further way to fix the curtain 10 , as shown in FIG. 2C, each of the ears 11 has a suction cup, so that the ears 11 are directly attached to the car window 2 . Alternatively, as shown in FIG. 2D, each of the ears 11 has a VELCRO, or similar hook and loop fastener, latch 32 d, with another Velcro latch 31 d glued to the car window. The latches 31 d, 32 d are easily connected and separated.
Referring again to FIG. 1, the curtain 10 has a plurality of pleats bordering on each other at pleat edges 15 . As shown in FIG. 3, the curtain 10 has a double outer membrane 13 , covering a central reinforcing layer 14 on both sides thereof and glued thereon at high pressure. Thus the curtain 10 from outside looks like a single layer. A reflecting surface layer of electro-coated metallic gloss is added to enhance the sun-protective effect of the curtain 10 .
Referring to FIGS. 3 and 4, the main characteristic of the present invention is that the curtain 10 is produced using high temperature and high pressure. Thus the curtain 10 is made of material which resists changes of form. On each of the pleat edges 15 the curtain 10 has a high form stability. Even when the curtain 10 is unfolded, the pleat edges 15 maintain a sharp V-shaped form. For the reinforcing layer 14 thin material, like textile, plastics or cardboard is used. Working the material at high temperature and high pressure ensures that the pleat edges 15 remain pronounced.
Therefore, as shown in FIG. 2, when the curtain 10 is unfolded and hung on the fixing elements 30 , covering the window 2 , the curtain 10 is stable against deformation due to the V-shaped pleat edges 15 . The curtain will not hang down, and no reduced protected area of the car window 2 will result.
Preferably, the width of the curtain 10 is slightly larger than the width of the car window 2 . Then, after hanging the ears 11 of the curtain 10 over the hooks 31 , with the curtain 10 unfolded, the curtain 10 will stay close to the car window 2 and will not bend down.
Referring to FIG. 5, the present invention in a second embodiment has on one of the reinforcing strips 20 a holding element 40 . The holding element 40 has a main part 41 with an inner side facing the reinforcing strip. The main part 41 is by a pin 43 hingedly connected to one of the reinforcing strips 20 . An L-shaped catch 42 is attached to the inner side, leaving a gap with a width that is larger than the folded thickness of the curtain 10 and the reinforcing strips 20 , allowing to hold the pleated curtain together when folded. As shown in FIG. 5A, after folding the pleated curtain, the user turns, on each of the reinforcing strips 20 , the main part 41 by 90 degrees, so that the catch 42 keeps the curtain 10 and the reinforcing strips 20 together like a bundle.
Referring to FIG. 6, in a third embodiment of the present invention, each of the ears 11 additionally has a holding function like the holding element 40 of the second embodiment. Each of the ears 11 has an inner side and is hingedly connected to one the reinforcing strips 20 via a pin 16 . When the pleated curtain of the present invention is folded, the curtain 10 and the reinforcing strips 20 form a compact body with a folded thickness. For each of the ears 11 , an L-shaped catch 17 is attached to the inner side, leaving a gap with a width that is larger than the folded thickness of the curtain 10 and the reinforcing strips 20 , allowing to hold the pleated curtain together when folded. After folding the pleated curtain, a user turns the ears 11 by 90 degrees, so that on each of the left and right ends of the curtain 10 the catch 17 keeps the curtain 10 and the reinforcing strips 20 together. Thus folding and storing of the pleated curtain of the present invention is convenient.
Referring to FIG. 7, the present invention in a fourth embodiment has short reinforcing strips 20 b, leaving an upper section 10 a of the curtain 10 and a lower section 10 b of the curtain 10 uncovered. This allows the user to reduce the height of the curtain 10 easily by scissors 50 , adapting to the car window 2 for optimum sun-protection.
The pleated car curtain of the present invention has the following advantages:
1. The curtain 10 is light and is, when not in use, stored in a compact bundle with little space requirement, making use thereof convenient.
2. When the pleated curtain is hung up, the curtain 10 will not sag, due to the pleated edges 15 . With the reinforcing strips 20 stably connected to the fixing elements, the pleated curtain will not drop away from the car window 2 .
3. Since the curtain 10 is made of thin material, the user easily adapts the pleated curtain to the car window 2 by cutting the upper and lower sections 10 a, 10 b of the curtain 10 , as needed.
4. For fixing the pleated curtain, no structural parts of the car, like the rear-view mirror and the sun visors, need to be employed.
5. A simple structure makes the present invention suitable for mass production.
6. As compared to a conventional sun-protective shield, the present invention has a small volume when folded, which makes storing more convenient.
While the invention has been described with reference to preferred embodiments thereof, it is to be understood that modifications or variations may be easily made without departing from the spirit of this invention which is defined by the appended claims. | A pleated car curtain for covering a car window, includes: a curtain made of thin, sun-protective material, having a plurality of pleats parallel to lateral edges and a plurality of pleated edges between said pleats; two reinforcing strips on the lateral edges of the curtain; two ears, respectively attached to the two reinforcing strips; and two fixing elements, fixed on the car window on two sides thereof, respectively holding the two ears when the curtain is in use. The curtain is produced using high temperatures and pressures so that the shape of the plurality of pleated edges is preserved as acute angles when the curtain is folded and unfolded. | 8 |
This application claims priority of United States Provisional Application No. 60/058,234, filed Sep. 9, 1997. The present invention is directed toward an apparatus for controlling the use of carbon dioxide in dry cleaning clothes and/or fabrics.
FIELD OF INVENTION
Carbon dioxide is an environmentally safe medium for cleaning clothes, garments and fabrics as it is a naturally occurring gas. Presently, clothes, garments and fabrics are cleaned using solvents such as percholoeythylene which present exposure health risks.
The present invention employs a cleaning chamber, a carbon dioxide condenser, a carbon dioxide storage tank, a compressor, a warm-up vessel, a pump, a distillation vessel, and a programmable logic controller. Piping, air operated valves (AOVs), and manually operated valves (not shown) interconnect the process components of the invention. Instrumentation and wiring (not shown) interconnect to the programmable logic controller. The programmable logic controller controls the AOVs, motor starters, heater power and pumps.
The cleaning chamber is the place where the clothes, garments and fabrics reside during the cleaning process. The cleaning chamber employs nozzles as taught, disclosed and claimed in copending U.S. patent application Ser. No. 09/005,866, filed Jun. 12, 1998.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 5,467,492 to Chao et al. discloses and claims an apparatus and method for DRY CLEANING OF GARMENTS USING LIQUID CARBON DIOXIDE UNDER AGITATION AS CLEANING MEDIUM. The '492 patent does not illustrate a compressor which is used in a reclaim mode.
U.S. Pat. No. 5,456,759 to Stanford, Jr. et al. discloses sonication cleaning using megasonic energy. The '759 patent does not include equipment to reclaim gaseous carbon dioxide left over in the cleaning chamber after the wash cycle. In column 7, lines 12 et seq. it is disclosed that contamination, be it organic or particulate, can be removed through decompression, filtration, or a combination of both.
U.S. Pat. No. 5,683,473 to Jureller, et al. at column 19, lines 60 et seq. also discloses the separation of dirt and spent cleaning agents through decompression. The '473 does not show or claim reclamation of the carbon dioxide
U.S. Pat. No. 5,267,455 to Dewees, et al. illustrates and claims a vaporizer 11 in combination with other equipment. No reclamation apparatus is disclosed or claimed in the '455 patent.
None of the related art discloses or claims an apparatus for reclaiming gaseous carbon dioxide from the cleaning chamber, nor does any of the related art disclose the reclaiming apparatus and process in combination with a distilling and purging process for removing contaminants from the liquid or from the carbon dioxide.
SUMMARY OF THE INVENTION
The system operates in eight modes. The first mode is for loading the cleaning chamber with clothes and/or fabrics. After the cleaning chamber is loaded, it is evacuated in an evacuation mode to remove air and/or moisture therefrom. The cleaning chamber is then filled with carbon dioxide gas first from the top of the distillation vessel and then from the storage tank. The filling of the cleaning chamber with carbon dioxide gas is known as the prefill mode. Next, the cleaning chamber is filled with liquid carbon dioxide from the storage tank. This is the pressurization mode.
After the cleaning chamber has been filled with liquid carbon dioxide, the wash mode begins and the clothes/fabrics are agitated by the continuous flow of liquid carbon dioxide alternating between two sets of nozzles. During the wash mode, liquid carbon dioxide is constantly passed through a lint trap, a filter, and through a condenser where it then is recirculated from storage and pumped back to the cleaning chamber. Wash mode time can be controlled by the operator by way of interface to a programmable logic controller.
At the conclusion of the wash mode, the liquid carbon dioxide is drained in the drain mode back to the carbon dioxide storage tank. Before reaching the storage tank, the liquid passes through the pump, the filter, and the carbon dioxide condenser.
The storage tank is controlled between 690 and 775 psig by means of a programmable logic controller which monitors the pressure of the storage tank and compares it to a set point. At these pressures the carbon dioxide is in the temperature range of approximately 10 to 14° C. The signal difference is then acted upon by the programmable logic controller which controls the refrigeration compressor.
Following the drain mode comes the reclaim mode. In the first step of the reclaim mode, the carbon dioxide gas remaining in the cleaning chamber is pumped out by the carbon dioxide compressor to the condenser where it is converted to liquid and then is sent back to the storage tank. In a second step of reclamation, known as the reclaim warm-up step, the carbon dioxide gas is pumped through a warm-up vessel by the compressor and is then recirculated to the cleaning chamber. This prevents the formation of solid carbon dioxide (dry ice) on or in the clothes, garments or fabrics in the cleaning chamber. In a third step of reclamation, known as the final reclaim step, the compressor is used as a two stage compressor. Following the reclaim mode, the cleaning chamber is vented in the vent mode.
There are several maintenance modes. For instance, periodically make up carbon dioxide must be added to the system, the distillation vessel's sludge must be dumped and the filter must be changed. The user of the apparatus supplies a make-up source of liquid carbon dioxide which is usually a pressurized carbon dioxide bottle at 700 to 860 psig at ambient temperatures. The customer supplied carbon dioxide source is interconnected to liquid feed pump referred to herein as the second feed pump. Alternatively, carbon dioxide may be input to the distillation vessel to make up lost carbon dioxide.
One of the maintenance modes is the distillation mode. Liquid carbon dioxide is continuously boiled off in the distillation mode leaving behind spent cleaning agents, dirt and other contaminants left over from the wash cycle.
It is a further object of the present invention to provide a carbon dioxide cleaning system which includes the reclamation of the carbon dioxide gas from the cleaning chamber to increase the cost efficiency of the carbon dioxide cleaning system.
It is a further object of the present invention to provide a carbon dioxide cleaning system which includes a cleaning chamber, a compressor, a filter, a condenser, a storage tank, a pump, a warm-up vessel, and a programmable logic controller to control the system.
It is a further object of the present invention to provide an apparatus for distilling and cleaning the carbon dioxide used in laundering clothes garments and fabrics.
It is a further object of the present invention to provide a liquid level sensing apparatus for determining the level of liquid in a tank or other vessel comprising a thermocouple, a heater, a protective covering surrounding the thermocouple, such that the protective covering extends within the tank. It has been found that the temperature change when the protective covering is immersed in the fluid is significant and enables liquid level control within the system.
It is a further object of the present invention to provide a process for cleaning carbon dioxide used to clean clothes, garments, and fabrics comprising the steps of: filling a distillation vessel with liquid carbon dioxide from a storage tank until a predetermined high level in the distillation vessel is reached; heating and boiling the liquid carbon dioxide in the distillation vessel to generate gaseous carbon dioxide; removing the gaseous carbon dioxide from the distillation vessel and compressing the gaseous carbon dioxide with the compressor; condensing the gaseous carbon dioxide in the condenser into liquid carbon dioxide; and, returning the liquid carbon dioxide to the storage tank.
It is a further object of the present invention to provide a process for cleaning carbon dioxide which includes a step of heating and boiling the liquid carbon dioxide in the distillation vessel to generate gaseous carbon dioxide resulting in the lowering of the liquid level in the distillation vessel until a predetermined low level in the distillation vessel is reached which initiates the filling of the distillation vessel with liquid from the bottom of the storage tank.
It is a further object of the present invention to provide a process for reclaiming gaseous carbon dioxide from a cleaning chamber employing carbon dioxide to launder clothes, garments or fabrics utilizing a compressor, condenser and storage tank, comprising the steps of: compressing the gaseous carbon dioxide; condensing the gaseous carbon dioxide into liquid carbon dioxide; and, storing the liquid carbon dioxide in a storage tank.
It is a further object of the present invention to provide an apparatus for reclaiming gaseous carbon dioxide from the cleaning chamber comprising a two stage compressor, a warm-up vessel, a condenser and a storage tank.
It is a further object of the present invention to provide an apparatus for providing reclamation of gaseous carbon dioxide from the cleaning chamber in three steps. In the first step the compressor pumps (using two parallel stages) the gaseous carbon dioxide from the cleaning chamber to the condenser where heat is removed therefrom and it is liquified and returned to the storage tank. In the second step the compressor pumps (using two parallel stages) the gaseous carbon dioxide through the warm-up vessel and back to the cleaning chamber thus preventing the formation of solid carbon dioxide (dry ice) on and in the clothes, garments or fabrics within the cleaning chamber. Alternatively, the compressor could pump a portion of the gaseous carbon dioxide to the condenser and back to the storage tank. In the third step the compressor initially pumps the gaseous carbon dioxide using two parallel stages until a certain pressure is reached within the cleaning chamber. Then, the compressor is utilized as a two stage compressor utilizing the stages of compression in series rather than in parallel. Two stages of compression in series are utilized to remove as much of the gaseous carbon dioxide as possible from the cleaning chamber and pump it to the condenser.
It is a further object of the present invention to provide a closed loop apparatus for controlling the use of carbon dioxide in cleaning clothes, garments or fabrics which includes an on-board storage tank, carbon dioxide pump, cleaning chamber, carbon dioxide warm-up vessel, compressor, condenser, programmable logic controller, and interconnecting lines and air operated valves. Air operated valves are employed throughout the apparatus for control thereof. Electric power, air pressure, and cooling water are supplied by the user to operate the components and air operated valves of the apparatus.
It is an object of the present invention to provide a cleaning chamber which includes an alternating three-way valve controlling the flow of liquid carbon dioxide admitted to nozzles residing within the cleaning chamber.
The objects of the invention will be best understood when taken in conjunction with the following Brief Description Of The Drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustrating just the essential equipment elements in the apparatus for cleaning clothes, garments or fabrics including the compressor, cleaning chamber, warm-up vessel, pump, condenser and storage tank and their interconnection and valving.
FIG. 2 is a schematic illustrating the essential elements in the apparatus for cleaning clothes, garments or fabrics together with a second pump for making up (adding) liquid carbon dioxide to the apparatus and equipment for distilling cleaning agents and dirt from the liquid carbon dioxide.
FIG. 3 is a schematic similar to FIG. 2 additionally illustrating a lint trap, filter train, vacuum pump for evacuating the cleaning chamber and a line and valve interconnecting the storage tank and the top (gas side) of the distillation vessel.
FIG. 3A is a schematic of the preferred embodiment of the invention. FIG. 3 illustrates, among other things, a pressure transducer monitoring the pressure in the storage tank, a three-way valve interposed between the storage tank, pump and cleaning chamber, and a three-way valve controlling the flow into nozzles leading into the cleaning chamber. Additionally, FIG. 3A also illustrates three way 25A and 65 interconnecting the pump, cleaning chamber and the filter train. FIG. 3A also illustrates that the PLC controls the apparatus.
FIG. 4 is a partial cross-sectional view of the heated thermocouple used to detect, indicate, and control level of the liquid carbon dioxide in the storage tank.
FIG. 5 is a schematic diagram of block 1, the cleaning chamber 1, illustrating a three-way valve for alternately directing the flow of liquid carbon dioxide into two sets of nozzles in the cleaning chamber.
FIG. 6 is a cross-sectional view of the heated thermocouple in the tank with the liquid carbon dioxide level below the protective covering of the thermocouple.
FIG. 7 is a cross-sectional view of the heated thermocouple in the tank with the liquid carbon dioxide level above the protective covering of the thermocouple.
FIG. 8 is a table illustrating the valve positions corresponding to the functional modes of the preferred embodiment of the apparatus as illustrated in FIG. 3A. FIG. 8A and FIG. 3A should be considered together. FIG. 8 should not be considered together with any figure other than FIG. 3A.
DESCRIPTION OF THE INVENTION
FIG. 1 is a schematic illustrating just the essential equipment elements in the apparatus including the compressor 5, cleaning chamber 1, warm-up vessel 4, pump 2, condenser 8, and storage tank 3, and the interconnection and valving for cleaning clothes, garments or fabrics. The pump 2 is a positive displacement pump and is capable of outputting a variable amount of liquid carbon dioxide. The pump 2 is rated for 50 gallons per minute of liquid carbon dioxide at system pressure which is nominally 690 to 775 psig. All of the elements of the apparatus are controlled by a programmable logic controller 61. See FIG. 3A. The programmable logic controller used in the instant invention is a KOYO DL 405.
The hydraulic two stage compressor 5 employed in the invention includes a first stage 6 and a second stage 7 Reference numeral 13 indicates the first stage input of the compressor and reference numeral 14 indicates the first stage output of the compressor. Reference numeral 15 indicates the second stage input of the compressor and reference numeral 16 indicates the second stage output of the compressor. Reference numeral 67 indicates a check valve as will be readily understood by those skilled in the art for controlling the direction of the flow of gaseous carbon dioxide through the compressor. First valve 9 controls the flow in the first line 10 communicating between the cleaning chamber 1 and the compressor 9. Second valve 11 controls the flow in a second line 12 communicating between the warm-up vessel 4 and the cleaning chamber 1.
Third valve 18 controls the flow in third line 17 interconnecting between the first stage output 14 and the second stage output 16 of the compressor. Fourth valve 20 controls the flow in the fourth line 19 interconnecting the first stage output of the compressor to the second input of the compressor.
Fifth valve 22 controls the flow in fifth line 21 interconnecting the compressor 5 with the condenser 8. Sixth line 23 interconnects the condenser with the storage tank 3 and seventh line 24 interconnects the storage tank and the pump. A vent valve 36 and vent line 37 provide for venting of the cleaning chamber.
The equipment schematically illustrated in FIG. 1 is sufficient to perform a washing cycle. Line 75' and valve 76 permit a simple washing cycle flow path, namely, between the storage tank, pump, cleaning chamber, condenser and return to the storage tank.
FIG. 2 is a schematic illustrating the essential elements in apparatus for cleaning clothes, garments or fabrics together with a second pump for making up (adding) liquid carbon dioxide to the apparatus and also includes equipment for distilling cleaning agents, and dirt from the liquid carbon dioxide.
FIG. 2 illustrates an air drive liquid carbon dioxide pump 33, sometimes referred to as second pump 33, for filling or making up liquid carbon dioxide to the storage tank 3 The second pump 33 is interconnected to the storage tank by line 34. Valve 35 permits or controls the admission of the liquid carbon dioxide into the storage tank. FIG. 2 additionally illustrates valve 27 controlling flow in line 28 interconnecting the storage tank and the distillation vessel 30. Distillation vessel 30 includes heater 63 whose function will be described in detail hereinbelow.
Still referring to FIG. 2, valve 76 controls flow in line 75' which interconnects the cleaning chamber and the condenser. Valve 32 resides in line 31 and controls flow between the distillation vessel and line which leads to condenser 8 Finally, still referring to FIG. 2, valve 29 controls the flow in line 29' interconnecting the distillation vessel and the compressor.
FIG. 3 is a schematic similar to FIG. 2 further illustrating a lint trap 44 and a filter train 45. Line 47 interconnecting the top of the storage tank to the top of the distillation vessel is also illustrated. Additionally, FIG. 3 illustrates a valve 49 controlling the flow in line 50 interconnecting the cleaning chamber 1 and the vacuum pump 48. FIG. 3 also illustrates valve 62 controlling flow in line 24 between the storage tank 3 and the pump 2. Line 75 interconnects the filter train and the condenser.
FIG. 3A illustrates the preferred embodiment. FIG. 3A illustrates valve 62A, a three-way valve, which is capable of allowing flow through any two paths at one point in time but not through all three paths at the same time. The paths are labeled x, y and z on FIG. 3A. Also see FIG. 8 which is a tabulation of the valve positions versus the functional mode of the preferred embodiment of the apparatus as illustrated in FIG. 3A. Similarly, FIG. 3A illustrates valve 65 as a three-way valve interposed in line 71 between pump 2 and valve 46. Valve 46 is also a three-way valve and functions under the direction of the programmable logic controller and intermediate hardware to alternately send liquid carbon dioxide through one set of nozzles 51, 52 and then the second set of nozzles 53, 54. Also, see FIG. 5.
A check valve 39 in line 31 is interposed between line 47 and the distillation vessel.
Valve 65 is a three-way valve and its paths are labeled x, y and z. See FIG. 8 for a table of the positioning of valve 65 versus the functional modes of the apparatus.
Referring still to FIG. 3A, line 72 interconnects three-way valve 65 and three-way valve 25A. Three-way valve 25A and line 26 interconnect the filter train 45 and the lint trap 44. The valve position versus functional mode of valve 25A are shown in FIG. 8.
FIG. 3A also illustrates line 73 interconnecting the cleaning chamber 1 and the valve 62A. FIG. 3A also illustrates the distillation vessel 30 having a distillation dump valve 66. The distillation dump valve is operated when an accumulation of dirt and other solids accumulate on the bottom of the distillation vessel over a period of time. The distillation vessel functions to clean the liquid carbon dioxide by boiling off the clean liquid carbon dioxide and leaving behind the dirt and spent cleaning agents.
The present invention includes a reclamation process or mode. See FIGS. 8 and 3A. During reclamation, gaseous carbon dioxide resides in the cleaning chamber 1 and the clothes/fabrics therein. To improve efficiency and to remove the gaseous carbon dioxide from the clothes/fabric, the carbon dioxide must be evacuated from the cleaning chamber 1 Referring to FIG. 3A, carbon dioxide gas is removed through first valve 9 by the carbon dioxide compressor 5.
In this first step of reclaiming carbon dioxide gas from the cleaning chamber, the compressor 5 is used as a dual single stage compressor. In other words the compressor has two stages operating in parallel. After compression, the carbon dioxide gas is forwarded to the carbon dioxide condenser 8 via line 21 and valve 22 (which is open) where it is returned to the storage tank 3 as a liquid.
When the cleaning chamber pressure drops to approximately 450 psig, the second step of reclaiming gaseous carbon dioxide begins and the compressor pumps the gaseous carbon dioxide gas from the cleaning chamber through the warm-up vessel 4 and returns it to the cleaning chamber. Valve 22 closes to force the compressed gas into warm-up vessel 4 and through valve 11 which opens to admit heated and compressed carbon dioxide gas into the cleaning chamber. This keeps the gas in the cleaning chamber 1 in the gaseous state and prevents formation of dry ice (solid carbon dioxide) in the clothes/fabrics. Those skilled in the art will recognize that other pressures may be utilized to initiate the second step of the reclamation process or mode.
A third reclamation step follows the warm-up step which is similar to the first reclamation stage. The compressor operates in the parallel mode, to wit, as a dual single stage compressor until such time as the pressure drops below 125 psig. When the cleaning chamber pressure drops below 125 psig the compressor is used as a two stage compressor operating in series. Valves 18 and 11 close and valve 20 opens allowing a first stage of compression and subsequently a second stage of compression. Valve 22 opens to allow the gas to pass to the condenser. Following the reclamation process or stages, the cleaning chamber is vented through line 37 and vent valve 36. This is known as the vent mode or evacuation mode.
Next, upon completion of the venting process, the cleaning chamber is opened to load/unload clothes and fabrics. The cleaning chamber has an inside length of 26 inches and an inside diameter of 26 inches. Upon closing the door to the cleaning chamber, the cleaning chamber is then evacuated through vacuum line 50 and valve 49 by means of a vacuum pump 49 as shown in FIG. 3A. Refer to FIG. 8 for the valve lineup for the evacuation mode of the preferred embodiment illustrated in FIG. 3A. This removes the air and/or water from the cleaning chamber.
The next mode is the prefill mode. Carbon dioxide gas is prefilled from the distillation vessel 30 through valves 9 and 29. Carbon dioxide gas is brought to the cleaning chamber from the distillation vessel and when the differential pressure between the cleaning chamber and the distillation vessel is less than or equal to 200 psi, then valves 9 and 29 are closed and prefilling gas from the top of the storage tank 3 begins.
The prefilling from the top of the storage tank 3 occurs through valves 32, 22 and 11. At this time, valve 27 is open to allow the distillation vessel to boil off some of the carbon dioxide which results in pressurizing the storage tank 3 so as to provide needed net positive suction head to the pump 2 Filling the cleaning chamber with carbon dioxide gas from the distillation vessel 30 and the storage tank 3 prevents the blockage of the flow nozzles with dry ice that would occur if filling liquid carbon dioxide directly from the storage tank to the cleaning chamber were attempted. When the storage tank/cleaning chamber differential pressure is less than 100 psi, the carbon dioxide gas is no longer brought from the top of the storage tank.
Once the cleaning chamber is filled with carbon dioxide gas as aforestated, the next mode is the pressurization mode. Valve 27 is closed. The cleaning chamber is initially filled from the storage tank by gravity and in pump 2 After some time the pump 2 is energized and finishes the filling of the cleaning chamber.
Liquid enters the cleaning chamber through valve 62A via ports x-z, valve 65 via ports z-y, and valve 46 through one of its paths. Pump 2 starts after a short time delay following the positioning of valve 65 to allow flow through ports z-y. The carbon dioxide gas is removed from the cleaning chamber through the lint trap, valve 25A via ports y-z, through the filter train, through line 75 and ultimately passes through the condenser where it is liquified and sent to the storage tank.
The wash cycle or mode is next. During the wash cycle the cleaning chamber is completely filled, with liquid carbon dioxide. Valve 46 is a three-way valve having one input and selectively outputs from one of two outputs. Valve 46 alternately permits fluid to flow to a first set of nozzles (51, 52) and a second set of nozzles (53, 54). This provides the agitation to the cleaning chamber so as to agitate the clothes/fabrics therein and to dislodge dirt from the clothes/fabrics. The wash cycle time is controlled and set by the operator as desired on the programmable logic controller. During the wash cycle liquid carbon dioxide is continuously pumped into the cleaning chamber and continuously removed from the cleaning chamber through the lint trap 44, through valve 25A via ports y-z, through the filter train 45, through line 75 and into the carbon dioxide condenser 8 where it is subcooled. The pressure in the storage tank is continuously monitored by a pressure transmitter 64 which transmits the pressure to a pressure indicating controller in the programmable logic controller, which provides on-off control for operation of a freon pump which controls the cooling circulation within the carbon dioxide condensing unit. The pressure set point, or the point about which control is maintained in the storage tank, is approximately 775 psig.
At the conclusion of the washing cycle or mode, the drain mode is entered. See, FIG. 3A and FIG. 8. Liquid is drained from the cleaning chamber through valve 62A via ports y-z to and through pump 2, through valve 65 via ports z-x, through valve 25A via ports x-z, through the filter train 45, through the carbon dioxide condenser 8 and ultimately to the storage tank 3.
During the drain mode pump 2 is not running. Upon conclusion of the drain mode (which is controlled by a drain timer) the first step of the reclaim mode is initiated.
Maintenance modes are indicated in FIG. 8 such as the mode for storage fill which is the carbon dioxide makeup mode. Similarly a valve lineup for the distillation of contaminants in the distillation mode is indicated in FIG. 8.
Referring to FIG. 3, the distillation mode, the electric heater 63 is energized provided the liquid carbon dioxide is above a low level setpoint. If the liquid carbon dioxide drops below the low level setpoint then the heater 63 is deenergized.
Above the low level setpoint, distillation vessel heater 63 is energized and boils the liquid carbon dioxide into gaseous carbon dioxide. The gaseous carbon dioxide is removed from the distillation vessel through valve 29 by the compressor 5. The distillation vessel pressure is reduced by the compressor 5 until it is 100 psi below the pressure of the storage tank. Valve 27 opens filling the distillation vessel with liquid carbon dioxide until the high level setpoint is reached. Valve 27 closes, compressor 5 shuts down, and vessel valve 29 closes when the liquid carbon dioxide reaches the high level setpoint. The distillation vessel heater remains powered when the liquid carbon dioxide is at or above the high level setpoint and boils off the liquid until it is below the high level setpoint which results in the opening of valve 29 and the starting of the compressor 5 The high and low setpoints are sensed by the heated thermocouple shown in FIGS. 4, 6 and 7.
In the storage tank fill mode, which is another maintenance mode, an air driven pump 33 supplies liquid carbon dioxide through valve 35 provided the liquid carbon dioxide is below the high level setpoint of the storage tank 3 There are four heated thermocouples as disclosed in FIGS. 4, 6 and 7 used to monitor and control the level of liquid carbon dioxide in the storage tank. Similarly, there are two heated thermocouples in the distillation vessel.
The programmable logic controller controls receives inputs from various pressure transmitters, position switches, pressure switches, limit switches, differential pressure switches, and temperature switches which are input into the programmable logic controller and are then manipulated by the programmable logic controller upon certain conditions being present. The programmable logic controller subsequently outputs certain signals for operation of relays, interposing relays and solenoids which control the apparatus and position the valves as shown in FIG. 8.
It has been discovered that the use of a Type T thermocouple 57 with a heater 58 wrapped around the wires of the thermocouple as illustrated in FIG. 4 can be used to sense liquid level and, in particular, can sense the level of liquid carbon dioxide in a pressurized container. The Type T thermocouple is a copper-constantan combination and may or may not physically engage the protective covering 56 which is exposed to the liquid/gaseous carbon dioxide inside the storage tank. The protective covering is an incoloy sheath. Two watts are supplied at 24 volts D.C. to the heater. The signal wires are connected to a voltage measuring device which is input to the PLC.
When liquid carbon dioxide 55 covers the protective covering of the thermocouple a dramatic decrease in temperature is indicated. See, FIG. 7. When liquid carbon dioxide 55 is below the protective covering of the thermocouple a dramatic increase in temperature is indicated. See, FIG. 6. Therefore, carbon dioxide liquid level can be inferred from the measured temperature. Use of the thermocouple is an inexpensive, simple way of sensing the liquid level in a pressurized carbon dioxide storage tank 59. The thermocouple is affixed to the carbon dioxide storage tank by threaded connection or other means.
It will be apparent to those of skill in the art that the invention has been set forth by way of example only and that certain modifications can be made to the invention as described above without departing from the spirit and scope of the appended claims. | An apparatus and method for controlling the use of carbon dioxide in drying cleaning clothes, garments and other fabrics is disclosed and claimed. The components of the invention include a distillation vessel, a compressor, a warm-up vessel, a cleaning chamber, a condenser, and a carbon dioxide storage tank. A programmable logic controller is utilized to control the apparatus. Several modes of use are disclosed. One mode, the reclaim mode, enables the efficient operation of the apparatus. As the name implies the reclaim mode recovers most of the carbon dioxide gas remaining in the cleaning chamber is removed therefrom. There are three steps of the reclaim mode: in the first steps the compressor pumps the gaseous carbon dioxide in two parallel stages from the cleaning chamber to the condenser where heat is removed therefrom and it is liquified; in the second step the compressor pumps the gaseous carbon dioxide through the warm-up vessel and back to the cleaning chamber thus preventing the formation of solid carbon dioxide (dry ice) on the clothes, garments or fabrics in the cleaning chamber; and, in the third step two stages of compression are utilized to remove as much of the gaseous carbon dioxide as possible from the cleaning chamber and pump it to the condenser. The carbon dioxide used in the apparatus is cleaned, in part, by a distillation vessel. Heated thermocouples are used to detect the level of liquid carbon dioxide in the storage tank and the distillation vessel. | 3 |
BACKGROUND OF THE INVENTION
[0001] The invention relates to a system and method for handling moist bulk granular material and in particular to a system and method for handling and transporting moist animal feed.
[0002] It has been known in the feeding industry that it is desirable to provide cereal grain by-products, including moist corn gluten meal and/or corn gluten feed, to animals such as cattle to rapidly increase their weight and bring them to market early. Grain by-products are generally defined and described by the Association of American Feed Control Officials, Incorporated (2001, at page 243) and include, for example corn gluten feed. In the past it has been possible to supply moist grain by-products to animals if the animals were located in the vicinity of a corn processing plant. The moist grain by-products could be shipped by truck. This mode of transportation, however, is inefficient and costly, particularly if bulk quantities of moist grain by-products were being shipped over long distances. In addition, the likelihood that the shipment of moist grain by-products ending up being contaminated at the point of delivery increases significantly when shipped over long distances, such as thousands of miles. This is because the moisture in the product allows for the growth of microorganisms such as bacteria, fungi, yeast, and the like.
[0003] In the past in order to solve this problem, grain by-products have been dried and generally pelletized before shipping. The dried, pelletized product has an increased shelf life and the shipping costs are considerably reduced because water is not being shipped with the product. However, drying the product causes a significant decrease in nutritional value of the grain by-product feed to animals. This would be desirable to avoid. Hence, it would be desirable to ship a product that is not dried to ensure that the animals are fed a product that is high in nutritional value.
[0004] Investigations have been made as to whether conventional rail systems could be used to ship moist grain by-products. Unfortunately, most rail cars such as a hopper or coal car are designed in such a way that an unloading orifice or chute has a reduced cross-section. This reduced cross-section would tend to restrict the flow of moist material, such as the instant moist grain by-products, out of the car. With moist grain by-products, it would be almost impossible to empty such a car having a restricted chute. The moist product would stick and clog the orifice or chute. If a coal car was used to haul moist grain by-products, and dumped using a standard coal-type receptacle, this also would contemplate a very deep hole with very narrow cone-like receptacles used to receive coal. These systems would not work, if at all, with moist grain by-products.
[0005] Further, the high moisture content of the moist grain by-products (which generally is from about 30 to about 70 percent weight), together with a relatively acid pH of the meal, would cause an uncoated or unlined steel car coal car to corrode. This corrosion would cause the moist product to stick onto the rough corroded interior surface of the car, as well as potentially contaminate the grain by-product.
[0006] What is needed then is a system for shipping and handling a moist perishable product, such as moist grain by-products over long distance while maintaining the product in substantially stable uncontaminated condition to maintain its nutritional value.
SUMMARY OF THE INVENTION
[0007] This invention is directed to a method of supplying a bulk quantity of moist grain by-products using an invertible railroad container or car which is capable of being inverted and unloaded into containers below the grade of the inverted railroad container or car without uncoupling adjacent railroad cars. The container or body of the car is supported by a plurality of trucks or wheel assemblies for engagement with rails. The method of the invention also contemplates unloading the bulk quantity of moist grain by-products to road transport containers which are effective for distributing the moist grain by-products to customers and/or users of the by-products or to locations not served by rail.
[0008] In one aspect, the invertible railroad container or car has an aluminum body so that it will not corrode. In another aspect, an invertible railroad container or car may have a steel body which is lined with an extremely durable coating, such as an epoxy coating which resists abrasive wear to protect the body from corrosion. It is important that the car does not corrode for product integrity, such that rust and scale do not contaminate the product being hauled. It also is important that the interior of the car be smooth, stay smooth and retain a proper coefficient of friction between the interior surface of the railroad car and moist grain by-products over time, such that the moist product will not stick or be retained by the railroad car when it is inverted.
[0009] In order to distribute moist grain by-products economically, the rail system of the invention includes using invertible railroad containers or cars to transport the moist grain by-products and which will not have the moist product stick thereto during inverting and unloading. In an important aspect, the railroad container or car is covered, such as with a tarp, to maintain feed purity, maintain the moisture content of the feed within a desired range of from about 30 to about 70 weight percent and maintain the resulting nutritional value of the grain by-products. The cover over the product also protects the product from the contamination from soil, rain, snow and other contaminants.
[0010] Wind screens, which may be semi-circular in shape, are located at least at the front end of the car, and in another aspect at the front and the rear end of the aluminum railroad car body. The wind screens protect the flexible cover or tarp over the moist bulk feed from being displaced and/or lifted by air rushing over the railroad car when the car is in motion. A wind screen at each end of the car and facing the direction of travel will ensure that the car need not be uncoupled or realigned. With two wind screens, one wind screen will always face the direction of travel.
[0011] A plurality of flexible ribs or bows are used to support the flexible cover in a convex fashion over the moist feed within a car body and help prevent moisture being collected on the tarp. Because an aluminum car body may lack the strength of a steel car body, the aluminum body may be prone to being pulled inward during the inversion of the car and unloading. The moist feed also may hang up in the car because the tarp bows may hold product in the car when the car is being dumped. To prevent stress or a load from being transferred from the tarp bows to the walls of the car (tending to pull them inward) and to prevent catastrophic mechanical failure of the bows themselves, one end of each bow is designed to sever from its attachment point to the car body to permit the flow of material out of the car. In one aspect, at least one end of each of the ribs attached to the upper portion of the car body is easily severable from the car body. This is so that when the railcar is inverted for unloading the ribs do not support the weight of the moist feed which would tend to pull the walls of the railroad car inward.
[0012] In order to continuously transport the moist feed from the railroad car after it has been inverted, the moist feed is loaded onto a moving conveyor. In one aspect, a reciprocating floor arrangement will be positioned beneath the unloading area of the railroad car to move the moist feed to a conveyor. The conveyor or reciprocating floor then will carry the moist by-products to road transport containers or trucks which are effective for distributing the by-products to customers or users of the feed, or to one or more mixing tanks where the feed may be mixed and then may be dispensed to trucks for distribution.
[0013] The invention also contemplates and permits the minimization of permanent on-site storage facilities for feed or moist grain by-products, both at the production point where the feed is produced and at the receiving point where the feed is received from the railroad cars. With two trains having about 50 or more cars as described herein with one train unloading at the receiving point and one train loading at the production point with a week or less train-transit time between the receiving and production points, considerable savings result in practicing the invention because of the lower cost of rail shipping versus truck shipping and because the invention is effective for permitting all of the by-product production being stored in the train cars as described herein, both at the production and receiving points. The invention permits storage of the grain by-products at the production point without any special “fast loading” equipment with delivery of the by-product at a rail-end or receiving point without any permanent storage silos at the receiving point. In one aspect, less than about a one week supply of feed needs to be stored in plastic bags as a buffer in the event of a rail delay.
[0014] It is a principal object of the present invention to provide a system and method for transporting moist bulk grain by-products by rail without by-products being contaminated or the nutritional value being reduced.
[0015] It is another object of the present invention to provide a system and method for transporting moist bulk grain by-products which can quickly and conveniently unloaded in large quantities for immediate transport to customers and users of the grain products or to locations not served by rail.
[0016] It is another object of the invention to transport in large quantities of moist grain by-products without prolonged storage in separate containers which are not located on the railroad car or trucks.
[0017] Other aspects of the present invention will become obvious to one of ordinary skill in the art upon review of the following specification and claims in light of the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] [0018]FIG. 1 is a perspective of a system for handling and transporting wet feed embodying the present invention; and
[0019] [0019]FIG. 2 is a perspective view partially in section of the system shown in FIG. 1, showing a rail car positioned inverted within a rail car inverter.
[0020] [0020]FIG. 3 is a perspective view of a tarp assembly for the rail car, illustrating support framework;
[0021] [0021]FIG. 4 is a perspective view of the tarp assembly, illustrating the support framework and a tarp;
[0022] [0022]FIG. 5 is a perspective view of the tarp assembly;
[0023] [0023]FIG. 6 is a perspective view of the tarp assembly, illustrating the tarp in a closed position; and
[0024] [0024]FIG. 7 is a partial section view of the rail car of FIG. 1, across the longitudinal axis thereof.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Referring now to the drawings and especially to FIG. 1, a system for handling and delivering moist bulk feed is shown therein and generally identified by reference numeral 10 . The system 10 includes an invertible railroad car 12 having a railroad car body 14 preferably comprised of aluminum. The car body 14 can receive and hold feed during shipment, preferably a moist grain by-product. These moist grain by-products include, by way of example, aspirated grain fractions, brewers dried grains, buckwheat middlings, condensed distillers solubles, condensed fermented corn extractives with germ meal bran, corn bran, corn flour, corn germ meal (wet and dry milled), corn gluten feed, corn gluten meal, corn grits, corn distillers dried grains, corn distillers dried grains/solubles, corn distillers dried solubles, grain sorghum distillers dried grains, grain sorghum distillers grains/solubles, grain sorghum distillers dried solubles, grain sorghum flour, barley distillers dried grains, barley distillers dried grains/solubles, barley distillers dried solubles, barley flour, wheat distillers dried grains, wheat distillers dried grains/solubles, wheat distillers dried solubles, wheat flour, hominy feed, malt sprouts, oat groats, oatmeal feed, pearl barley by-products, peanut skins, rice bran, rice polishings, rye middlings, sorghum grain flour gelatinized, sorghum grain flour partially and partially aspirated gelatinized, wheat bran, wheat shorts, wheat germ meal, wheat germ meal defatted, wheat middlings, wheat mill run, and wheat red dog. The aluminum body resists the corrosive effects of the moist grain by-product which is loaded into the car body. By-products, such as corn gluten feed, typically have a pH of about 4.0 to about 4.5, which together with the high moisture content of the corn gluten feed, would tend to corrode a steel car. A plurality of trucks 16 is connected to the railroad car body 14 and supports the railroad car body 14 over a pair of rails 18 , as may best be seen at an unloading station 20 , shown in FIG. 1.
[0026] The railroad car body 14 includes a front end 22 and a rear end 24 , with a front end wind screen 26 and a rear end wind screen 28 respectively positioned thereon. The wind screens 26 and 28 disrupt the flow of air over the car body 14 when the railroad car 12 is being moved. The wind screen facing the direction in which the car is to move (i.e., facing the flow of oncoming air) is effective for reducing displacement of a flexible cover 30 as air rushes over the cover 30 when the railroad car 12 moves. At the production facility, the moist grain by-products may be loaded onto the uncovered car with a conveyor to a distant site for loading onto a truck for further transport to a site remote from the rail facility, such as a feed lot.
[0027] The railroad car inverter 40 includes a pair of arcuate members 42 and 44 for rotatably supporting other portions of the car inverter 40 and the railroad car 12 . The tarp 30 is removed from the loaded railroad car 12 . The car inverter 40 then receives the railroad car 12 loaded with moist grain by-product in clamping fashion and rotates it at least about 120 to about 180 degrees to upend the car 12 to allow the moist bulk feed to drop into a feed unloading area 46 . The car inverter 40 avoids problems with feed clogging that would occur with a typical hopper car. In addition the car 12 may be unloaded without uncoupling it from other cars on a train.
[0028] At a bottom portion 46 of the unloading area is a reciprocating floor 48 for delivery of the moist bulk feed from the railcar body 14 to a conveyor assembly 50 . The reciprocating floor as describe in U.S. Pat. No. 4,508,211 may be used, the disclosure of which patent is incorporated by reference herein. The conveyor assembly 50 carries the moist bulk feed to trucks or like vehicles for immediate delivery to customers or users. The conveyor may also transport the feed to a processing station which may include a pair of mixers 52 and 54 for mixing the feed before loading the feed onto a truck. The conveyor 50 conveys the meal or feed to the mixer at a rate of about 1,000 ton per hour.
[0029] While the feed may be stored in storage compartments, such as plastic bags, tanks or silos, where it will be available for shipment via truck or the like, in one aspect the method and system of the invention generally contemplates moving the grain by-products from production facility, then by rail and then by truck to an end user or customer without storage. Further, the system and method embodying the present invention provide convenient transport of large quantities of feed, in particular moist corn gluten feed without losing the nutritional properties of the feed or contaminating or losing any feed along the way.
[0030] FIGS. 3 - 7 illustrate a tarp assembly 300 for protecting the feed within the railroad car 12 in accordance with aspects of the invention. The tarp assembly 300 also assists in maintaining feed purity by retaining moisture within the interior of the railroad car 12 . The tarp assembly 300 includes the flexible cover 30 , which may comprise a selectively retractable tarp 310 for covering the open top of the railroad car 12 and protecting the load therewithin from the elements, such as moisture, wind, and dirt or other debris. The tarp 310 protects the load from contamination, prevents product from being blown from the car while being transported and prevents a loss of the nutritional properties of the moist by-products. The tarp 310 is movable between an open position, wherein access to the interior of the railroad car 12 is permitted, and a closed position, wherein the open end of the railroad car 12 is covered by the tarp 310 .
[0031] As illustrated in FIGS. 3 and 4, the tarp assembly 300 includes a supporting frame assembly 320 for supporting the tarp 310 when in its closed position covering the open end of the railroad car 12 . The supporting frame assembly 320 comprises a plurality of rib members 322 for extending between longitudinal sides of the railroad car 12 . A first end 324 of each rib member 322 is pivotably attached to a bracket member 330 , mounted along the top surfaces of the railroad car 12 . A second end of each rib member 326 is hollow and slidably fitted over a rib shank member 328 attached relative to the top surfaces of the railroad car 12 , opposite the bracket members 330 , as will be described further hereinbelow.
[0032] The rib shank members 328 are fixed to longitudinally extending frame members 340 , extending substantially the length of the railroad car 12 . The rib and rib shank members 322 and 328 are bowed in a convex manner between the sides of the railroad car 12 and have an apex approximately in the center of the railroad car 12 . The convex bowing of the rib and rib shank members 322 and 328 is effective to allow moisture to prevent moisture from collecting on the tarp 300 thereover. Any moisture on the closed tarp 300 may be directed over the sides of the railroad car 12 by the convex shape imparted to the tarp 300 by the rib and rib shank members 322 and 328 .
[0033] Extending parallel to the longitudinal sides of the railroad car 12 and between the midsections of the rib members 322 are a pair of ridge straps 350 , as shown in FIG. 4, for supporting the tarp 310 between the rib members 322 . The ridge straps 350 are secured to the rib members 322 with ridge strap retainers 352 . The ridge strap retainers 352 wrap around the rib members 322 and between the pair of ridge straps 350 to maintain the spacing between the ridge straps 350 . In one aspect of the invention, the ridge straps 350 and ridge strap retainers 352 are formed of nylon, although other materials may be equally suitable.
[0034] Attached at opposite ends 22 and 24 of the railroad car 12 to the upper surfaces thereof are a pair of pan assemblies 360 . The pan assemblies 360 are substantially L-shaped, as illustrated in FIG. 4. Each pan assembly 360 includes a horizontally oriented flat surface 362 positioned in a corner of the railroad car 12 for allowing the railroad car 12 to be contacted by the inverter 40 for dumping the load from the railroad car 12 . The pair of pan assemblies 360 are configured so that their respective flat surfaces 362 are both positioned on the same side of the railroad car 12 for contacting by the inverter 40 .
[0035] The pan assemblies 360 each also include an arcuate portion 364 that extends upwardly and along the respective end of the railroad car 12 . The wind screens 26 and 28 may comprise wind screens 366 attached along the top of the arcuate portion 364 of each pan assembly 360 to restrict air from moving beneath the tarp 310 in its closed position and lifting the tarp 310 relative to the frame assembly 320 . The wind screens 366 are placed on each of the pan assemblies 360 to ensure that air is restricted from flowing beneath the closed tarp 310 regardless of the direction of travel of the railroad car 12 .
[0036] The tarp 310 is sized to extend between the sides and ends of the railroad car 12 to cover the open end thereof when the tarp 310 is in its closed position. The tarp 310 includes a first longitudinal edge 312 securable via a retainer strip 318 to the edge of the railroad car 12 having the brackets 330 attached thereto. The second longitudinal edge of the tarp 314 , opposite the first edge 312 , has lengthwise extending pocket 316 for receiving a rod 370 .
[0037] In the closed position, the tarp 310 covers the open end of the railroad car 12 , as illustrated in FIGS. 5 and 6. As described above, the first edge 312 of the tarp 310 is secured to the edge of the railroad car 12 . The second edge 314 is held in place by positioning the rod 370 within a semi-circular groove 342 formed in an outwardly facing surface of the frame members 340 , as illustrated in FIG. 7. The frame members 340 include three portions, a middle portion 344 and a pair of end portions 346 and 348 . The end portions 346 and 348 are space apart from the middle portion 344 to leave gaps for inverter 40 to contact the railroad car 12 . The grooves 342 are formed in each of the middle and end portions 344 , 346 , and 348 .
[0038] When the rod 370 is seated in the groove 342 , a locking member 372 may be used to secure the rod 370 therein and prevent inadvertent removal of the rod 370 and thus the tarp 310 . The locking member 372 has an aperture 374 through an end thereof for insertion of an end of the rod 370 . Once the rod 370 is inserted into the aperture 374 of the locking member 372 , the locking member 372 is secured relative to the respective pan assembly 360 , such as by wedging in a slot formed therein. The locking members 374 are provided at both ends of the rod 370 .
[0039] When the tarp 310 is in the closed position, the configuration of the tarp assembly 300 is such that it does not significantly protrude, if at all, beyond the perimeter edges of the railroad car 12 . Accordingly, the frame members 340 and the pan assemblies 360 are sized to not significantly protrude beyond the perimeter edges of the railroad car 12 . It can be desirable for the tarp assembly 300 to not significantly protrude beyond the perimeter edges of the railroad car 12 to ensure that the profile of the railroad car 12 remains within acceptable limits, as may be required by the railroads. The configuration of the tarp assembly 310 may also be effective to allow for retrofitting of existing railway cars, and to prevent interference between the tarp assembly 310 and the car inverter 40 .
[0040] To move the tarp 310 to the open position from the closed position, such as for loading or dumping of the interior of the railroad car 12 , the locking members 372 are first removed from the ends of the rod 370 . Next, the rod 370 is rotated to roll the tarp 310 therearound. A winch or other mechanism may be provided to assist in rolling the tarp 310 around the rod 370 . For this purpose, the ends of the rod 370 may be splined for engagement with the winch mechanism. As the tarp 310 is wound around the rod 370 , the rod 370 is moved toward the side of the railroad car 12 opposite the frame members 340 .
[0041] The tarp 310 is not completely wound around the rod 370 . Instead, the tarp 310 is wound around the rod 370 until the rod 370 abuts against stop members 380 . The stop members 380 , as illustrated in FIG. 6, are positioned to prevent the rod 370 and tarp 310 wound therearound from moving over the flat surfaces 362 of the pan assemblies 360 , thereby assuring that the tarp 310 in its open position does not interfere with the operation of the inverter 40 . The stop members 380 extend vertically from the pan assembly 360 and rib members 322 . In one aspect, a pair of stop members 380 are attached to each pan assembly 360 and a pair of stop members 380 are attached to ribs members 322 located in the mid-section of the railroad car 12 .
[0042] To empty the railroad car 12 , the tarp 310 is moved to its open position, as described above. The inverter 40 may contact the railroad car 12 on the flat surfaces 362 of the pan assemblies 360 and between the middle and end portions 344 , 346 , and 348 of the frame members 340 . The railroad car 12 may then be rotated to an upended position, allowing the load within the interior to fall therefrom. The load falls between the rib members 322 and the ridge straps 350 , which preferably remain in place.
[0043] However, the slidable engagement of the rib members 322 to the rib shank members 328 allows the rib members 322 to move relative to the shanks 328 , permitting limited movement of the rib members 322 in response to the load falling therepast. If the load exerts sufficient forces on the rib elements 322 , some or all of the rib elements 322 may completely slide off of the rib shank members 328 and pivot about their hinge connection to the brackets 330 to a position out of the way of the falling load. Once the load is emptied from the railcar, any rib members 322 disengaged from their respective shank elements 328 can be replaced thereover.
[0044] In addition, the telescoping engagement between the rib and rib shank members 322 and 328 permits expansion and contraction therebetween to ensure that the members 322 and 328 extend between the sides of the railroad car 12 . For example, when the railroad car 12 is empty, the engaged rib and rib shank members may be at first position relative to each other. As the railroad car 12 is loaded, the sides may tend to spread apart due to the weight of the load, requiring the rib and rib shank members 322 and 328 to telescopingly expend relative to each other. The spreading of the sides of the railroad car 12 may not be uniform. For example, after loading the distance between the sides of the railroad car 12 at the center may be greater than toward the ends thereof. In addition, the telescoping rib and rib shank members 322 and 328 are effective to reduce hang up of the moist by-product on the frame assembly 320 when the railroad car 12 is unloaded by upending it in a car inverter 40 . This can prevent the aluminum car body 14 from being damaged during unloading in the car inverter 40 by the weight of the feed on the rib and rib shank members 322 and 328 pulling the sides of the aluminum car body 14 inward. Accordingly, the rib and rib shank members 322 and 328 may be configured to compensate for spanning variable distances between the sides of the railroad car 12 .
[0045] While there has been illustrated and described a particular embodiment of the present invention, it will be appreciated the numerous changes and modifications where will occur to those skilled in the art, and is intended in the appended claims to cover all those changes and modifications which fall within the true spirit and scope of the present invention. | A system and method for handling and transporting moist bulk grain by-products include a rail car having an aluminum car body carried by a plurality of trucks for engaging rails. A flexible top cover, supported by a plurality of breakaway curved ribs, is positioned over an open top of the rail car to protect the moist bulk grain by-products carried therein. The car body has a front end and a rear end each having a wind screen for spoiling or deflecting the flow of air over the car as it moves to prevent the flexible top cover from being lost or damaged. The car may be emptied by a car inverter over a conveyor, such as a reciprocating floor which carries the moist grain by-products to a mixer, or transportation vehicles for distribution to customers or users of the grain by-products. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a Continuation of application Ser. No. 11/429,627, filed on May 4, 2006 now U.S. Pat No. 7,582,440, which is a Continuation of application Ser. No. 10/416,090, filed on Oct. 15, 2003 now U.S. Pat. No. 7,498,034, which is a national stage filing under 35 U.S.C. §371 of PCT International application PCT/GB2001/04906 designating the United States of America, and filed Nov. 6, 2001, the entire contents of which are hereby incorporated herein by reference. This application also claims the benefit under 35 U.S.C. §119(e) to U.S. Provisional Application Ser. Nos. 60/245,566, filed on Nov. 6, 2000 and 60/273,662, filed on Mar. 7, 2001, the entire contents of which are hereby incorporated by reference.
The present invention relates to genes whose expression is selective for the endothelium and use of these genes or gene products, or molecules which bind thereto, in imaging, diagnosis and treatment of conditions involving the vascular endothelium.
The endothelium plays a central role in many physiological and pathological processes and it is known to be an exceptionally active transcriptional site. Approximately 1,000 distinct genes are expressed in an endothelial cell. In contrast red blood cells were found to express 8, platelets 22 and smooth muscle 127 separate genes (Adams et al, 1995). Known endothelial specific genes attract much attention from both basic research and the clinical community. For example, the endothelial specific tyrosine kinases Tie, TIE2/TEK, KDR, and flt1 are crucial players in the regulation of vascular integrity, endothelium-mediated inflammatory processes and angiogenesis (Sato et al, 1993, Sato et al, 1995, Fong et al, 1995, Shalaby et al, 1995, Alello et al, 1995). Angiogenesis is now widely recognised as a rate-limiting process for the growth of solid tumours. It is also implicated in the formation of atherosclerotic plaques and restenosis. Finally endothelium plays a central role in the complex and dynamic system regulating coagulation and hemostasis.
Of the many distinct genes expressed in an endothelial cell, not all are entirely endothelial cell selective and so the genes and their products, and molecules which bind thereto are not generally useful in the imaging, diagnosis and treatment of disease. Thus, there remains a need for endothelial cell specific or selective molecules.
We report here identification of two highly endothelial selective genes which we have called: endothelial cell-specific molecule 1 (ECSM1) and magic roundabout (endothelial cell-specific molecule 4; ECSM4). The terms ECSM1 and ECSM4 are also used to indicate, as the context will make clear, the cDNA and polypeptides encoded by the genes. These genes, and especially ECSM4, are surprisingly specific in their cell expression profile. ECSM4, for example, shows similar endothelial-cell selectivity to the marker currently accepted in the art as the best endothelial cell marker (von Willibrand Factor). Clearly, such a high level of endothelial cell specificity is both unprecedented and unexpected.
ECSM1 (UniGene entry Hs.13957) has no protein or nucleotide homologues. It is most likely to code for a small protein of 103 aa (the longest and most up-stream open reading frame which was identified in the contig sequence). ECSM1 contains two sequence tagged sites which are unique and definite within the genome (STS sites; dbSTS G26129 and G28043) and localise to chromosome 19. A polynucleotide comprising the complement of part of the ECSM1 gene is described in WO 99/06423 (Human Genome Sciences) (termed “gene 22”; page 31-32) as being expressed primarily in umbilical cord endothelial cells and to a lesser extent in human adipose tissue. However, WO 99/06423 discloses an open reading frame (ORF) in the polynucleotide which encodes a polypeptide of only 45 amino acids. According to our analyses, this does not represent the correct polypeptide of 103 amino acids, as the actual start codon in ECSM1 is further 5′ than the one identified in WO 99/06423.
The human magic roundabout (ECSM4) cDNA clone with a long ORF of more than 417 aa (GenBank Accession No AK000805) and described in WO 99/46281 as a 3716 nucleotide sequence was identified by BLAST searches for the Hs.111518 contig. This sequence is rich in prolines and has several regions of low amino acid complexity. BLAST PRODOM search (protein families database at HGMP, UK) identified a 120 bp region of homology to the cytoplasmic domain conserved family of transmembrane receptors involved in repulsive axon guidance (ROBO1 DUTT1 protein family, E=4e-07). Homology was extended to 468 aa (E=1.3e-09) when a more rigorous analysis was performed using ssearch (Smith and Waterman 1981) but the region of similarity was still contained to the cytoplasmic domain. The ROBO1 DUTT1 family comprises the human roundabout homologue 1 (ROBO1), the mouse gene DUTT1 and the rat ROBO1 (Kidd et al, 1998, Brose et al, 1999). Because of this region of homology we called the gene represented by Hs. 111518 “magic roundabout” (ECSM4). Additionally, BLAST SBASE (protein domain database at HGMP) suggested a region of similarity to the domain of the intracellular neural cell adhesion molecule long domain form precursor (E=2e-11). It should be noted that the true protein product for magic roundabout is likely to be larger than the 417 aa coded in the AK000805 clone since the ORF has no apparent up-stream limit, and size comparison to human roundabout 1 (1651 aa) suggests a much bigger protein. This is confirmed in FIG. 3 which shows the translation product of human ECSM4 to be around 118 kDa. However, ECSM4 is smaller than other members of the roundabout family, sharing only two of the five Ig domains and two of the three fibronectin domains in the extracellular region. The intracellular putative proline rich region that is homologous to those in roundabout are thought to couple to c-abl. FIG. 12 shows the full length amino acid sequence of human ECSM4 (1105aa), and the sequence of the mouse homologue is shown in FIG. 13 . Nucleotide coding sequences which display around 99% identity to the ECSM4 nucleotide sequence given in FIG. 12 are disclosed in WO 99/11293 and WO 99/53051.
Additional sequences which display homology to the ECSM4 polypeptide or polynucleotide sequence are disclosed in EP 1 074 617, WO 00/53756, WO 99/46281, WO 01/23523 and WO 99/11293. However, none of these publications disclose that the sequences are selectively expressed in the vascular endothelium, nor suggest that they may be so expressed.
Recently intriguing associations between neuronal differentiation genes and endothelial cells have been discovered. For example, a neuronal receptor for vascular endothelial growth factor (VEGF) neuropilin 1 (Soker et al, 1998) was identified. VEGF was traditionally regarded as an exclusively endothelial growth factor. Processes similar to neuronal axon guidance are now being implicated in guiding migration of endothelial cells during angiogenic capillary sprouting. Thus ephrinB ligands and EphB receptors are involved in demarcation of arterial and venous domains (Adams et al, 1999). It is possible that magic roundabout (ECSM4) may be an endothelial specific homologue of the human roundabout 1 involved in endothelial cell repulsive guidance, presumably with a different ligand since similarity is contained within the cytoplasmic i.e. effector region and guidance receptors are known to have highly modular architecture (Bashaw and Goodman 1999).
However, to date there has been no mention of the existence of an endothelial counterpart, nor the expression pattern of the magic roundabout (ECSM4) gene being restricted to endothelial cells especially angiogeneic endothelial cells, nor of any function of the encoded polypeptide.
It should be noted that a surprising result of our RT-PCR analysis, described in Example 1, was that genes identified here appear to show endothelial specificity ( FIG. 1 ) comparable with the classic endothelial marker von Willebrand factor (vWF). Expression of known endothelial specific genes is not usually 100% restricted to the endothelial cell. Data presented herein shows the quite unanticipated finding that ECSM4 is not expressed at detectable levels (at least using the methods described in the examples) in cell types other than endothelial cells, given the less than 100% selectivity of known endothelial cell markers. Ribonuclease protection analysis has confirmed and extended this observation ( FIG. 14 a ). ECSM4 expression was seen to be restricted to endothelium (three different isolates) and absent from fibroblast, carcinoma and neuronal cells. KDR and FLT1 are both expressed in the male and female reproductive tract: on spermatogenic cells (Obermair et al, 1999), trophoblasts, and in decidua (Clark et al, 1996). KDR has been shown to define haematopoietic stem cells (Ziegler et al, 1999). FLT1 is also present on monocytes. In addition to endothelial cells vWF is strongly expressed in megakaryocytes (Sporn et al, 1985, Nichols et al, 1985), and in consequence present on platelets. Similarly, multimerin is present both in endothelial cells (Hayward et al, 1993) and platelets (Hayward et al, 1998).
Generally speaking, endothelial and haematopoietic cells descend from same embryonic precursors: haemangioblasts and many cellular markers are shared between these two cell lineages (for review see Suda et al, 2000). Hence, the finding that the genes ECSM1 and ECSM4 are not expressed in cells other than those of the vascular endothelium is highly surprising.
Determination of genes whose expression is selective for the vascular endothelium allows selective targeting to these cells and thereby the specific delivery of molecules for imaging, diagnosis, prognosis, treatment, prevention and evaluation of therapies for conditions associated with normal or aberrant vascular growth.
A first aspect of the invention provides a compound comprising (i) a moiety which selectively binds the polypeptide ECSM4 and (ii) a further moiety.
By “the polypeptide ECSM4” we include a polypeptide whose sequence comprises or consists of the amino acid sequence given in FIG. 4 or 5 or 7 or 12 or 13 or whose sequence is encoded by the nucleotide sequence given in FIG. 4 between nucleotides 1 and 1395 or between nucleotides 2 and 948 of FIG. 5 or FIG. 7 or between nucleotides 71 and 3442 of FIG. 12 or between nucleotides 6 and 3050 of FIG. 13 and natural variants thereof. Preferably, the ECSM4 polypeptide is one whose amino acid sequence comprises the sequence given in FIG. 4 or FIG. 12 .
By “the polypeptide ECSM4” we include a polypeptide represented by SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293, or the polypeptide represented by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00/53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 or SEQ ID No 31 of WO 99/11293.
By “the polypeptide ECSM4” we also include any naturally occurring polypeptide which comprises a consecutive 50 amino acid residue portion or natural variants thereof of the polypeptide sequence given in FIG. 4 or 5 or 7 or 12 or 13 . Preferably, the polypeptide is a human polypeptide.
Embodiments and features of this aspect of the invention are as described in more detail below.
A second aspect of the invention provides a compound comprising (i) a moiety which selectively binds the polypeptide ECSM1 and (ii) a further moiety.
Preferably, in the first and second aspects of the invention, the binding moiety and further moiety are covalently attached.
By “the polypeptide ECSM1” we include a polypeptide whose amino acid sequence comprises or consists of the sequence given in FIG. 2 and natural variants thereof.
By “the polypeptide ECSM1” we also include any naturally occurring polypeptides which comprises a consecutive 50 amino acid residue portion or natural variants thereof of the polypeptide sequence given in FIG. 2 . Preferably, the polypeptide is a human polypeptide.
Preferably, the polypeptide ECSM1 amino acid sequence comprises the sequence given in FIG. 2 but does not comprise the amino acid sequence encoded by ATCC deposit No 209145 made on Jul. 17, 1997 for the purposes of WO 99/06423.
By “natural variants” we include, for example, allelic variants. Typically, these will vary from the given sequence by only one or two or three, and typically no more than 10 or 20 amino acid residues. Typically, the variants have conservative substitutions.
In a preferred embodiment of the first or second aspects of the invention, the moiety capable of selectively binding to the specified polypeptide is an antibody.
Preferably, an antibody which selectively binds ECSM1 or a natural variant thereof is not one which binds a polypeptide encoded by SEQ ID No 32 of WO 99/06423 or encoded by the nucleic acid of ATCC deposit No 209145 made on Jul. 17, 1997 for the purposes of WO 99/06423.
Preferably, an antibody which selectively binds ECSM1 is one which binds a polypeptide whose amino acid sequence comprises the sequence given in FIG. 2 or a natural variant thereof but which polypeptide does not comprise the amino acid sequence encoded by ATCC deposit No 209145 made on Jul. 17, 1997.
Preferably, an antibody which selectively binds ECSM4 is one which selectively binds a polypeptide with the sequence GGDSLLGGRGSL, LLQPPARGHAHDGQALSTDL, EPQDYTEPVE, TAPGGQGAPWAEE or ERATQEPSEHGP or a sequence which is located in the extracellular portion of ECSM4. As described in more detail below, these sequences represent amino acid sequences which are only found in the human ECSM4 and are not found in the mouse ECSM4 polypeptide sequence.
Preferably, the moiety which selectively binds ECSM4, such as an antibody, is one which binds a polypeptide whose amino acid sequence comprises the sequence given in any one of FIGS. 4 , 5 , 7 , 12 or 13 or a natural variant thereof but does not bind the polypeptide represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293, or encoded by any one of the nucleotide sequences represented by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00 53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 and SEQ ID No 31 of WO 99/11293.
By “antibody” we include not only whole immunoglobulin molecules but also fragments thereof such as Fab, F(ab′)2, Fv and other fragments thereof that retain the antigen-binding site. Similarly the term “antibody” includes genetically engineered derivatives of antibodies such as single chain Fv molecules (scFv) and domain antibodies (dAbs). The term also includes antibody-like molecules which may be produced using phage-display techniques or other random selection techniques for molecules which bind to ECSM1 or ECSM4.
The variable heavy (V H ) and variable light (V L ) domains of the antibody are involved in antigen recognition, a fact first recognised by early protease digestion experiments. Further confirmation was found by “humanisation” of rodent antibodies. Variable domains of rodent origin may be fused to constant domains of human origin such that the resultant antibody retains the antigenic specificity of the rodent parented antibody (Morrison et al (1984) Proc. Natl. Acad. Sci. USA 81, 6851-6855).
That antigenic specificity is conferred by variable domains and is independent of the constant domains is known from experiments involving the bacterial expression of antibody fragments, all containing one or more variable domains. These molecules include Fab-like molecules (Better et al (1988) Science 240, 1041); Fv molecules (Skerra et al (1988) Science 240, 1038); single-chain Fv (ScFv) molecules where the V H and V L partner domains are linked via a flexible oligopeptide (Bird et al (1988) Science 242, 423; Huston et al (1988) Proc. Natl. Acad. Sci. USA 85, 5879) and single domain antibodies (dabs) comprising isolated V domains (Ward et al (1989) Nature 341, 544). A general review of the techniques involved in the synthesis of antibody fragments which retain their specific binding sites is to be found in Winter & Milstein (1991) Nature 349, 293-299.
By “ScFv molecules” we mean molecules wherein the V H and V L partner domains are linked via a flexible oligopeptide.
The advantages of using antibody fragments, rather than whole antibodies, are several-fold. The smaller size of the fragments may lead to improved pharmacological properties, such as better penetration to the target site. Effector functions of whole antibodies, such as complement binding, are removed. Fab, Fv, ScFv and dAb antibody fragments can all be expressed in and secreted from E. coli , thus allowing the facile production of large amounts of the said fragments.
Whole antibodies, and F(ab′) 2 fragments are “bivalent”. By “bivalent” we mean that the said antibodies and F(ab′)2 fragments have two antigen combining sites. In contrast, Fab, Fv, ScFv and dAb fragments are monovalent, having only one antigen combining site.
Although the antibody may be a polyclonal antibody, it is preferred if it is a monoclonal antibody. In some circumstance, particularly if the antibody is going to be administered repeatedly to a human patient, it is preferred if the monoclonal antibody is a human monoclonal antibody or a humanised monoclonal antibody.
Suitable monoclonal antibodies which are reactive as said may be prepared by known techniques, for example those disclosed in “ Monoclonal Antibodies; A manual of techniques” , H Zola (CRC Press, 1988) and in “ Monoclonal Hybridoma Antibodies: Techniques and Application” , SGR Hurrell (CRC Press, 1982). Polyclonal antibodies may be produced which are polypepcific or monospecific. It is preferred that they are monospecific.
Chimaeric antibodies are discussed by Neuberger et al (1998, 8 th International Biotechnology Symposium Part 2, 792-799).
Suitably prepared non-human antibodies can be “humanised” in known ways, for example by inserting the CDR regions of mouse antibodies into the framework of human antibodies.
The antibodies may be human antibodies in the sense that they have the amino acid sequence of human anti-ECSM1 or -ECSM4 antibodies but they may be prepared using methods known in the art that do not require immunisation of humans. For example, transgenic mice are available which contain, in essence, human immunoglobulin genes (see Vaughan et al (1998) Nature Biotechnol. 16, 535-539.
In an alternative embodiment, the moiety capable of selectively binding to a polypeptide is a peptide. The ECSM4/magic roundabout polypeptide shows homology with the Drosophila , mouse and human roundabout proteins, which are cell surface receptors for secreted Slit proteins (Li et al (1996) Cell 96:807-818). Any cognate ligand for ECSM4/magic roundabout which is capable of selectively binding the region of the polypeptide which is located extracellularly may be useful. The extracellular region of ECSM4 is likely to be located within residues 1-467 of the ECSM4 polypeptide sequence given in FIG. 12 . It is believed that certain peptides may be cognate ligands for ECSM4. Such a peptide will be a suitable moiety for selectively binding ECSM4/magic roundabout. Peptides binding ECSM4 can be identified by means of a screen. A suitable method or screen for identifying peptides or other molecules which selectively bind ECSM4 may comprise contacting the ECSM4 polypeptide with a test peptide or other molecule under conditions where binding can occur, and then determining if the test molecule or peptide has bound ECSM4. Methods of detecting binding between two moieties are well known in the art of biochemistry. Preferably, the known technique of phage display is used to identify peptides or other ligand molecules which bind to ECSM4. An alternative method includes the yeast two hybrid system.
Peptides or other agents which selectively bind ECSM4 include those which modulate or block the function of ECSM4.
Suitable peptides may be synthesised as described in more detail below.
The further moiety may be any further moiety which confers on the compound a useful property with respect to the treatment or imaging or diagnosis of diseases or other conditions or states which involve undesirable neovasculature formation. Such diseases or other conditions or states are described in more detail below. In particular, the further moiety is one which is useful in killing or imaging neovasculature associated with the growth of a tumour. Preferably, the further moiety is one which is able to kill the endothelial cells to which the compound is targeted.
In a preferred embodiment of the invention the further moiety is directly or indirectly cytotoxic. In particular the further moiety is preferably directly or indirectly toxic to cells in neovasculature or cells which are in close proximity to and associated with neovasculature.
By “directly cytotoxic” we include the meaning that the moiety is one which on its own is cytotoxic. By “indirectly cytotoxic” we include the meaning that the moiety is one which, although is not itself cytotoxic, can induce cytotoxicity, for example by its action on a further molecule or by further action on it.
In one embodiment the cytotoxic moiety is a cytotoxic chemotherapeutic agent. Cytotoxic chemotherapeutic agents are well known in the art.
Cytotoxic chemotherapeutic agents, such as anticancer agents, include: alkylating agents including nitrogen mustards such as mechlorethanine (HN 2 ), cyclophosphamide, ifosfamide, melphalan (L-sarcolysin) and chlorambucil; ethylenimines and methylmelamines such as hexamethylmelamine, thiotepa; alkyl sulphonates such as busulfan; nitrosoureas such as carmustine (BCNU), lomustine (CCNU), semustine (methyl-CCNU) and streptozocin (streptozotocin); and triazenes such as decarbazine (DTIC; dimethyltriazenoimidazole-carboxamide); Antimetabolites including folic acid analogues such as methotrexate (amethopterin); pyrimidine analogues such as fluorouracil (5-fluorouracil; 5-FU), floxuridine (fluorodeoxyuridine; FUdR) and cytarabine (cytosine arabinoside); and purine analogues and related inhibitors such as mercaptopurine (6-mercaptopurine; 6-MP), thioguanine (6-thioguanine; TG) and pentostatin (2′-deoxycoformycin). Natural Products including vinca alkaloids such as vinblastine (VLB) and vincristine; epipodophyllotoxins such as etoposide and teniposide; antibiotics such as dactinomycin (actinomycin D), daunorubicin (daunomycin; rubidomycin), doxorubicin, bleomycin, plicamycin (mithramycin) and mitomycin (mitomycin C); enzymes such as L-asparaginase; and biological response modifiers such as interferon alphenomes. Miscellaneous agents including platinum coordination complexes such as cisplatin (cis-DDP) and carboplatin; anthracenedione such as mitoxantrone and anthracycline; substituted urea such as hydroxyurea; methyl hydrazine derivative such as procarbazine (N-methylhydrazine, M1H); and adrenocortical suppressant such as mitotane (o,p′-DDD) and aminoglutethimide; taxol and analogues/derivatives; and hormone agonists/antagonists such as flutamide and tamoxifen.
Various of these agents have previously been attached to antibodies and other target site-delivery agents, and so compounds of the invention comprising these agents may readily be made by the person skilled in the art. For example, carbodiimide conjugation (Bauminger & Wilchek (1980) Methods Enzymol. 70, 151-159; incorporated herein by reference) may be used to conjugate a variety of agents, including doxorubicin, to antibodies or peptides.
Carbodiimides comprise a group of compounds that have the general formula R—N═C═N—RN, where R and RN can be aliphatic or aromatic, and are used for synthesis of peptide bonds. The preparative procedure is simple, relatively fast, and is carried out under mild conditions. Carbodiimide compounds attack carboxylic groups to change them into reactive sites for free amino groups.
The water soluble carbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) is particularly useful for conjugating a functional moiety to a binding moiety and may be used to conjugate doxorubicin to tumor homing peptides. The conjugation of doxorubicin and a binding moiety requires the presence of an amino group, which is provided by doxorubicin, and a carboxyl group, which is provided by the binding moiety such as an antibody or peptide.
In addition to using carbodiimides for the direct formation of peptide bonds, EDC also can be used to prepare active esters such as N-hydroxysuccinimide (NHS) ester. The NHS ester, which binds only to amino groups, then can be used to induce the formation of an amide bond with the single amino group of the doxorubicin. The use of EDC and NHS in combination is commonly used for conjugation in order to increase yield of conjugate formation (Bauminger & Wilchek, supra, 1980).
Other methods for conjugating a functional moiety to a binding moiety also can be used. For example, sodium periodate oxidation followed by reductive alkylation of appropriate reactants can be used, as can glutaraldehyde cross-linking. However, it is recognised that, regardless of which method of producing a conjugate of the invention is selected, a determination must be made that the binding moiety maintains its targeting ability and that the functional moiety maintains its relevant function.
In a further embodiment of the invention, the cytotoxic moiety is a cytotoxic peptide or polypeptide moiety by which we include any moiety which leads to cell death. Cytotoxic peptide and polypeptide moieties are well known in the art and include, for example, ricin, abrin, Pseudomonas exotoxin, tissue factor and the like. Methods for linking them to targeting moieties such as antibodies are also known in the art. The use of ricin as a cytotoxic agent is described in Burrows & Thorpe (1993) Proc. Natl. Acad. Sci. USA 90, 8996-9000, incorporated herein by reference, and the use of tissue factor, which leads to localised blood clotting and infarction of a tumour, has been described by Ran et al (1998) Cancer Res. 58, 4646-4653 and Huang et al (1997) Science 275, 547-550. Tsai et al (1995) Dis. Colon Rectum 38, 1067-1074 describes the abrin A chain conjugated to a monoclonal antibody and is incorporated herein by reference. Other ribosome inactivating proteins are described as cytotoxic agents in WO 96/06641. Pseudomonas exotoxin may also be used as the cytotoxic polypeptide moiety (see, for example, Aiello et al (1995) Proc. Natl. Acad. Sci. USA 92, 10457-10461; incorporated herein by reference).
Certain cytokines, such as TNFα and IL-2, may also be useful as cytotoxic agents.
Certain radioactive atoms may also be cytotoxic if delivered in sufficient doses. Thus, the cytotoxic moiety may comprise a radioactive atom which, in use, delivers a sufficient quantity of radioactivity to the target site so as to be cytotoxic. Suitable radioactive atoms include phosphorus-32, iodine-125, iodine-131, indium-111, rhenium-186, rhenium-188 or yttrium-90, or any other isotope which emits enough energy to destroy neighbouring cells, organelles or nucleic acid. Preferably, the isotopes and density of radioactive atoms in the compound of the invention are such that a dose of more than 4000 cGy (preferably at least 6000, 8000 or 10000 cGy) is delivered to the target site and, preferably, to the cells at the target site and their organelles, particularly the nucleus.
The radioactive atom may be attached to the binding moiety in known ways. For example EDTA or another chelating agent may be attached to the binding moiety and used to attach 111 In or 90 Y. Tyrosine residues may be labelled with 125 I or 131 I.
The cytotoxic moiety may be a suitable indirectly cytotoxic polypeptide. In a particularly preferred embodiment, the indirectly cytotoxic polypeptide is a polypeptide which has enzymatic activity and can convert a relatively non-toxic prodrug into a cytotoxic drug. When the targeting moiety is an antibody this type of system is often referred to as ADEPT (Antibody-Directed Enzyme Prodrug Therapy). The system requires that the targeting moiety locates the enzymatic portion to the desired site in the body of the patient (ie the site expressing ECSM1 or ECSM4, such as new vascular tissue associated with a tumour) and after allowing time for the enzyme to localise at the site, administering a prodrug which is a substrate for the enzyme, the end product of the catalysis being a cytotoxic compound. The object of the approach is to maximise the concentration of drug at the desired site and to minimise the concentration of drug in normal tissues (see Senter, P. D. et al (1988) “Anti-tumor effects of antibody-alkaline phosphatase conjugates in combination with etoposide phosphate” Proc. Natl. Acad. Sci. USA 85, 4842-4846; Bagshawe (1987) Br. J. Cancer 56, 531-2; and Bagshawe, K. D. et al (1988) “A cytotoxic agent can be generated selectively at cancer sites” Br. J. Cancer. 58, 700-703.)
Clearly, any ECSM1 or ECSM4 binding moiety may be used in place of an anti-ECSM1 or anti-ECSM4 antibody in this type of directed enzyme prodrug therapy system.
The enzyme and prodrug of the system using an ECSM1 or ECSM4 targeted enzyme as described herein may be any of those previously proposed. The cytotoxic substance may be any existing anti-cancer drug such as an alkylating agent; an agent which intercalates in DNA; an agent which inhibits any key enzymes such as dihydrofolate reductase, thymidine synthetase, ribonucleotide reductase, nucleoside kinases or topoisomerase; or an agent which effects cell death by interacting with any other cellular constituent. Etoposide is an example of a topoisomerase inhibitor.
Reported prodrug systems include: a phenol mustard prodrug activated by an E. coli β-glucuronidase (Wang et al, 1992 and Roffler et al, 1991); a doxorubicin prodrug activated by a human β-glucuronidase (Bosslet et al, 1994); further doxorubicin prodrugs activated by coffee bean α-galactosidase (Azoulay et al, 1995); daunorubicin prodrugs, activated by coffee bean α-D-galactosidase (Gesson et al, 1994); a 5-fluorouridine prodrug activated by an E. coli β-D-galactosidase (Abraham et al, 1994); and methotrexate prodrugs (eg methotrexate-alanine) activated by carboxypeptidase A (Kuefner et al, 1990, Vitols et al, 1992 and Vitols et al, 1995). These and others are included in the following table.
Enzyme Prodrug Carboxypeptidase G2 Derivatives of L-glutamic acid and benzoic acid mustards, aniline mustards, phenol mustards and phenylenediamine mustards; fluorinated derivatives of these Alkaline phosphatase Etoposide phosphate Mitomycin phosphate Beta-glucuronidase p-Hydroxyaniline mustard-glucuronide Epirubicin-glucuronide Penicillin-V-amidase Adriamycin-N phenoxyacetyl Penicillin-G-amidase N-(4′-hydroxyphenyl acetyl) palytoxin Doxorubicin and melphalan Beta-lactamase Nitrogen mustard-cephalosporin p-phenylenediamine; doxorubicin derivatives; vinblastine derivative-cephalosporin, cephalosporin mustard; a taxol derivative Beta-glucosidase Cyanophenylmethyl-beta-D-gluco- pyranosiduronic acid Nitroreductase 5-(Azaridin-1-yl-)-2,4-dinitrobenzamide Cytosine deaminase 5-Fluorocytosine Carboxypeptidase A Methotrexate-alanine
(This table is adapted from Bagshawe (1995) Drug Dev. Res. 34, 220-230, from which full references for these various systems may be obtained; the taxol derivative is described in Rodrigues, M. L. et al (1995) Chemistry & Biology 2, 223).
Suitable enzymes for forming part of the enzymatic portion of the invention include: exopeptidases, such as carboxypeptidases G, G1 and G2 (for glutamylated mustard prodrugs), carboxypeptidases A and B (for MTX-based prodrugs) and aminopeptidases (for 2-α-aminocyl MTC prodrugs); endopeptidases, such as eg thrombolysin (for thrombin prodrugs); hydrolases, such as phosphatases (eg alkaline phosphatase) or sulphatases (eg aryl sulphatases) (for phosphylated or sulphated prodrugs); amidases, such as penicillin amidases and arylacyl amidase; lactamases, such as β-lactamases; glycosidases, such as β-glucuronidase (for β-glucuronomide anthracyclines), α-galactosidase (for amygdalin) and β-galactosidase (for β-galactose anthracycline); deaminases, such as cytosine deaminase (for 5FC); kinases, such as urokinase and thymidine kinase (for gancyclovir); reductases, such as nitroreductase (for CB1954 and analogues), azoreductase (for azobenzene mustards) and DT-diaphorase (for CB1954); oxidases, such as glucose oxidase (for glucose), xanthine oxidase (for xanthine) and lactoperoxidase; DL-racemases, catalytic antibodies and cyclodextrins.
The prodrug is relatively non-toxic compared to the cytotoxic drug. Typically, it has less than 10% of the toxicity, preferably less than 1% of the toxicity as measured in a suitable in vitro cytotoxicity test.
It is likely that the moiety which is able to convert a prodrug to a cytotoxic drug will be active in isolation from the rest of the compound but it is necessary only for it to be active when (a) it is in combination with the rest of the compound and (b) the compound is attached to, adjacent to or internalised in target cells.
When each moiety of the compound is a polypeptide, the two portions may be linked together by any of the conventional ways of cross-linking polypeptides, such as those generally described in O'Sullivan et al (1979) Anal. Biochem. 100, 100-108. For example, the ECSM1 or ECSM4 binding moiety may be enriched with thiol groups and the further moiety reacted with a bifunctional agent capable of reacting with those thiol groups, for example the N-hydroxysuccinimide ester of iodoacetic acid (NHIA) or N-succinimidyl-3-(2-pyridyldithio)propionate (SPDP). Amide and thioether bonds, for example achieved with m-maleimidobenzoyl-N-hydroxysuccinimide ester, are generally more stable in vivo than disulphide bonds.
Alternatively, the compound may be produced as a fusion compound by recombinant DNA techniques whereby a length of DNA comprises respect-ive regions encoding the two moieties of the compound of the invention either adjacent one another or separated by a region encoding a linker peptide which does not destroy the desired properties of the compound. Conceivably, the two portions of the compound may overlap wholly or partly.
The DNA is then expressed in a suitable host to produce a polypeptide comprising the compound of the invention.
The invention also provides a kit of parts (or a therapeutic system) comprising (1) a compound of the invention wherein the further moiety which is able to convert a relatively non-toxic prodrug into a cytotoxic drug and (2) a relatively non-toxic prodrug. The kit of parts may comprise any of the compounds of the invention and appropriate prodrugs as herein disclosed.
The invention also provides a kit of parts (or a therapeutic system) comprising (1) a compound of the invention wherein the further moiety is able to bind selectively to a directly or indirectly cytotoxic moiety or to a readily detectable moiety and (2) any one of a directly or indirectly cytotoxic or a readily detectable moiety to which the further moiety of the compound is able to bind.
The cytotoxic moiety may be a radiosensitizer. Radiosensitizers include fluoropyrimidines, thymidine analogues, hydroxyurea, gemcitabine, fludarabine, nicotinamide, halogenated pyrimidines, 3-aminobenzamide, 3-aminobenzodiamide, etanixadole, pimonidazole and misonidazole (see, for example, McGinn et al (1996) J. Natl. Cancer Inst. 88, 1193-11203; Shewach & Lawrence (1996) Invest. New Drugs 14, 257-263; Horsman (1995) Acta Oncol. 34, 571-587; Shenoy & Singh (1992) Clin. Invest. 10, 533-551; Mitchell et al (1989) Int. J. Radiat. Biol. 56, 827-836; Iliakis & Kurtzman (1989) Int. J. Radiat. Oncol. Biol. Phys. 16, 1235-1241; Brown (1989) Int. J. Radiat. Oncol. Biol. Phys. 16, 987-993; Brown (1985) Cancer 55, 2222-2228).
Also, delivery of genes into cells can radiosensitise them, for example delivery of the p53 gene or cyclin D (Lang et al (1998) J. Neurosurg. 89, 125-132; Coco Martin et al (1999) Cancer Res. 59, 1134-1140).
The further moiety may be one which becomes cytotoxic, or releases a cytotoxic moiety, upon irradiation. For example, the boron-10 isotope, when appropriately irradiated, releases α particles which are cytotoxic (see for example, U.S. Pat. No. 4,348,376 to Goldenberg; Primus et al (1996) Bioconjug. Chem. 7, 532-535).
Similarly, the cytotoxic moiety may be one which is useful in photodynamic therapy such as photofrin (see, for example, Dougherty et al (1998) J. Natl. Cancer Inst. 90, 889-905).
The further moiety may comprise a nucleic acid molecule which is directly or indirectly cytotoxic. For example, the nucleic acid molecule may be an antisense oligonucleotide which, upon localisation at the target site is able to enter cells and lead to their death. The oligonucleotide, therefore, may be one which prevents expression of an essential gene, or one which leads to a change in gene expression which causes apoptosis.
Examples of suitable oligonucleotides include those directed at bcl-2 (Ziegler et al (1997) J. Natl. Cancer Inst. 89, 1027-1036), and DNA polymerase a and topoisomerase Ia (Lee et al (1996) Anticancer Res. 16, 1805-1811.
Peptide nucleic acids may be useful in place of conventional nucleic acids (see Knudsen & Nielsen (1997) Anticancer Drugs 8, 113-118).
In a further embodiment, the binding moiety may be comprised in a delivery vehicle for delivering nucleic acid to the target. The delivery vehicle may be any suitable delivery vehicle. It may, for example, be a liposome containing nucleic acid, or it may be a virus or virus-like particle which is able to deliver nucleic acid. In these cases, the moiety which selectively binds to ECSM1 or ECSM4 is typically present on the surface of the delivery vehicle. For example, the moiety which selectively binds to ECSM1 or ECSM4, such as a suitable antibody fragment, may be present in the outer surface of a liposome and the nucleic acid to be delivered may be present in the interior of the liposome. As another example, a viral vector, such as a retroviral or adenoviral vector, is engineered so that the moiety which selectively binds to ECSM1 or ECSM4 is attached to or located in the surface of the viral particle thus enabling the viral particle to be targeted to the desired site. Targeted delivery systems are also known such as the modified adenovirus system described in WO 94/10323 wherein, typically, the DNA is carried within the adenovirus, or adenovirus-like, particle. Michael et al (1995) Gene Therapy 2, 660-668 describes modification of adenovirus to add a cell-selective moiety into a fibre protein. Targeted retroviruses are also available for use in the invention; for example, sequences conferring specific binding affinities may be engineered into preexisting viral env genes (see Miller & Vile (1995) Faseb J 9, 190-199 for a review of this and other targeted vectors for gene therapy).
Immunoliposomes (antibody-directed liposomes) may be used in which the moiety which selectively binds to ECSM1 or ECSM4 is an antibody. For the preparation of immuno-liposomes MPB-PE (N-[4-(p-maleimidophenyl)butyryl]-phosphatidylethanolamine) is synthesised according to the method of Martin & Papahadjopoulos (1982) J. Biol. Chem. 257, 286-288. MPB-PE is incorporated into the liposomal bilayers to allow a covalent coupling of the anti-ECSM1 or -ECSM4 antibody, or fragment thereof, to the liposomal surface. The liposome is conveniently loaded with the DNA or other genetic construct for delivery to the target cells, for example, by forming the said liposomes in a solution of the DNA or other genetic construct, followed by sequential extrusion through polycarbonate membrane filters with 0.6 μm and 0.2 μm pore size under nitrogen pressures up to 0.8 MPa. After extrusion, entrapped DNA construct is separated from free DNA construct by ultracentrifugation at 80 000×g for 45 min. Freshly prepared MPB-PE-liposomes in deoxygenated buffer are mixed with freshly prepared antibody (or fragment thereof) and the coupling reactions are carried out in a nitrogen atmosphere at 4° C. under constant end over end rotation overnight. The immunoliposomes are separated from unconjugated antibodies by ultracentrifugation at 80 000×g for 45 min. Immunoliposomes may be injected intraperitoneally or directly into the tumour.
The nucleic acid delivered to the target site may be any suitable DNA which leads, directly or indirectly, to cytotoxicity. For example, the nucleic acid may encode a ribozyme which is cytotoxic to the cell, or it may encode an enzyme which is able to convert a substantially non-toxic prodrug into a cytotoxic drug (this latter system is sometime called GDEPT: Gene Directed Enzyme Prodrug Therapy).
Ribozymes which may be encoded in the nucleic acid to be delivered to the target are described in Cech and Herschlag “Site-specific cleavage of single stranded DNA” U.S. Pat. No. 5,180,818; Altman et al “Cleavage of targeted RNA by RNAse P” U.S. Pat. No. 5,168,053, Cantin et al “Ribozyme cleavage of HIV-1 RNA” U.S. Pat. No. 5,149,796; Cech et al “RNA ribozyme restriction endoribonucleases and methods”, U.S. Pat. No. 5,116,742; Been et al “RNA ribozyme polymerases, dephosphorylases, restriction endonucleases and methods”, U.S. Pat. No. 5,093,246; and Been et al “RNA ribozyme polymerases, dephosphorylases, restriction endoribonucleases and methods; cleaves single-stranded RNA at specific site by transesterification”, U.S. Pat. No. 4,987,071, all incorporated herein by reference. Suitable targets for ribozymes include transcription factors such as c-fos and c-myc, and bcl-2. Durai et al (1997) Anticancer Res. 17, 3307-3312 describes a hammerhead ribozyme against bcl-2.
EP 0 415 731 describes the GDEPT system. Similar considerations concerning the choice of enzyme and prodrug apply to the GDEPT system as to the ADEPT system described above.
The nucleic acid delivered to the target site may encode a directly cytotoxic polypeptide.
Alternatively, the further portion may comprise a polypeptide or a polynucleotide encoding a polypeptide which is not either directly or indirectly cytotoxic but is of therapeutic benefit. Examples of such polypeptides include anti-proliferative or anti-inflammatory cytokines which could be of benefit in artherosclerosis, and anti-proliferative, immunomodulatory or factors influencing blood clotting may be of benefit in treating cancer.
The further moiety may usefully be an inhibitor of angiogenesis such as the peptides angiostatin or endostatin. The further moiety may also usefully be an enzyme which converts a precursor polypeptide to angiostatin or endostatin. Human matrix metallo-proteases such as macrophage elastase, gelatinase and stromolysin convert plasminogen to angiostatin (Cornelius et al (1998) J. Immunol. 161, 6845-6852). Plasminogen is a precursor of angiostatin.
In a further embodiment of the invention, the further moiety comprised in the compound of the invention is a readily detectable moiety.
By a “readily detectable moiety” we include the meaning that the moiety is one which, when located at the target site following administration of the compound of the invention into a patient, may be detected, typically non-invasively from outside the body and the site of the target located. Thus, the compounds of this embodiment of the invention are useful in imaging and diagnosis.
Typically, the readily detectable moiety is or comprises a radioactive atom which is useful in imaging. Suitable radioactive atoms include technetium-99m or iodine-123 for scintigraphic studies. Other readily detectable moieties include, for example, spin labels for magnetic resonance imaging (MRI) such as iodine-123 again, iodine-131, indium-111, fluorine-19, carbon-13, nitrogen-15, oxygen-17, gadolinium, manganese or iron. Clearly, the compound of the invention must have sufficient of the appropriate atomic isotopes in order for the molecule to be readily detectable.
The radio- or other labels may be incorporated in the compound of the invention in known ways. For example, if the binding moiety is a polypeptide it may be biosynthesised or may be synthesised by chemical amino acid synthesis using suitable amino acid precursors involving, for example, fluorine-19 in place of hydrogen. Labels such as 99m Tc, 123 I, 186 Rh, 188 Rh and 111 In can, for example, be attached via cysteine residues in the binding moiety. Yttrium-90 can be attached via a lysine residue. The IODOGEN method (Fraker er al (1978) Biochem. Biophys. Res. Comm. 80, 49-57) can be used to incorporate iodine-123. Reference (“Monoclonal Antibodies in Immunoscintigraphy”, J-F Chatal, CRC Press, 1989) describes other methods in detail.
In a further preferred embodiment of the invention the further moiety is able to bind selectively to a directly or indirectly cytotoxic moiety or to a readily detectable moiety. Thus, in this embodiment, the further moiety may be any moiety which binds to a further compound or component which is cytotoxic or readily detectable.
The further moiety may, therefore be an antibody which selectively binds to the further compound or component, or it may be some other binding moiety such as streptavidin or biotin or the like. The following examples illustrate the types of molecules that are included in the invention; other such molecules are readily apparent from the teachings herein.
A bispecific antibody wherein one binding site comprises the moiety which selectively binds to ECSM1 or ECSM4 and the second binding site comprises a moiety which binds to, for example, an enzyme which is able to convert a substantially non-toxic prodrug to a cytotoxic drug.
A compound, such as an antibody which selectively binds to ECSM1 or ECSM4, to which is bound biotin. Avidin or streptavidin which has been labelled with a readily detectable label may be used in conjunction with the biotin labelled antibody in a two-phase imaging system wherein the biotin labelled antibody is first localised to the target site in the patient, and then the labelled avidin or streptavidin is administered to the patient. Bispecific antibodies and biotin/streptavidin (avidin) systems are reviewed by Rosebrough (1996) Q J Nucl. Med. 40, 234-251.
In a preferred embodiment of the invention, the moiety which selectively binds to ECSM1 or ECSM4 and the further moiety are polypeptides which are fused.
The compounds of the first and second aspects of the invention are useful in treating, imaging or diagnosing disease, particularly diseases in which there may be undesirable neovasculature formation, as described in more detail below.
In a preferred embodiment of the first and second aspects of the invention, the compounds are suitable for use in medicine.
A third aspect of the invention provides a nucleic acid molecule encoding a compound of either the first or second aspects of the invention wherein the selective binding moiety and the further moiety are polypeptides which are fused.
Methods of linking polynucleotides are described in more detail below.
A fourth aspect of the invention provides a pharmaceutical composition comprising a compound according to the invention and a pharmaceutically acceptable carrier. The compound of the invention includes those described in the first, second and third aspects. The invention also includes pharmaceutical composition comprising any of an antibody, polypeptide, peptide, polynucleotide, expression vector or other agent which may be delivered to an individual as described below and a pharmaceutically acceptable carrier.
By “pharmaceutically acceptable” is included that the formulation is sterile and pyrogen free. Suitable pharmaceutical carriers are well known in the art of pharmacy.
The carrier(s) must be “acceptable” in the sense of being compatible with the compound of the invention and not deleterious to the recipients thereof. Typically, the carriers will be water or saline which will be sterile and pyrogen free; however, other acceptable carriers may be used.
Typically the pharmaceutical compositions or formulations of the invention are for parenteral administration, more particularly for intravenous administration.
Formulations suitable for parenteral administration include aqueous and non-aqueous sterile injection solutions which may contain anti-oxidants, buffers, bacteriostats and solutes which render the formulation isotonic with the blood of the intended recipient; and aqueous and non-aqueous sterile suspensions which may include suspending agents and thickening agents.
A fifth aspect of the invention provides a method of imaging vascular endothelium in the body of an individual the method comprising administering to the individual an effective amount of a compound according to either of the first or second aspects of the invention wherein the further moiety is a readily detectable moiety.
Typically the vascular endothelium is associated with angiogenesis.
As discussed above in relation to the first and second aspects of the invention, the moiety of the compound which selectively binds ECSM4 or ECSM1 may be an antibody. Preferred antibodies are as outlined above.
In a preferred embodiment of this aspect of the invention, the method of imaging the vascular endothelium in an individual comprises the further step of detecting the location of the compound in the individual.
Detecting the compound or antibody can be achieved using methods well known in the art of clinical imaging and diagnostics. The specific method required will depend on the type of detectable label attached to the compound or antibody. For example, radioactive atoms may be detected using autoradiography or in some cases by magnetic resonance imaging (MRI) as described above.
Imaging the vascular endothelium in the body is useful because it can provide information about the health of the body. It is particularly useful when the vascular endothelium is diseased, or is proliferating due to a cancerous growth. Imaging cancer in a patient is especially useful, because it can be used to determine the size of a tumour and whether it is responding to treatment. Since metastatic disease involves new blood vessel formation, the method is useful in assessing whether metastasis has occurred.
Hence, in a preferred embodiment of the fifth aspect of the invention, the vascular endothelium is neovasculature, such as that produced in cancer.
A sixth aspect of the invention provides a method of diagnosing or prognosing in an individual a condition which involves the vascular endothelium the method comprising administering to the individual an effective amount of a compound according to either of the first or second aspects of the invention wherein the further moiety is a readily detectable moiety.
The condition may be one which involves aberrant or excessive growth of vascular endothelium, such as cancer, artherosclerosis, restenosis, diabetic retinopathy, arthritis, psoriasis, endometriosis, menorrhagia, haemangiomas and venous malformations.
As discussed in relation to the first and second aspects of the invention, the compound may comprise an antibody. The antibody may be any antibody which selectively binds the polypeptide ECSM1 or ECSM4 as required. Preferred antibodies which bind the polypeptide ECSM4 are as outlined above.
The method may be one which is an aid to diagnosis.
In a preferred embodiment of this aspect of the invention, the method of diagnosing, or aiding diagnosis of, a condition involving the vascular endothelium in an individual comprises the further step of detecting the location of the compound in the individual. Preferably the endothelium is in neovasculature; ie, angiogenic vasculature.
The function of ECSM4 or ECSM1 may not be to promote proliferation of vascular endothelial cells. Therefore the level of expression of these polypeptides within an endothelial cell may not be informative about the health of the vascular endothelium. However, the location of expression of the polypeptides may be informative, as they represent the growth of blood vessels. Abnormal cell proliferation such as cancer may be diagnosed by the detection of new vasculature.
A seventh aspect of the invention provides a method of treating an individual in need of treatment, the method comprising administering to the individual an effective amount of a compound according to the first or second aspects of the invention wherein the further moiety is a cytotoxic or therapeutic moiety.
In one embodiment of this aspect, the patient in need of treatment has a proliferative disease or a condition involving the vascular endothelium.
A number of diseases and conditions involve undesirable neovasculature formation. Neovasculature formation is associated with cancer, psoriasis, atherosclerosis, menorrhagia, arthritis (both inflammatory and rheumatoid), macular degeneration, Paget's disease, retinopathy and its vascular complications (including proliferative and of prematurity, and diabetic), benign vascular proliferations and fibroses.
By cancer is included Kaposi's sarcoma, leukaemia, lymphoma, myeloma, solid carcinomas (both primary and secondary (metastasis), vascular tumours including haemangioma (both capillary and juvenile (infantile)), haemangiomatosis and haemagioblastoma.
Thus, the invention comprises a method of treating a patient who has a disease in which angiogenesis contributes to pathology the method comprising the step of administering to the patient an effective amount of a compound of the first or second aspect of the invention wherein the further moiety of the compound is one which either directly or indirectly is of therapeutic benefit to the patient.
Typically, the disease is associated with undesirable neovasculature formation and the treatment reduces this to a useful extent.
The tumours that may be treated by the methods of the invention include any tumours which are associated with new blood vessel production.
The term “tumour” is to be understood as referring to all forms of neoplastic cell growth, including tumours of the lung, liver, blood cells, skin, pancreas, stomach, colon, prostate, uterus, breast, lymph glands and bladder. Solid tumours are especially suitable. However, blood cancers, including leukaemias and lymphomas are now also believed to involve new blood vessel formation and may be treated by the methods of the invention.
Typically in the above-mentioned methods of treatment, the further moiety is one which destroys or slows or reverses the growth of the neovasculature.
It will readily be appreciated that, depending on the particular compound used in imaging, diagnosis or treatment, the timing of administration may vary and the number of other components used in therapeutic systems disclosed herein may vary.
For example, in the case where the compound of the invention comprises a readily detectable moiety or a directly cytotoxic moiety, it may be that only the compound, in a suitable formulation, is administered to the patient. Of course, other agents such as immunosuppressive agents and the like may be administered.
In respect of compounds which are detectably labelled, imaging takes place once the compound has localised at the target site.
However, if the compound is one which requires a further component in order to be useful for treatment, imaging or diagnosis, the compound of the invention may be administered and allowed to localise at the target site, and then the further component administered at a suitable time thereafter.
For example, in respect of the ADEPT and ADEPT-like systems above, the binding moiety-enzyme moiety compound is administered and localises to the target site. Once this is done, the prodrug is administered.
Similarly, for example, in respect of the compounds wherein the further moiety comprised in the compound is one which binds a further component, the compound may be administered first and allowed to localise at the target site, and subsequently the further component is administered.
Thus, in one embodiment a biotin-labelled anti-ECSM1 or -ECSM4 antibody is administered to the patient and, after a suitable period of time, detectably labelled streptavidin is administered. Once the streptavidin has localised to the sites where the antibody has localised (ie the target sites) imaging takes place.
Where the compound whose moiety which selectively binds is an antibody, the antibody may be any antibody which selectively binds the polypeptide ECSM1 or ECSM4 as required. Preferred antibodies are as outlined in the first and second aspects of the invention.
It is believed that the compounds of the invention wherein the further moiety is a readily detectable moiety may be useful in determining the angiogenic status of tumours or other disease states in which angiogenesis contributes to pathology. This may be an important factor influencing the nature and outcome of future therapy.
An eighth aspect of the invention provides a method of introducing genetic material selectively into vascular endothelial cells the method comprising contacting the cells with a compound according to either of the first or second aspects of the invention as described above wherein the further moiety is a nucleic acid.
The vascular endothelial cells may be any vascular endothelial cells such as those in tissue culture or in a living organism. It is preferred if the cells are in a living organism. It is further preferred if the organism is a human. It is still more preferred if the vascular endothelial cells are those in neovasculature, ie they are angiogenic endothelial cells.
Preferably, the binding moiety is an antibody. The antibody may be any antibody which selectively binds the polypeptide ECSM1 or ECSM4 as required. Preferably, the antibody is one as defined above in relation to the first or second aspects of the invention. Typically, the binding moiety is comprised in a delivery vehicle and preferably, the delivery vehicle is a liposome, as described in further detail above. In this embodiment, the further moiety is nucleic acid and is comprised within the liposome, also as described above. Typically, the method is used in gene therapy, and the genetic material is therapeutically useful. Therapeutically useful genetic material includes that which encodes a therapeutic protein.
A ninth aspect of the invention provides a use of a compound according to either of the first or second aspects of the invention wherein the further moiety is a readily detectable label in the manufacture of a diagnostic or prognostic agent for a condition which involves the vascular endothelium.
As discussed above, the compound may comprise an antibody as the moiety which selectively binds. The antibody may be any antibody which selectively binds the polypeptide ECSM1 or ECSM4 as required.
A tenth aspect of the invention provides a use of a compound according to either of the first or second aspects of the invention wherein the further moiety is a cytotoxic or therapeutic moiety in the manufacture of a medicament for treating a condition involving the vascular endothelium.
Conditions which involve the vascular endothelium are described above.
As described above, the compound may comprise an antibody as the moiety which selectively binds. The antibody may be any suitable antibody which selectively binds the polypeptide ECSM1 or ECSM4 as required.
An eleventh aspect of the invention provides a polypeptide comprising or consisting of a fragment or variant or fusion of the ECSM4 polypeptide or a fusion of said fragment or variant provided that it is not a polypeptide consisting of the amino acid sequence given between residues 49 and 466 of FIG. 4 .
The ECSM4 polypeptide includes a polypeptide comprising or consisting of the amino acid sequence given in FIG. 4 or FIG. 5 or FIG. 7 or FIG. 12 or FIG. 13 or the polypeptide encoded by the nucleotide sequence of either FIG. 4 between positions 1 and 1395 or FIG. 5 between positions 2 and 948 or FIG. 7 or FIG. 12 or FIG. 13 is that of the ECSM4 polypeptide. Preferably, the ECSM4 polypeptide of the invention comprises but does not consist of the amino acid sequence given in FIG. 4 .
Preferably, the ECSM4 polypeptide of the invention does not consist of any of the amino acid sequences represented by SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293, or any of the amino acid sequences encoded by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00/53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 or SEQ ID No 31 of WO 99/11293.
A twelfth aspect of the invention provides a polypeptide comprising or consisting of the ECSM1 polypeptide or a fragment or variant or fusion thereof or a fusion of said fragment or variant.
The ECSM1 polypeptide includes a polypeptide comprising or consisting of the amino acid sequence given in FIG. 2 . Preferably, the ECSM1 polypeptide or fragment is not a polypeptide whose sequence is given in SEQ ID No 120 of WO 99/06423 or which is encoded by SEQ ID No 32 of WO 99/06423 or encoded by the nucleic acid of ATCC deposit No 209145 made on Jul. 17, 1997 for the purposes of WO 99/06423.
The invention includes peptides which are derived from the ECSM4 or ECSM1 polypeptides. These peptides may be considered “fragments” of the ECSM4 or ECSM1 polypeptides but may be produced by de novo synthesis or by fragmentation of the polypeptide.
“Fragments” of the ECSM4 or ECSM1 polypeptide include polypeptides which comprise at least five consecutive amino acids of the ECSM4 or ECSM1 polypeptide. Preferably, a fragment of the polypeptide comprises an amino acid sequence which is useful, for example, a fragment which retains activity of the polypeptide, or a fragment for use in a binding assay or is useful as a peptide for producing an antibody which is specific for the ECSM4 or ECSM1 polypeptide. An activity of the ECSM4 polypeptide may be in endothelial cell repulsive guidance. Repulsive guidance may be tested in vivo by constructing appropriate transgenic or knock-out animal models, for example mice or zebrafish. It may also be tested in vivo on cell migration assays such as Boyden chamber or video microscopy. Typically, the fragments have at least 8 consecutive amino acids, preferably at least 10, more preferably at least 12 or 15 or 20 or 30 or 40 or 50 consecutive amino acids of the ECSM4 or ECSM1 polypeptide. Preferably, fragments of the ECSM4 polypeptide comprise but do not consist of the amino acid sequence given in FIG. 4 or FIG. 5 or FIG. 7 or FIG. 12 or FIG. 13 . Preferably, fragments of the ECSM4 polypeptide comprise but do not consist of any of the amino acid sequences represented by SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293, or any of the amino acid sequences encoded by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00 53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 or SEQ ID No 31 of WO 99/11293.
Typically, the fragments of ECSM4 polypeptide are ones which have portions of the amino acid sequence shown in FIG. 4 or FIG. 12 .
Typically, the fragments of ECSM1 polypeptide are ones which have portions of the amino acid sequence shown in FIG. 2 .
In a preferred embodiment of the thirteenth aspect of the invention, a fragment of the ECSM4 polypeptide is a fragment which has the sequence LSQSPGAVPQALVAWRA (SEQ ID NO:6), DSVLTPEEVALCLEL (SEQ ID NO:7), TYGYISVPTA (SEQ ID NO:8), KGGVLLCPPRPCLTPT (SEQ ID NO:9), WLADTW (SEQ ID NO:10), WLADTWRSTSGSRD (SEQ ID NO:11), SPPTTYGYIS (SEQ ID NO:12), GSLANGWGSASEDNAASARASLVSSSDGSFLAD (SEQ ID NO:13) or FARALAVAVD (SEQ ID NO:14) or has a sequence of at least 5 or 8 or 10 residues of any of these sequences. These peptides correspond to amino acids 213-229, 322-336, 359-368, 384-399, 56-61, 56-69, 355-364, 403-435 and 438-447 respectively of the human ECSM4 polypeptide shown in FIG. 4 . Peptides WLADTW (SEQ ID NO:10), WLADTWRSTSGSRD (SEQ ID NO:11), SPPTTYGYIS (SEQ ID NO:12), GSLANGWGSASEDNAASARASLVSSSDGSFLAD (SEQ ID NO:13) and FARALAVAVD (SEQ ID NO:14) represent conserved regions between the mouse and human homologues of the ECSM4 polypeptide, and between the ECSM4 polypeptide and the mouse duttl protein. The peptides LSQSPGAVPQALVAWRA (SEQ ID NO:6), DSVLTPEEVALCLEL (SEQ ID NO:7), TYGYISVPTA (SEQ ID NO:8) and KGGVLLCPPRPCLTPT (SEQ ID NO:9) may be useful in raising antibodies.
Preferred peptides are peptides of at least 5 or 8 or 10 or 12 or 15 or 20 consecutive amino acid residues from these conserved sequences. Peptides of ECSM4 which affect cell migration and/or growth and/or vascular development are particularly preferred. They can be identified in suitable screening systems.
In a further preferred embodiment of this aspect of the invention, a fragment of the ECSM4 polypeptide is a fragment which has the sequence GGDSLLGGRGSL, LLQPPARGHAHDGQALSTDL, EPQDYTEPVE, TAPGGQGAPWAEE or ERATQEPSEHGP or has a sequence of at least 5 or 8 or 10 residues of any of these sequences. These peptides correspond to regions of the human ECSM4 polypeptide (located at residues 4-16, 91-109, 227-236, 288-300 and 444-455 respectively in the sequence given in FIG. 12 ) which are not, or are poorly, conserved in the mouse homologue (see FIG. 14 ). As described below, such peptides may be particularly useful in raising antibodies to the human ECSM4 polypeptide.
According to the transmembrane domain predicting software program called PRED-TMR (available at the Biophys.Biol. internet site) and an amino acid sequence alignment with the human protein Robol (whose transmembrane region is known), residues 1-467 as shown in FIG. 12 are likely to be extracellular, and in addition to being extracellularly exposed, may include the binding site of the natural ligand. Hence fragments of ECSM4 which include or consist of a sequence within the extracellular domain of residues 1-467 of FIG. 12 may represent useful fragments for raising antibodies selective for cells expressing ECSM4 on their surface and which may also be useful in modulating the activity of the polypeptide ECSM4.
Hence, preferred fragments of the ECSM4 polypeptide are those fragments of the polypeptide sequence of FIG. 12 which comprise at least 1, 3 or 5, amino acid residues which are not conserved when compared to the mouse ECSM4 (as shown in FIG. 13 ). More preferably at least 7, 9, 11 or 13 amino acid residues in the fragment are not conserved between human ECSM4 and mouse ECSM4, and still more preferably at least 15, 17, 19 or 21 residues of the fragment are not conserved between human ECSM4 and mouse ECSM4. The sequence of such fragments may be determined from the alignment of the human and mouse amino acid sequences shown in FIG. 14 .
It will be appreciated that fragments of the ECSM4 or ECSM1 polypeptide of the invention are particularly useful when fused to other polypeptides, such as glutathione-S-transferase (GST), green fluorescent protein (GFP), vesicular stomatitis virus glycoprotein (VSVG) or keyhole limpet haemacyanin (KLH). Fusions of the polypeptide, or fusions of fragments or variants of the polypeptide of the invention are included in the scope of the invention.
Other useful fragments of ECSM4 are those which are able to bind a ligand selective for ECSM4. Suitable methods for identification of ligands such as peptides or other molecules which bind ECSM4 is discussed in more detail above. Such peptides or other ECSM4-binding molecules can be used to identify the amino acid sequences present in ECSM4 which are responsible for ligand binding. Identification of those fragments of ECSM4 which, when isolated from the rest of the molecule, are still able to bind a ligand of ECSM4 can be achieved by means of a screen. Typically, such a screen will comprise contacting a ligand of ECSM4 with a test fragment of the ECSM4 polypeptide and determining if the test fragment binds the ligand. Fragments of ECSM4 are within the scope of the invention, and may be particularly useful in medicine. A fragment of ECSM4 which binds the natural ECSM4 ligand may neutralise the effect of the ligand and thereby affect endothelial cell migration, growth and/or vascular development. Hence, administration of fragments of ECSM4 may be useful in the treatment of diseases or conditions where endothelial cell migration, growth and/or vascular development need to be modulated. Examples of such diseases include cancer and artherosclerosis.
A “fusion” of the ECSM4 or ECSM1 polypeptide or a fragment or variant thereof provides a molecule comprising a polypeptide of the invention and a further portion. It is preferred that the said further portion confers a desirable feature on the said molecule; for example, the portion may useful in detecting or isolating the molecule, or promoting cellular uptake of the molecule. The portion may be, for example, a biotin moiety, a radioactive moiety, a fluorescent moiety, for example a small fluorophore or a green fluorescent protein (GFP) fluorophore, as well known to those skilled in the art. The moiety may be an immunogenic tag, for example a Myc tag, as known to those skilled in the art or may be a lipophilic molecule or polypeptide domain that is capable of promoting cellular uptake of the molecule or the interacting polypeptide, as known to those skilled in the art.
A “variant” of the ECSM4 or ECSM1 polypeptide includes natural variants, including allelic variants and naturally-occurring mutant forms and variants with insertions, deletions and substitutions, either conservative or non-conservative, where such changes do not substantially alter the activity of the said polypeptide. In the case of the ECSM4 polypeptide, as an endothelial specific homologue of the human roundabout 1 it may well be involved in endothelial cell repulsive guidance. In addition, polypeptides which are elongated as a result of an insertion or which are truncated due to deletion of a region are included in the scope of the invention. For example, deletion of cytoplasmically-located regions may be useful in creation of “dominant negative” or “dominant positive” forms of the polypeptide. Similarly, deletion of a transmembrane region of the polypeptide may produce such forms.
By “conservative substitution” is intended combinations such as Gly, Ala; Val, Ile, Leu; Asp, Glu; Asn, Gln; Ser, Thr; Lys, Arg; and Phe, Tyr.
By “non-conservative substitution” we include other substitutions, such as those where the substituted residue mimics a particular modification of the replaced residue, for example a phosphorylated tyrosine or serine may be replaced by aspartate or glutamate due to the similarity of the aspartate or glutamate side chain to a phosphorylated residue (ie they carry a negative charge at neutral pH).
Further non-conservative substitutions which are included in the term “variants” are point mutations which alter one, sometimes two, and usually no more than three amino acids. Such mutations are well known in the art of biochemistry and are usually designed to insert or remove a defined characteristic of the polypeptide. Another type of non-conservative mutation is the alteration or addition of a residue to a cysteine or lysine residue which can then be used with maleimide or succinimide cross-linking reagents to covalently conjugate the polypeptide to another moiety. Non-glycosylated proteins may be mutated to convert an asparagine to the recognition motif N—X—S/T for N-linked glycosylation. Such a modification may be useful to create a tag for purification of the polypeptide using Concanavalin A-linked beads.
Such variants may be made using the methods of protein engineering and site-directed mutagenesis well known in the art.
Variants of the ECSM4 polypeptide include polypeptides comprising a sequence with at least 65% identity to the amino acid sequence given in FIG. 4 or FIG. 7 or FIG. 12 or FIG. 13 , preferably at least 70% or 80% or 85% or 90% identity to said sequence, and more preferably at least 95% or 98% identity to said amino acid sequence.
Variants of the ECSM1 polypeptide include polypeptides comprising a sequence with at least 65% identity to the amino acid sequence given in FIG. 2 , preferably at least 70% or 80% or 85% or 90% identity to said sequence, and more preferably at least 95% or 98% identity to said amino acid sequence.
Percent identity can be determined by, for example, the LALIGN program (Huang and Miller, Adv. Appl. Math . (1991) 12:337-357) at the Expasy facility internet site using as parameters the global alignment option, scoring matrix BLOSUM62, opening gap penalty -14, extending gap penalty -4.
A thirteenth aspect of the invention provides a polynucleotide encoding the ECSM4 polypeptide of the invention, or the complement thereof or a polynucleotide which selectively hybridises to either of these which polynucleotide is not any one of the clones corresponding to GenBank Accession No AK000805 or the ESTs whose GenBank Accession Nos are given in Table 11 or Table 12.
GenBank Accession No AK000805 corresponds to a cDNA sequence cloned in the vector pME18SFL3. ESTs listed in Table 11 represent nucleotide sequences which can be assembled into the contig sequence shown in FIG. 5 . ESTs listed in Table 12 represent nucleotide sequences which can be assembled into the mouse nucleotide cluster sequence (Mm.27782) given in FIG. 7 .
Preferably, the polynucleotide of this aspect of the invention does not consist of any one of the nucleotide sequences represented by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00 53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 or SEQ ID No 31 of WO 99/11293, or their complement.
Also preferably, the polynucleotide of this aspect of the invention is not a polynucleotide which encodes a polypeptide consisting of the amino acid sequence represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293
Polynucleotides of the thirteenth aspect of the invention are described in more detail below.
A fourteenth aspect of the invention provides a polynucleotide encoding the ECSM1 polypeptide or the complement thereof or a polynucleotide which selectively hybridises to either of these, according to the twelfth aspect of the invention provided that the polynucleotide is not one present in ATCC deposit No 209145 or the clone corresponding to GenBank Accession No AC011526 or the ESTs whose GenBank Accession Nos are given in Table 10.
By “encoding a polypeptide according to the twelfth aspect of the invention” we mean that the polynucleotide is one which encodes an ECSM1 polypeptide of the invention and is not one which encodes a polypeptide whose sequence is given in SEQ ID No 120 of WO 99/06423 or which is encoded by SEQ ID No 32 or by the nucleic acid included in the microbiological deposit corresponding to American Type Culture Collection (ATCC) No. 209145 made on 17 Jul. 1997.
ATCC deposit No 209145 comprises a pSport1 vector which includes a 765 base nucleotide sequence.
The polynucleotide sequence given in SEQ ID No 32 of WO 99/06423 is similar to the nucleotide sequence shown in FIG. 2 . The sequence of SEQ ID No 32 given in WO 99/06423 may be capable of encoding part of the ECSM1 polypeptide of the invention. Due to degeneracy of the genetic code however, a polynucleotide sequence may encode the ECSM1 polypeptide of the invention without having a nucleotide sequence as given in WO 99/06423. In a similar manner, a polynucleotide sequence may encode the (full length) ECSM4 polypeptide of the invention without having the same sequence as that given in FIG. 4 or FIG. 5 or FIG. 12 . Such polynucleotides are within the scope of this invention.
Hence, it will be appreciated that a polynucleotide of the thirteenth aspect of the invention is preferably not one whose nucleotide sequence is given in FIG. 4 , and that a polynucleotide of the fourteenth aspect of the invention is preferably not a polynucleotide which is disclosed in WO 99/06423, such as SEQ ID No 32 disclosed therein or its complement or variants or the corresponding cDNA sequence deposited under Accession No 209145 at the ATCC or a polynucleotide fragment capable of encoding a polypeptide whose amino acid sequence comprises the sequence given in SEQ ID No 120 of WO 99/06423.
A polynucleotide of the thirteenth or fourteenth aspects of the invention may encode a variant of the ECSM4 or ECSM1 polypeptide as described above. In addition, the insertions and/or deletions within the ECSM4 or ECSM1 polypeptide may lead to frameshift mutations which may encode truncated (or elongated) polypeptide products, and insertions, deletions or other mutations may lead to the introduction of stop codons which encode truncate polypeptide products.
The polynucleotide of the invention may be DNA or RNA. It is preferred if it is DNA.
The polynucleotide may or may not contain introns. It is preferred if it does not contain introns.
The polynucleotide may be single stranded or double stranded or a mixture of either.
The polynucleotide of the invention has at least 10 nucleotides, and preferably at least 15 nucleotides and more preferably at least 30 nucleotides. In a further preference, the polynucleotide is more than 50 nucleotides, more preferably at least 100 nucleotides, and still more preferably the polynucleotide is at least 500 nucleotides. The polynucleotide may be more than 1 kb, and may comprise more than 5 kb.
The invention also includes a polynucleotide which is able to selectively hybridise to a polynucleotide which encodes the ECSM4 or ECSM1 polypeptide or a fragment or variant or fusion thereof, or a fusion of said variant or fragment. Preferably, said polynucleotide is at least 10 nucleotides, more preferably at least 15 nucleotides and still more preferably at least 30 nucleotides in length. The said polynucleotide may be longer than 100 nucleotides and may be longer than 200 nucleotides, but preferably the said polynucleotide is not longer than 250 nucleotides. Such polynucleotides are useful in procedures as a detection tool to demonstrate the presence of the polynucleotide in a sample. Such a sample may be a sample of DNA, such as a bacterial colony, fixed on a membrane or filter.
Preferably, the polynucleotide which is capable of selectively hybridising as said is not any one of the nucleotide sequences represented by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00 53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 or SEQ ID No 31 of WO 99/11293.
By “selectively hybridise” we mean that the polynucleotide hybridises under conditions of high stringency. DNA-DNA, DNA-RNA and RNA-RNA hybridisation may be performed in aqueous solution containing between 0.1×SSC and 6×SSC and at temperatures of between 55° C. and 70° C. It is well known in the art that the higher the temperature or the lower the SSC concentration the more stringent the hybridisation conditions. By “high stringency” we mean 2×SSC and 65° C. 1×SSC is 0.15M NaCl/0.015M sodium citrate. Polynucleotides which hybridise at high stringency are included within the scope of the claimed invention.
In another embodiment, the polynucleotide can be used as a primer in the polymerase chain reaction (PCR), and in this capacity a polynucleotide of between 15 and 30 nucleotides is preferred. A polynucleotide of between 20 and 100 nucleotides is preferred when the fragment is to be used as a mutagenic PCR primer. It is particularly preferred if the PCR primer (when not being used to mutate a nucleic acid) contains about 15 to 30 contiguous nucleotides (ie perfect matches) from the nucleotide sequence given in FIG. 4 or FIG. 7 or FIG. 12 or FIG. 13 from the nucleotide sequence given in FIG. 2 . Clearly, if the PCR primers are used for mutagenesis, differences compared to the sequence will be present.
Primers which are suitable for use in a polymerase chain reaction (PCR; Saiki et al (1988) Science 239, 487-491) are preferred. Suitable PCR primers may have the following properties:
It is well known that the sequence at the 5′ end of the oligonucleotide need not match the target sequence to be amplified.
It is usual that the PCR primers do not contain any complementary structures with each other longer than 2 bases, especially at their 3′ ends, as this feature may promote the formation of an artifactual product called “primer dimer”. When the 3′ ends of the two primers hybridize, they form a “primed template” complex, and primer extension results in a short duplex product called “primer dimer”.
Internal secondary structure should be avoided in primers. For symmetric PCR, a 40-60% G+C content is often recommended for both primers, with no long stretches of any one base. The classical melting temperature calculations used in conjunction with DNA probe hybridization studies often predict that a given primer should anneal at a specific temperature or that the 72° C. extension temperature will dissociate the primer/template hybrid prematurely. In practice, the hybrids are more effective in the PCR process than generally predicted by simple T m calculations.
Optimum annealing temperatures may be determined empirically and may be higher than predicted. Taq DNA polymerase does have activity in the 37-55° C. region, so primer extension will occur during the annealing step and the hybrid will be stabilised. The concentrations of the primers are equal in conventional (symmetric) PCR and, typically, within 0.1- to 1 nM range.
When a pair of suitable nucleic acids of the invention are used in a PCR it is convenient to detect the product by gel electrophoresis and ethidium bromide staining. As an alternative to detecting the product of DNA amplification using agarose gel electrophoresis and ethidium bromide staining of the DNA, it is convenient to use a labelled oligonucleotide capable of hybridising to the amplified DNA as a probe. When the amplification is by a PCR the oligonucleotide probe hybridises to the interprimer sequence as defined by the two primers. The probe may be labelled with a radionuclide such as 32 P, 33 P and 35 S using standard techniques, or may be labelled with a fluorescent dye. When the oligonucleotide probe is fluorescently labelled, the amplified DNA product may be detected in solution (see for example Balaguer et al (1991) “Quantification of DNA sequences obtained by polymerase chain reaction using a bioluminescence adsorbent” Anal. Biochem. 195, 105-110 and Dilesare et al (1993) “A high-sensitivity electrochemiluminescence-based detection system for automated PCR product quantitation” BioTechniques 15, 152-157.
PCR products can also be detected using a probe which may have a fluorophore-quencher pair or may be attached to a solid support or may have a biotin tag or they may be detected using a combination of a capture probe and a detector probe.
Fluorophore-quencher pairs are particularly suited to quantitative measurements of PCR reactions (eg RT-PCR). Fluorescence polarisation using a suitable probe may also be used to detect PCR products.
Oligonucleotide primers can be synthesised using methods well known in the art, for example using solid-phase phosphoramidite chemistry.
A polynucleotide or oligonucleotide primer of the invention may contain one or more modified bases or may contain a backbone which has been modified for stability purposes or for other reasons. By modified we included for example, tritylated bases and unusual bases such as inosine. A variety of modifications can be made to DNA and RNA and these are included in the scope of the invention.
In a preferred embodiment, the polynucleotides of the invention are detectably labelled. Suitable detectable labels are described in detail above.
A fifteenth aspect of the invention provides an expression vector comprising a polynucleotide as described above. Typically, the polynucleotides are those which encode the polypeptides ECSM1 or ECSM4 or a fragment, variant or fusion thereof.
By “expression vector” we mean one which is capable, in an appropriate host, of expressing a polypeptide encoded by the polynucleotide.
Such vectors may be useful in expressing the encoded polypeptide in a host cell for production of useful quantities of the polypeptide, or may be useful in medicine. Expression vectors comprising a polynucleotide according to the thirteenth or fourteenth aspects of the invention which are suitable for use in gene therapy are within the scope of the invention. Administration of a gene therapy vector capable of expressing the ECSM4 polypeptide may be useful in modulating or inhibiting angiogenesis, since this polypeptide is likely to be a repulsive guidance receptor. Similarly, gene therapy vectors capable of expressing fragments or mutants of ECSM4 on the cell surface, which fragments or mutants are capable of binding the ECSM4 cognate ligand but are not able to convey the normal downstream signal (for example, because the necessary cytosolic portion of the polypeptide is deleted or mutated so as to not be functional or capable of binding normally interacting cellular proteins) may also be useful in modulating angiogenesis in an individual.
Hence, in a preferred embodiment, the vector is one which is suitable for use in gene therapy. Examples of suitable vectors and methods of their introduction into cells are given in more detail below. In particular, the gene therapy methods and vectors described in relation to the use of promoters of ECSM4 may also be used in relation to the use of ECSM4 coding sequences or antisense in gene therapy.
It will be appreciated that the polynucleotide comprised within the expression vector of this aspect of the invention may be one which encodes the polypeptide ECSM4 or ECSM1 or a fragment or variant thereof, or the polynucleotide may be one which is capable of selectively hybridising to the ECSM4 or ECSM1 coding region. Polynucleotides which are capable of hybridising to the ECSM4 or ECSM1 coding region are useful as antisense polynucleotides which may decrease the expression level of ECSM4 or ECSM1 within a target cell. The design of suitable and effective antisense polynucleotides based on a known coding sequence is known in the art of gene therapy.
Preferably, the expression vector of this aspect of the invention is one which does not contain a polynucleotide sequence represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293 or their complement. Also preferably, the said vector is one which does not contain a polynucleotide encoding a polypeptide whose amino acid sequence is represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293.
Both the amount of therapeutic protein or therapeutic polynucleotide produced and the duration of production are important issues in gene therapy. Consequently, the use of viral vectors capable of cellular gene integration (eg retroviral vectors) may be more beneficial than non-integrating alternatives (eg adenovirus derived vectors) when repeated therapy is undesirable for immunogenicity reasons.
By “therapeutic polynucleotide” or “therapeutic protein” we include ECSM4 and ECSM1 coding sequences, the polypeptide product encoded by said coding sequences, and ECSM4 antisense polynucleotides. The therapeutic effect of said polynucleotides or proteins may include pro-angiogenic or anti-angiogenic effects, depending on the precise therapeutic agent administered. For example, an expression vector suitable for gene therapy which comprises a polynucleotide which is antisense to at least part of the ECSM4 coding region may have anti-angiogenic activity when expressed in a host cell or patient if it suppresses expression of a molecule which is required for angiogenesis. If the polynucleotide comprised within the expression vector encodes a polypeptide which is required for inhibition of angiogenesis (for example, because said polypeptide has endothelial cell repulsive guidance activity), then expression of the antisense may also be anti-angiogenic.
Conversely, if said the expression vector comprises a polynucleotide of the invention which polynucleotide suppresses expression of a molecule whose activity is required to decrease vascular growth (for example, because said molecule is an endothelial cell repulsive guidance molecule) or encodes a polypeptide whose activity is required for angiogenesis, administration of the said vector may be pro-angiogenic.
Where the therapeutic gene is maintained extrachromosomally, the highest level of expression is likely to be achieved using viral promoters, for example, the Rous sarcoma virus long terminal repeat (Ragot et al (1993) Nature 361, 647-650; Hyde et al (1993) Nature 362, 250-255) and the adenovirus major late promoter. The latter has been used successfully to drive the expression of a cystic fibrosis transmembrane conductance regulator (CFTR) gene in lung epithelium (Rosenfeld et al (1992) Cell 68, 143-155). Since these promoters function in a broad range of tissues they may not be suitable to direct cell-type-specific expression unless the delivery method can be adapted to provide the specificity. However, somatic enhancer sequences could be used to give cell-type-specific expression in an extrachromosomal setting.
As described in more detail below, the ECSM4 regulatory/promoter region is an example of a regulatory region capable of conferring endothelial cell selective expression, preferably selective to endothelial cells of neovasculature (ie, angiogenic endothelial cells) on an operatively linked coding region. As outlined above, such a coding region may encode an antisense polynucleotide.
Where withdrawal of the gene-vector construct is not possible, it may be necessary to add a suicide gene to the system to abort toxic reactions rapidly. The herpes simplex virus thymidine kinase gene, when transduced into cells, renders them sensitive to the drug ganciclovir, creating the option of killing the cells quickly.
The use of ectotropic viruses, which are species specific, may provide a safer alternative to the use of amphotropic viruses as vectors in gene therapy. In this approach, a human homologue of the non-human, ectotropic viral receptor is modified in such a way so as to allow recognition by the virus. The modified receptor is then delivered to cells by constructing a molecule, the front end of which is specified for the targeted cells and the tail part being the altered receptor. Following delivery of the receptor to its target, the genetically engineered ectotropic virus, carrying the therapeutic gene, can be injected and will only integrate into the targeted cells.
Virus-derived gene transfer vectors can be adapted to recognise only specific cells so it may be possible to target to an endothelial cell, such as endothelial cells within a tumour. Similarly, it is possible to target expression of an therapeutic gene to the endothelial cell, using an endothelial cell-specific promoter such as that for the ECSM4 or ECSM1 genes.
One of the ECSM genes or a part of the genes or a polynucleotide comprising an antisense to the gene may be introduced into the cell in a vector such that the gene remains extrachromosomal. In such a situation, the gene will be expressed by the cell from the extrachromosomal location. Vectors for introduction of genes both for recombination and for extrachromosomal maintenance are known in the art, and any suitable vector may be used. Methods for introducing DNA into cells such as electroporation, calcium phosphate co-precipitation and viral transduction are known in the art, and the choice of method is within the competence of the ordinary skilled person. Cells transformed with the wild-type novel gene can be used as model systems to study cancer remission and drug treatments which promote such remission.
A variety of methods have been developed to operably link polynucleotides, especially DNA, to vectors, for example, via complementary cohesive termini. For instance, complementary homopolymer tracts can be added to the DNA segment to be inserted into the vector DNA. The vector and DNA segment are then joined by hydrogen bonding between the complementary homopolymeric tails to form recombinant DNA molecules.
Synthetic linkers containing one or more restriction sites provide an alternative method of joining the DNA segment to vectors. The DNA segment, generated by endonuclease restriction digestion as described earlier, is treated with bacteriophage T4 DNA polymerase or E. coli DNA polymerase I, enzymes that remove protruding, 3′-single-stranded termini with their 3′-5′-exonucleolytic activities, and fill in recessed 3′-ends with their polymerising activities.
The combination of these activities therefore generates blunt-ended DNA segments. The blunt-ended segments are then incubated with a larger molar excess of linker molecules in the presence of an enzyme that is able to catalyse the ligation of blunt-ended DNA molecules, such as bacteriophage T4 DNA ligase. Thus, the products of the reaction are DNA segments carrying polymeric linker sequences at their ends. These DNA segments are then cleaved with the appropriate restriction enzyme and ligated to an expression vector that has been cleaved with an enzyme that produces termini compatible with those of the DNA segment.
Synthetic linkers containing a variety of restriction endonuclease site are commercially available from a number of sources including International Biotechnologies Inc., New Haven, Conn., USA.
A desirable way to modify the DNA encoding the polypeptide of the invention is to use PCR. This method may be used for introducing the DNA into a suitable vector, for example by engineering in suitable restriction sites, or it may be used to modify the DNA in other useful ways as is known in the art.
In this method the DNA to be enzymatically amplified is flanked by two specific primers which themselves become incorporated into the amplified DNA. The said specific primers may contain restriction endonuclease recognition sites which can be used for cloning into expression vectors using methods known in the art.
The DNA (or in the case of retroviral vectors, RNA) is then expressed in a suitable host to produce a polypeptide comprising the polypeptide of the invention. Thus, the DNA encoding the polypeptide constituting the polypeptide of the invention may be used in accordance with known techniques, appropriately modified in view of the teachings contained herein, to construct an expression vector, which is then used to transform an appropriate host cell for the expression and production of the polypeptide of the invention. Such techniques include those disclosed in U.S. Pat. Nos. 4,440,859 issued 3 Apr. 1984 to Rutter et al, 4,530,901 issued 23 Jul. 1985 to Weissman, 4,582,800 issued 15 Apr. 1986 to Crowl, 4,677,063 issued 30 Jun. 1987 to Mark et al, 4,678,751 issued 7 Jul. 1987 to Goeddel, 4,704,362 issued 3 Nov. 1987 to Itakura et al, 4,710,463 issued 1 Dec. 1987 to Murray, 4,757,006 issued 12 Jul. 1988 to Toole, Jr. et al, 4,766,075 issued 23 Aug. 1988 to Goeddel et al and 4,810,648 issued 7 Mar. 1989 to Stalker, all of which are incorporated herein by reference.
The DNA (or in the case or retroviral vectors, RNA) encoding the polypeptide constituting the polypeptide of the invention may be joined to a wide variety of other DNA sequences for introduction into an appropriate host. The companion DNA will depend upon the nature of the host, the manner of the introduction of the DNA into the host, and whether episomal maintenance or integration is desired.
Generally, the DNA is inserted into an expression vector, such as a plasmid, in proper orientation and correct reading frame for expression. If necessary, the DNA may be linked to the appropriate transcriptional and translational regulatory control nucleotide sequences recognised by the desired host, although such controls are generally available in the expression vector. The vector is then introduced into the host through standard techniques. Generally, not all of the hosts will be transformed by the vector. Therefore, it will be necessary to select for transformed host cells. One selection technique involves incorporating into the expression vector a DNA sequence, with any necessary control elements, that codes for a selectable trait in the transformed cell, such as antibiotic resistance. Alternatively, the gene for such selectable trait can be on another vector, which is used to co-transform the desired host cell.
Host cells that have been transformed by the expression vector of the invention are then cultured for a sufficient time and under appropriate conditions known to those skilled in the art in view of the teachings disclosed herein to permit the expression of the polypeptide, which can then be recovered.
Many expression systems are known, including bacteria (for example, E. coli and Bacillus subtilis ), yeasts (for example Saccharomyces cerevisiae ), filamentous fungi (for example Aspergillus ), plant cells, animal cells and insect cells.
The vectors typically include a prokaryotic replicon, such as the ColE1 ori, for propagation in a prokaryote, even if the vector is to be used for expression in other, non-prokaryotic, cell types. The vectors can also include an appropriate promoter such as a prokaryotic promoter capable of directing the expression (transcription and translation) of the genes in a bacterial host cell, such as E. coli , transformed therewith.
A promoter is an expression control element formed by a DNA sequence that permits binding of RNA polymerase and transcription to occur. Promoter sequences compatible with exemplary bacterial hosts are typically provided in plasmid vectors containing convenient restriction sites for insertion of a DNA segment of the present invention.
Typical prokaryotic vector plasmids are pUC18, pUC19, pBR322 and pBR329 available from Biorad Laboratories, (Richmond, Calif., USA) and pTrc99A and pKK223-3 available from Pharmacia, Piscataway, N.J., USA.
A typical mammalian cell vector plasmid is pSVL available from Pharmacia, Piscataway, N.J., USA. This vector uses the SV40 late promoter to drive expression of cloned genes, the highest level of expression being found in T antigen-producing cells, such as COS-1 cells.
An example of an inducible mammalian expression vector is pMSG, also available from Pharmacia. This vector uses the glucocorticoid-inducible promoter of the mouse mammary tumour virus long terminal repeat to drive expression of the cloned gene.
Useful yeast plasmid vectors are pRS403-406 and pRS413-416 and are generally available from Stratagene Cloning Systems, La Jolla, Calif. 92037, USA. Plasmids pRS403, pRS404, pRS405 and pRS406 are Yeast Integrating plasmids (YIps) and incorporate the yeast selectable markers HIS3, TRP1, LEU2 and URA3. Plasmids pRS413-416 are Yeast Centromere plasmids (Ycps).
Other vectors and expression systems are well known in the art for use with a variety of host cells.
A sixteenth aspect of the invention provides a recombinant host cell comprising a polynucleotide or vector of the invention.
The polynucleotide of the invention includes polynucleotides encoding a compound of the third aspect of the invention (where both the moiety which selectively binds and the further moiety are polypeptides which are fused) or an ECSM4 or ECSM1 polypeptide of the invention or a fragment or fusion or variant thereof as defined above.
The host cell can be either prokaryotic or eukaryotic. Bacterial cells are preferred prokaryotic host cells and typically are a strain of E. coli such as, for example, the E. coli strains DH5 available from Bethesda Research Laboratories Inc., Bethesda, Md., USA, and RR1 available from the American Type Culture Collection (ATCC) of Rockville, Md., USA (No. ATCC 31343). Preferred eukaryotic host cells include yeast, insect and mammalian cells, preferably vertebrate cells such as those from a mouse, rat, monkey or human fibroblastic and kidney cell lines. Yeast host cells include YPH499, YPH500 and YPH501 which are generally available from Stratagene Cloning Systems, La Jolla, Calif. 92037, USA. Preferred mammalian host cells include Chinese hamster ovary (CHO) cells available from the ATCC as CRL 1658 and 293 cells which are human embryonic kidney cells. Preferred insect cells are Sf9 cells which can be transfected with baculovirus expression vectors.
Transformation of appropriate cell hosts with a DNA construct of the present invention is accomplished by well known methods that typically depend on the type of vector used. With regard to transformation of prokaryotic host cells, see, for example, Cohen et al (1972) Proc. Natl. Acad. Sci. USA 69, 2110 and Sambrook et al (1989) Molecular Cloning, A Laboratory Manual, Cold Spring Harbor Laboratory, Cold Spring Harbor, N.Y. Transformation of yeast cells is described in Sherman et al (1986) Methods In Yeast Genetics , A Laboratory Manual, Cold Spring Harbor, N.Y. The method of Beggs (1978) Nature 275, 104-109 is also useful. With regard to vertebrate cells, reagents useful in transfecting such cells, for example calcium phosphate and DEAE-dextran or liposome formulations, are available from Stratagene Cloning Systems, or Life Technologies Inc., Gaithersburg, Md. 20877, USA.
Electroporation is also useful for transforming and/or transfecting cells and is well known in the art for transforming yeast cells, bacterial cells, insect cells and vertebrate cells.
For example, many bacterial species may be transformed by the methods described in Luchansky et al (1988) Mol. Microbiol. 2, 637-646 incorporated herein by reference. The greatest number of transformants is consistently recovered following electroporation of the DNA-cell mixture suspended in 2.5 PEB using 6250V per cm at 25 μFD.
Methods for transformation of yeast by electroporation are disclosed in Becker & Guarente (1990) Methods Enzymol. 194, 182.
Successfully transformed cells, ie cells that contain a DNA construct of the present invention, can be identified by well-known techniques. For example, cells resulting from the introduction of an expression construct of the present invention can be grown to produce the polypeptide of the invention. Cells can be harvested and lysed and their DNA content examined for the presence of the DNA using a method such as that described by Southern (1975) J. Mol. Biol. 98, 503 or Berent et al (1985) Biotech. 3, 208. Alternatively, the presence of the protein in the supernatant can be detected using antibodies as described below.
In addition to directly assaying for the presence of recombinant DNA, successful transformation can be confirmed by well known immunological methods when the recombinant DNA is capable of directing the expression of the protein. For example, cells successfully transformed with an expression vector produce proteins displaying appropriate antigenicity.
Samples of cells suspected of being transformed are harvested and assayed for the protein using suitable antibodies.
The host cell may be a host cell within an animal body. Thus, transgenic animals which express a polypeptide of the first or third aspects of the invention by virtue of the presence of the transgene are included. Preferably, the transgenic animal is a rodent such as a mouse. Transgenic animals can be made using methods well known in the art.
Polynucleotides encoding the polypeptide ECSM4 may be useful in generating transgenic non-human mammals wherein the ECSM4 is mutated in some way. For example, the mouse ECSM4 genomic coding region may be mutated in a mouse so as to produce an ECSM4 polypeptide which is incapable of binding its natural ligand, or incapable of correctly interacting with intracellular components. Such a mutated ECSM4 polypeptide may produce a disease in the mouse which is very similar to a disease involving abnormal vascularisation in humans.
Hence, non-human mammals, especially rodents such as mice and rats, are useful as models of diseases involving abnormal vascularisation.
Alternatively, mammals lacking the ECSM4 gene (“knock-outs”) or lacking an ECSM4 genomic coding region which is capable of being transcribed or of expressing the ECSM4 polypeptide, may be useful in providing a means of generating antibodies selective for the human ECSM4 polypeptide. Such mammals, especially mice, are likely to be particularly useful since the high level of homology between the human and mouse ECSM4 polypeptides may prevent human ECSM4 polypeptide from being antigenic in mice who do express the ECSM4 polypeptide.
A potentially more accurate animal model of diseases involving abnormal vascularisation may be made by addition to the genome of a transgenic animal as described above, or replacing the genomic ECSM4 of an animal with, the gene for human ECSM4 which has been mutated. Suitably, the human ECSM4 inserted will be under control of an endothelial selective promoter and regulatory region. Preferably, the promoter and regulatory regions are those of the host animal ECSM4 gene. An animal who genome is modified in this way will express the dysfunctional human ECSM4, and therefore will be useful in testing the efficacy of drugs and antibodies in the diagnosis, prognosis and treatment of diseases involving abnormal vascularisation in humans.
Such knockout or transgenic mammals are within the scope of the invention and antibodies generated using such mammals and compounds comprising them are also included within the scope of the invention.
A seventeenth aspect of the invention provides a method of producing a polypeptide of the invention, the method comprising expressing a polynucleotide as described above or culturing a host cell as described herein.
It will be appreciated that in order to produce the ECSM1 polypeptide, the host cell may comprise a polynucleotide encoding a polypeptide whose amino acid sequence includes the sequence given in FIG. 2 , and that in order to produce the ECSM4 polypeptide the host cell may comprise a polynucleotide encoding the polypeptide whose amino acid sequence is given in FIG. 4 or FIG. 7 or FIG. 12 and so on.
Preferably, the polynucleotide expressed does not consist of any one of the nucleotide sequences represented by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00/53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 and SEQ ID No 31 of WO 99/11293.
Also preferably, the polypeptide produced is not one with an amino acid sequence consisting of the sequence represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293.
Methods of cultivating host cells and isolating recombinant proteins are well known in the art. It will be appreciated that, depending on the host cell, the ECSM1 or ECSM4 polypeptides produced may differ from that which can be isolated from nature. For example, certain host cells, such as yeast or bacterial cells, either do not have, or have different, post-translational modification systems which may result in the production of forms of ECSM1 or ECSM4 which may be post-translationally modified in a different way to ECSM1 or ECSM4 isolated from nature. In order to obtain ECSM1 or ECSM4 which is post-translationally modified in a different way to human ECSM1 or ECSM4 it is preferred if the host cell is a non-human host cell; more preferably it is not a mammalian cell.
It is preferred that the ECSM1 or ECSM4 polypeptide is produced in a eukaryotic system, such as an insect cell.
According to a less preferred embodiment, the ECSM1 or ECSM4 polypeptide can be produced in vitro using a commercially available in vitro translation system, such as rabbit reticulocyte lysate or wheatgerm lysate (available from Promega). Preferably, the translation system is rabbit reticulocyte lysate. Conveniently, the translation system may be coupled to a transcription system, such as the TNT transcription-translation system (Promega). This system has the advantage of producing suitable mRNA transcript from an encoding DNA polynucleotide in the same reaction as the translation. Conveniently, where the expressed polypeptide comprises one or more transmembrane domains, the translation system can be supplemented with a source of endoplasmic reticulum-derived membranes and folding chaperones, such as dog pancreatic microsomes, to allow synthesis of the polypeptide in a native conformation.
Preferably, the production method of this aspect of the invention comprises a further step of isolating the ECSM1 or ECSM4 produced from the host cell or from the in vitro translation mix. Preferably, the isolation employs an antibody which selectively binds the expressed polypeptide of the invention.
It will be understood that the invention comprises the ECSM1 or ECSM4 polypeptides or the variants or fragments or fusions thereof, or a fusion of said variants or fragments obtainable by the methods herein disclosed, provided that the ECSM4 polypeptide is not one which consists of the amino acid sequence given in FIG. 4 . Preferably, the polypeptide is not one which consists of an amino acid sequence represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293. Preferably, the ECSM1 polypeptide produced by the methods herein disclosed is not one which is encoded by SEQ ID No 32 of WO 99/06423 or encoded by the nucleic acid of ATCC deposit No. 209145 made on Jul. 17, 1997 for the purposes of WO 99/06423.
An eighteenth aspect of the invention provides an antibody capable of selectively binding to either ECSM4 or ECSM1 as defined above.
Preferably, an antibody which selectively binds ECSM1 is not one which binds a polypeptide encoded by SEQ ID No 32 of WO 99/06423 or encoded by the nucleic acid of ATCC deposit No 209145 made on Jul. 17, 1997 for the purposes of the international patent application PCT/US98/15949.
Preferably, an antibody which selectively binds ECSM1 is one which binds a polypeptide whose amino acid sequence comprises the sequence given in FIG. 2 or a natural variant thereof but does not comprise the amino acid sequence encoded by ATCC deposit No 209145 made on Jul. 17, 1997.
Preferably, an antibody which selectively binds ECSM4 is one which binds a polypeptide whose amino acid sequence comprises the sequence given in any one of FIGS. 4 , 5 , 7 , 12 or 13 or a natural variant thereof but does not bind the polypeptide represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293, or encoded by any one of the nucleotide sequences represented by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00/53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 and SEQ ID No 31 of WO 99/11293.
By “selectively bind” we include antibodies which bind at least 10-fold more strongly to a polypeptide of the invention (such as ECSM4 or ECSM1) than to another polypeptide; preferably at least 50-fold more strongly and more preferably at least 100-fold more strongly. Such antibodies may be made by methods well known in the art using the information concerning the differences in amino acid sequence of ECSM4 or ECSM1 and another polypeptide which is not a polypeptide of the invention.
Antibodies which selectively bind ECSM4 may also modulate the function of the ECSM4 polypeptide. Antibodies which mimic the effect of binding of the cognate ligand by stimulating or activating ECSM4, or which bind and thereby prevent subsequent binding and activation or stimulation of ECSM4 by the cognate ligand, and such function-modulating antibodies are included in the scope of the invention. It will be appreciated that antibodies which modulate the function are useful as a tool in research, for example in studying the effects of ECSM4 stimulation or activation, or downstream processes triggered by such stimulation. Such antibodies are also useful in medicine, for example in modulating angiogenesis in an individual. Specifically, modulation of angiogenesis by administration of such an antibody may be useful in the treatment of a disease in an individual where modulation of angiogenesis would be beneficial, such as cancer.
The following peptides may be useful as immunogens in the generation of antibodies, such as rabbit polyclonal sera: LSQSPGAVPQALVAWRA (SEQ ID NO:6), DSVLTPEEVALCLEL (SEQ ID NO:7), TYGYISVPTA (SEQ ID NO:8) and KGGVLLCPPRPCLTPT (SEQ ID NO:9).
In a preferred embodiment of this aspect, the antibody of the invention selectively binds an amino acid sequence with the sequence GGDSLLGGRGSL (SEQ ID NO:1), LLQPPARGHAHDGQALSTDL (SEQ ID NO:2), EPQDYTEPVE (SEQ ID NO:3), TAPGGQGAPWAEE (SEQ ID NO:4) or ERATQEPSEHGP (SEQ ID NO:5). These sequences represent amino acid sequences which are not identical between the human and mouse ECSM4 polypeptide sequences. Generally, the human and mouse ECSM4 polypeptides display a high degree of identity, which makes the production of mouse antibodies to the human ECSM4 particularly difficult due to the lack of immunogenicity of much of the human ECSM4 sequence in mouse. Amino acid sequences which are absent from the mouse ECSM4 are more likely to more be immunogenic in a mouse than those sequences which are present in the mouse ECSM4 (an alignment of the human and mouse ECSM4 amino acid sequences is shown in FIG. 14 ). Hence, polypeptide fragments which contain sequences which are unique to human ECSM4 as described above are more useful than ECSM4 polypeptides whose sequence is found in both human and mouse ECSM4, in the production of antibodies which selectively bind the human ECSM4 polypeptide.
Antibodies generated as a result of use of amino acid sequences which are located in the extracellular portion of the ECSM4 polypeptide are likely to be useful as endothelial cell targeting molecules. Therefore, it is particularly preferred if the antibody of the invention is raised to, and preferably selectively binds, an amino acid sequence which is unique to the human ECSM4 polypeptide, which sequence is located towards the N-terminal end of the polypeptide and is found in the extracellular portion located between residues 1 and 467 of the amino acid sequence given in FIG. 12 . An example of an amino acid sequence which is suitable for raising antibody molecules selective for the ECSM4 extracellular region is given in FIG. 12 .
Although the amino acid sequences which are unique to the human ECSM4 may be used to produce polyclonal antibodies, it is preferred if they are used to produce monoclonal antibodies.
Peptides in which one or more of the amino acid residues are chemically modified, before or after the peptide is synthesised, may be used providing that the function of the peptide, namely the production of specific antibodies in vivo, remains substantially unchanged. Such modifications included forming salts with acids or bases, especially physiologically acceptable organic or in organic acids and bases, forming an ester or amid of a terminal carboxyl group, and attaching amino acid protecting groups such as N-t-butoxycarbonyl. Such modifications may protect the peptide from in vivo metabolism. The peptides may be present as single copies or as multiples, for example tandem repeats. Such tandem or multiple repeats may be sufficiently antigenic themselves to obviate the use of a carrier. It may be advantageous for the peptide to be formed as a loop, with the N-terminal and C-terminal ends joined together, or to add one or more Cys residues to an end to increase antigenicity and/or to allow disulphide bonds to be formed. If the peptide is covalently linked to a carrier, preferably a polypeptide, then the arrangement is preferably such that the peptide of the invention forms a loop.
According to current immunological theories, a carrier function should be present in any immunogenic formulation in order to stimulate, or enhance stimulation of, the immune system. It is though that the best carriers embody (or, together with the antigen, create) a T-cell epitope. The peptides may be associated, for example by cross-linking, with a separate carrier, such as serum albumins, myoglobins, bacterial toxoids and keyhole limpit haemocyanin. More recently developed carriers which induce T-cell help in the immune response include the hepatitis-B core antigen (also called the nucleocapsid protein), presumed T-cell epitopes such as Thr-Ala-Ser-Gly-Val-Ala-Glu-Thr-Thr-Asn-Cys, β-galactosidase and the 163-171 peptide of interleukin-1. The latter compound may variously be regarded as a carrier or as an adjuvant or as both. Alternatively, several copies of the same or different peptides of the invention may be cross-linked to one another; in this situation there is no separate carrier as such, but a carrier function may be provided by such cross-linking. Suitably cross-linking agents include those listed as such in the Sigma and Pierce catalogues, for example glutaraldehyde, carbodiimide and succinimidyl 4-(N-maleimidomethyl)cyclohexane-1-carboxylate, the latter agent exploiting the —SH group on the C-terminal cysteine residue (if present).
If the peptide is prepared by expression of a suitable nucleotide sequence in a suitable host, then it may be advantageous to express the peptide as a fusion product with a peptide sequence which acts as a carrier. Kabigen's “Ecosec” system is an example of such an arrangement.
Peptides may be synthesised by the Fmoc-polyamide mode of solid-phase peptide synthesis as disclosed by Lu et al (1981) J. Org. Chem. 46, 3433 and references therein. Temporary N-amino group protection is afforded by the 9-fluorenylmethyloxycarbonyl (Fmoc) group. Repetitive cleavage of this highly base-labile protecting group is effected using 20% piperidine in N,N-dimethylformamide. Side-chain functionalities may be protected as their butyl ethers (in the case of serine threonine and tyrosine), butyl esters (in the case of glutamic acid and aspartic acid), butyloxycarbonyl derivative (in the case of lysine and histidine), trityl derivative (in the case of cysteine) and 4-methoxy-2,3,6-trimethylbenzenesulphonyl derivative (in the case of arginine). Where glutamine or asparagine are C-terminal residues, use is made of the 4,4′-dimethoxybenzhydryl group for protection of the side chain amido functionalities. The solid-phase support is based on a polydimethyl-acrylamide polymer constituted from the three monomers dimethylacrylamide (backbone-monomer), bisacryloylethylene diamine (cross linker) and acryloylsarcosine methyl ester (functionalising agent). The peptide-to-resin cleavable linked agent used is the acid-labile 4-hydroxymethyl-phenoxyacetic acid derivative. All amino acid derivatives are added as their preformed symmetrical anhydride derivatives with the exception of asparagine and glutamine, which are added using a reversed N,N-dicyclohexyl-carbodiimide/1-hydroxybenzotriazole mediated coupling procedure. All coupling and deprotection reactions are monitored using ninhydrin, trinitrobenzene sulphonic acid or isotin test procedures. Upon completion of synthesis, peptides are cleaved from the resin support with concomitant removal of side-chain protecting groups by treatment with 95% trifluoroacetic acid containing a 50% scavenger mix. Scavengers commonly used are ethanedithiol, phenol, anisole and water, the exact choice depending on the constituent amino acids of the peptide being synthesised. Trifluoroacetic acid is removed by evaporation in vacuo, with subsequent trituration with diethyl ether affording the crude peptide. Any scavengers present are removed by a simple extraction procedure which on lyophilisation of the aqueous phase affords the crude peptide free of scavengers. Reagents for peptide synthesis are generally available from Calbiochem-Novabiochem (UK) Ltd, Nottingham NG7 2QJ, UK. Purification may be effected by any one, or a combination of, techniques such as size exclusion chromatography, ion-exchange chromatography and (principally) reverse-phase high performance liquid chromatography.
Analysis of peptides may be carried out using thin layer chromatography, reverse-phase high performance liquid chromatography, amino-acid analysis after acid hydrolysis and by fast atom bombardment (FAB) mass spectrometric analysis.
The peptide of the invention may be linked to other antigens to provide a dual effect.
Included in the scope of the invention is a method of producing an antibody according to this aspect of the invention.
Antibodies can be raised in an animal by immunising with an appropriate peptide. Appropriate peptides are described herein. Alternatively, with today's technology, it is possible to make antibodies as defined herein without the need to use animals. Such techniques include, for example, antibody phage display technology as is well known in the art. Appropriate peptides, as described herein, may be used to select antibodies produced in this way.
It will be appreciated that, with the advancements in antibody technology, it may not be necessary to immunise an animal in order to produce an antibody. Synthetic systems, such as phage display libraries, may be used. The use of such systems is included in the methods of the invention and the products of such systems are “antibodies” for the purposes of the invention.
It will be appreciated that such antibodies which recognise ECSM1 or ECSM4 and variants or fragments thereof are useful research reagents and therapeutic agents, particularly when prepared as a compound of the invention as described above. Suitably, the antibodies of the invention are detectably labelled, for example they may be labelled in such a way that they may be directly or indirectly detected. Conveniently, the antibodies are labelled with a radioactive moiety or a coloured moiety or a fluorescent moiety, or they may be linked to an enzyme. Typically, the enzyme is one which can convert a non-coloured (or non-fluorescent) substrate to a coloured (or fluorescent) product. The antibody may be labelled by biotin (or streptavidin) and then detected indirectly using streptavidin (or biotin) which has been labelled with a radioactive moiety or a coloured moiety or a fluorescent moiety, or the like or they may be linked to any enzyme of the type described above.
A nineteenth aspect of the invention provides a method of detecting endothelial damage or activation in an individual comprising obtaining a fluid sample from the individual and detecting the presence of fragments of ECSM1 or ECSM4 in the sample.
Preferably, the fluid sample is blood. Typically, the presence of peptide fragments derived from ECSM1 or ECSM4 are detected.
In a preferred embodiment of this aspect, the presence of peptide fragments of the ECSM1 or ECSM4 polypeptides are detected using an antibody selective for a polypeptide whose amino acid sequence comprises a sequence given in either one of FIG. 2 or FIG. 4 or FIG. 12 or fragments thereof. Preferably, the antibody is an antibody according to the eighteenth aspect of the invention. Typically, such an antibody would be detectably labelled.
Detecting or diagnosing endothelial cell damage in an individual is useful in diagnosing cancer or aiding diagnosis of cardiac disease, endometriosis or artheroslcerosis in that individual. It may be that certain levels of apparent cell damage are detected in individuals who do not have cancer, cardiac disease, endometriosis or artheroslcerosis. It may be necessary to compare the amount of endothelial cell damage detected with amounts or levels observed in individuals who are known to have cancer, cardiac disease, endometriosis or artheroslcerosis with the “normal” levels of apparent damage in the individual who does not have cancer, cardiac disease, endometriosis or artheroslcerosis.
Hence, detection of endothelial damage or activation in an individual may be useful as a means of detecting the presence or extent or growth rate of a tumour in that individual. The detection of vessel damage is an indirect report of the formation of tumour neovasculature. In this way, ECSM4 or ECSM1 may be surrogate markers of angiogenesis. The presence of ECSM4 or ECSM1 fragments in a sample from the individual, or more ECSM4 or ECSM1 polypeptide fragments than in an individual who does not have a tumour, may be a means of detecting a tumour, or growth of a known tumour, in that individual.
Furthermore, it will be appreciated that detection of neovasculature by means of detecting the presence of, or a certain level of, ECSM4 or ECSM1 in a sample from an individual may be useful in determining if a treatment in that individual is being effective, and/or to what extent the treatment is effective. Preferably the therapy is to treat a tumour or cancer in the individual.
Hence, an aspect of the invention provides a method of detecting a tumour or tumour neovasculature or cardiac disease or endometriosis or artherosclerosis in an individual comprising obtaining a fluid sample from the individual and detecting the presence of fragments of ECSM1 or ECSM4 in the sample.
As described above in relation to detecting or diagnosing endothelial cell damage, detection of the disease (such as a tumour or cardiac disease etc) by means of detecting the presence of, or a certain level of, ECSM4 or ECSM1 in a sample from an individual may be useful in determining the efficacy of a treatment in that individual.
In one embodiment, the therapy is gene therapy.
Preferably, the efficacy of the a treatment in an individual is determined using the amount of fragments of ECSM1 or ECSM4 found in the fluid sample of the individual and comparing it to either to the amount of ECSM1 or ECSM4 fragments in a sample from an individual who does not have cancer, cardiac disease, endometriosis or artherosclerosis and/or to the amount in a sample from the individual prior to commencement of said treatment. The comparison indicates the efficacy of treatment of the individual, wherein if there is no change in the amount of fragments determined before and during/after treatment this is indicative of poor efficacy of the treatment. A decrease in the amount of fragments found during or after treatment compared to the amount found before treatment was started indicates some efficacy of the treatment in ameliorating the condition of the individual.
Current methods of assessing the efficacy of various anti-angiogenic therapies being tested in clinical trials are invasive. The selective expression of ECSM4 on endothelial cells of angiogenic blood vessels means that detecting the presence, absence, increase or decrease in the level of ECSM1 or ECSM4 in a subject undergoing therapy is a means of determining the efficacy of the therapy in that subject without the need, or with a reduced need, for invasive biopsies, scans and the such like.
Hence, determination of the level of ECSM1 and or ECSM4 fragments in the blood of an individual undergoing an anti-angiogenic therapy (such as cancer therapy) may act as a “surrogate marker of angiogenesis”.
By “peptide fragments derived from ECSM1 or ECSM4” we mean peptides which have at least 5 consecutive amino acids of the ECSM4 or ECSM1 polypeptide. Typically, the fragments have at least 8 consecutive amino acids, preferably at least 10, more preferably at least 12 or 15 or 20 or 30 or 40 or 50 consecutive amino acids of the ECSM4 or ECSM1 polypeptide.
Methods for detecting the presence of fragments of peptides derived from larger polypeptides are known in the art.
A further aspect of the invention provides a method of modulating angiogenesis in an individual, the method comprising administering to the individual ESCM4 or a peptide fragment of ECSM4 or a ligand of ECSM4 or an antibody which selectively binds to ECSM4 or ECSM1.
Preferably, the peptide fragment or ligand or antibody is one which modulates the activity or function, either directly or indirectly, of the ECSM4 polypeptide of the individual.
Preferred antibodies are those as described in more detail above.
The production of antibodies which modulate the function of a polypeptide exposed on the cell surface is known in the art and is discussed in more detail above. Such antibodies may modulate the function by imitating the function of the natural ligand and stimulating the polypeptide into activity or function, or may modulate the polypeptide function by preventing stimulation of the polypeptide by the ligand by sterically obscuring the ligand binding site thereby preventing binding of the natural ligand.
Delivery of a ligand to magic roundabout might be an angiogenic inhibitor useful in therapy of cancer or other diseases involving hyper-angiogenesis. Also, introduction of the ECSM4 polypeptide to endothelial cells by gene therapy using the ECSM4 encoding polynucleotide might alter growth and migration.
A still further aspect of the invention provides a method of diagnosing a condition which involves aberrant or excessive growth of vascular endothelium in an individual comprising obtaining a sample containing nucleic acid from the individual and contacting said sample with a polynucleotide which selectively hybridises to a nucleic acid which encodes the ECSM4 polypeptide or the ECSM1 polypeptide or a fragment or natural variant thereof.
The method may be used for aiding diagnosis.
A condition which involves aberrant or excessive growth of vascular endothelium such as cancer, artherosclerosis, restenosis, diabetic retinopathy, arthritis, psoriasis, endometriosis, menorrhagia, haemangiomas and venous malformations may be caused by a mutation in the nucleic acid which encodes the ECSM1 or ECSM4 polypeptides.
By “selectively hybridising” is meant that the nucleic acid has sufficient nucleotide sequence similarity with the said human DNA or cDNA that it can hybridise under moderately or highly stringent conditions. As is well known in the art, the stringency of nucleic acid hybridization depends on factors such as length of nucleic acid over which hybridisation occurs, degree of identity of the hybridizing sequences and on factors such as temperature, ionic strength and CG or AT content of the sequence. Thus, any nucleic acid which is capable of selectively hybridising as said is useful in the practice of the invention.
Nucleic acids which can selectively hybridise to the said human DNA or cDNA include nucleic acids which have >95% sequence identity, preferably those with >98%, more preferably those with >99% sequence identity, over at least a portion of the nucleic acid with the said human DNA or cDNA. As is well known, human genes usually contain introns such that, for example, a mRNA or cDNA derived from a gene within the said human DNA would not match perfectly along its entire length with the said human DNA but would nevertheless be a nucleic acid capable of selectively hybridising to the said human DNA. Thus, the invention specifically includes nucleic acids which selectively hybridise to an ECSM4 or ECSM1 cDNA but may not hybridise to an ECSM4 or ECSM1 gene, or vice versa. For example, nucleic acids which span the intron-exon boundaries of the ECSM4 or ECSM1 gene may not be able to selectively hybridise to the ECSM4 or ECSM1 cDNA.
Typical moderately or highly stringent hybridisation conditions which lead to selective hybridisation are known in the art, for example those described in Molecular Cloning, a laboratory manual, 2nd edition, Sambrook et al (eds), Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y., USA, incorporated herein by reference.
An example of a typical hybridisation solution when a nucleic acid is immobilised on a nylon membrane and the probe nucleic acid is >500 bases or base pairs is:
6×SSC (saline sodium citrate) 0.5% sodium dodecyl sulphate (SDS) 100 μg/ml denatured, fragmented salmon sperm DNA
The hybridisation is performed at 68° C. The nylon membrane, with the nucleic acid immobilised, may be washed at 68° C. in 1×SSC or, for high stringency, 0.1×SSC.
20×SSC may be prepared in the following way. Dissolve 175.3 g of NaCl and 88.2 g of sodium citrate in 800 ml of H 2 O. Adjust the pH to 7.0 with a few drops of a 10 N solution of NaOH. Adjust the volume to 1 litre with H 2 O. Dispense into aliquots. Sterilize by autoclaving.
An example of a typical hybridisation solution when a nucleic acid is immobilised on a nylon membrane and the probe is an oligonucleotide of between 15 and 50 bases is:
3.0 M trimethylammonium chloride (TMACl) 0.01 M sodium phosphate (pH 6.8) 1 mm EDTA (pH 7.6) 0.5% SDS 100 μg/ml denatured, fragmented salmon sperm DNA 0.1% nonfat dried milk
The optimal temperature for hybridization is usually chosen to be 5° C. below the T i for the given chain length. T i is the irreversible melting temperature of the hybrid formed between the probe and its target sequence. Jacobs et al (1988) Nucl. Acids Res. 16, 4637 discusses the determination of T i s. The recommended hybridization temperature for 17-mers in 3 M TMACl is 48-50° C.; for 19-mers, it is 55-57° C.; and for 20-mers, it is 58-66° C.
By “nucleic acid which selectively hybridises” is also included nucleic acids which will amplify DNA from the said region of human DNA by any of the well known amplification systems such as those described in more detail below, in particular the polymerase chain reaction (PCR). Suitable conditions for PCR amplification include amplification in a suitable 1× amplification buffer:
10× amplification buffer is 500 mM KCl; 100 mM Tris.Cl (pH 8.3 at room temperature); 15 mM MgCl 2 ; 0.1% gelatin.
A suitable denaturing agent or procedure (such as heating to 95° C.) is used in order to separate the strands of double-stranded DNA.
Suitably, the annealing part of the amplification is between 37° C. and 60° C., preferably 50° C.
Although the nucleic acid which is useful in the methods of the invention may be RNA or DNA, DNA is preferred. Although the nucleic acid which is useful in the methods of the invention may be double-stranded or single-stranded, single-stranded nucleic acid is preferred under some circumstances such as in nucleic acid amplification reactions.
The sample may be directly derived from the patient, for example, by biopsy of a tissue which may be associated with aberrant vascular development, or it may be derived from the patient from a site remote from the tissue, for example because cells from the tissue have migrated from the tissue to other parts of the body. Alternatively, the sample may be indirectly derived from the patient in the sense that, for example, the tissue or cells therefrom may be cultivated in vitro, or cultivated in a xenograft model; or the nucleic acid sample may be one which has been replicated (whether in vitro or in vivo) from nucleic acid from the original source from the patient. Thus, although the nucleic acid derived from the patient may have been physically within the patient, it may alternatively have been copied from nucleic acid which was physically within the patient. When aberrant vascular development is believed to be associated with a tumour, tumour tissue may be taken from the primary tumour or from metastases.
It will be appreciated that a useful method of the invention includes the analysis of mutations in, or the detection of the presence or absence of, the ECSM4 or ECSM1 gene in any suitable sample. The sample may suitably be a freshly-obtained sample from the patient, or the sample may be an historic sample, for example a sample held in a library of samples.
Conveniently, the nucleic acid capable of selectively hybridising to the said human DNA and which is used in the methods of the invention further comprises a detectable label.
By “detectable label” is included any convenient radioactive label such as 32 P, 33 P or 35 S which can readily be incorporated into a nucleic acid molecule using well known methods; any convenient fluorescent or chemiluminescent label which can readily be incorporated into a nucleic acid is also included. In addition the term “detectable label” also includes a moiety which can be detected by virtue of binding to another moiety (such as biotin which can be detected by binding to streptavidin); and a moiety, such as an enzyme, which can be detected by virtue of its ability to convert a colourless compound into a coloured compound, or vice versa (for example, alkaline phosphatase can convert colourless O-nitrophenylphosphate into coloured o-nitrophenol). Conveniently, the nucleic acid probe may occupy a certain position in a fixed assay and whether the nucleic acid hybridises to the said region of human DNA can be determined by reference to the position of hybridisation in the fixed assay. The detectable label may also be a fluorophore-quencher pair as described in Tyagi & Kramer (1996) Nature Biotechnology 14, 303-308.
Conveniently, in this method of diagnosis of a condition in which vascular development is aberrant the nucleic acid which is capable of the said selective hybridisation (whether labelled with a detectable label or not) is contacted with a nucleic acid derived from the patient under hybridising conditions. Suitable hybridising conditions include those described above.
This method of diagnosing a condition in which vascular development is aberrant may involve sequencing of DNA at one or more of the relevant positions within the relevant region, including direct sequencing; direct sequencing of PCR-amplified exons; differential hybridisation of an oligonucleotide probe designed to hybridise at the relevant positions within the relevant region (conveniently this uses immobilised oligonucleotide probes in, so-called, “chip” systems which are well known in the art); denaturing gel electrophoresis following digestion with an appropriate restriction enzyme, preferably following amplification of the relevant DNA regions; S1 nuclease sequence analysis; non-denaturing gel electrophoresis, preferably following amplification of the relevant DNA regions; conventional RFLP (restriction fragment length polymorphism) assays; heteroduplex analysis; selective DNA amplification using oligonucleotides; fluorescent in-situ hybridisation (FISH) of interphase chromosomes; ARMS-PCR (Amplification Refractory Mutation System-PCR) for specific mutations; cleavage at mismatch sites in hybridised nucleic acids (the cleavage being chemical or enzymic); SSCP single strand conformational polymorphism or DGGE (discontinuous or denaturing gradient gel electrophoresis); analysis to detect mismatch in annealed normal/mutant PCR-amplified DNA; and protein truncation assay (translation and transcription of exons—if a mutation introduces a stop codon a truncated protein product will result). Other methods may be employed such as detecting changes in the secondary structure of single-stranded DNA resulting from changes in the primary sequence, for example, using the cleavase I enzyme. This system is commercially available from GibcoBRL, Life Technologies, 3 Fountain Drive, Inchinnan Business Park, Paisley PA4 9RF, Scotland.
It will be appreciated that the methods of the invention may also be carried out on “DNA chips”. Such “chips” are described in U.S. Pat. No. 5,445,934 (Affymetrix; probe arrays), WO 96/31622 (Oxford; probe array plus ligase or polymerase extension), and WO 95/22058 (Affymax; fluorescently marked targets bind to oligomer substrate, and location in array detected); all of these are incorporated herein by reference.
Detailed methods of mutation detection are described in “Laboratory Protocols for Mutation Detection” 1996, ed. Landegren, Oxford University Press on behalf of HUGO (Human Genome Organisation).
It is preferred if RFLP is used for the detection of fairly large (>500 bp) deletions or insertions. Southern blots may be used for this method of the invention.
PCR amplification of smaller regions (maximum 300 bp) to detect small changes greater than 3-4 bp insertions or deletions may be preferred. Amplified sequence may be analysed on a sequencing gel, and small changes (minimum size 3-4 bp) can be visualised. Suitable primers are designed as herein described.
In addition, using either Southern blot analysis or PCR restriction enzyme variant sites may be detected. For example, for analysing variant sites in genomic DNA restriction enzyme digestion, gel electrophoresis, Southern blotting, and hybridisation specific probe (for example any suitable fragment derived from the ECSM4 or ECSM1 cDNA or gene).
For example, for analysing variant sites using PCR DNA amplification, restriction enzyme digestion, gel detection by ethidium bromide, silver staining or incorporation of radionucleotide or fluorescent primer in the PCR.
Other suitable methods include the development of allele specific oligonucleotides (ASOs) for specific mutational events. Similar methods are used on RNA and cDNA for the suitable tissue.
Whilst it is useful to detect mutations in any part of the ECSM4 or ECSM1 gene, it is preferred if the mutations are detected in the exons of the gene and it is further preferred if the mutations are ones which change the coding sense. The detection of these mutations is a preferred aspect of the invention.
The methods of the invention also include checking for loss-of-heterozygosity (LOH; shows one copy lost). LOH may be a sufficient marker for diagnosis; looking for mutation/loss of the second allele may not be necessary. LOH of the gene may be detected using polymorphisms in the coding sequence, and introns, of the gene.
Particularly preferred nucleic acids for use in the aforementioned methods of the invention are those selected from the group consisting of primers suitable for amplifying nucleic acid.
Suitably, the primers are selected from the group consisting of primers which hybridise to the nucleotide sequences shown in any of the Figures which show ECSM4 or ECSM1 gene or cDNA sequences. It is particularly preferred if the primers hybridise to the introns of the ECSM4 or ECSM1 gene or if the primers are ones which will prime synthesis of DNA from the ECSM4 or ECSM1 gene or cDNA but not from other genes or cDNAs.
Primers which are suitable for use in a polymerase chain reaction (PCR; Saiki et al (1988) Science 239, 487-491) are preferred. Suitable PCR primers and methods of detecting products of PCR reactions are described in detail above.
Any of the nucleic acid amplification protocols can be used in the method of the invention including the polymerase chain reaction, QB replicase and ligase chain reaction. Also, NASBA (nucleic acid sequence based amplification), also called 3SR, can be used as described in Compton (1991) Nature 350, 91-92 and AIDS (1993), Vol 7 (Suppl 2), S108 or SDA (strand displacement amplification) can be used as described in Walker et al (1992) Nucl. Acids Res. 20, 1691-1696. The polymerase chain reaction is particularly preferred because of its simplicity.
The present invention provides the use of a nucleic acid which selectively hybridises to the human-derived DNA of genomic clones as described in Table 8 of Example 1 or to the ECSM4 or ECSM1 gene, or a mutant allele thereof, or a nucleic acid which selectively hybridises to ECSM4 or ECSM1 cDNA or a mutant allele thereof, or their complement in a method of diagnosing a condition in which vascular development is aberrant; or in the manufacture of a reagent for carrying out these methods.
Preferred polynucleotides which selectively hybridise to the ECSM4 gene or cDNA are as described above in relation to a method of diagnosis.
Also, the present invention provides a method of determining the presence or absence, or mutation in, the said ECSM4 or ECSM1 gene. Preferably, the method uses a suitable sample from a patient.
The methods of the invention include the detection of mutations in the ECSM4 or ECSM1 gene.
The methods of the invention may make use of a difference in restriction enzyme cleavage sites caused by mutation. A non-denaturing gel may be used to detect differing lengths of fragments resulting from digestion with an appropriate restriction enzyme.
An “appropriate restriction enzyme” is one which will recognise and cut the wild-type sequence and not the mutated sequence or vice versa. The sequence which is recognised and cut by the restriction enzyme (or not, as the case may be) can be present as a consequence of the mutation or it can be introduced into the normal or mutant allele using mismatched oligonucleotides in the PCR reaction. It is convenient if the enzyme cuts DNA only infrequently, in other words if it recognises a sequence which occurs only rarely.
In another method, a pair of PCR primers are used which match (ie hybridise to) either the wild-type genotype or the mutant genotype but not both. Whether amplified DNA is produced will then indicate the wild-type or mutant genotype (and hence phenotype). However, this method relies partly on a negative result (ie the absence of amplified DNA) which could be due to a technical failure. It therefore may be less reliable and/or requires additional control experiments.
A preferable method employs similar PCR primers but, as well as hybridising to only one of the wild-type or mutant sequences, they introduce a restriction site which is not otherwise there in either the wild-type or mutant sequences.
The nucleic acids which selectively hybridise to the ECSM4 or ECSM1 gene or cDNA, or which selectively hybridise to the genomic clones containing ECSM4 or ECSM1 as listed in Table 8 of Example 1 are useful for a number of purposes. They can be used in Southern hybridization to genomic DNA and in the RNase protection method for detecting point mutations already discussed above. The probes can be used to detect PCR amplification products. They may also be used to detect mismatches with the ECSM4 or ECSM1 gene or mRNA in a sample using other techniques. Mismatches can be detected using either enzymes (eg S1 nuclease or resolvase), chemicals (eg hydroxylamine or osmium tetroxide and piperidine), or changes in electrophoretic mobility of mismatched hybrids as compared to totally matched hybrids. These techniques are known in the art. Generally, the probes are complementary to the ECSM4 or ECSM1 gene coding sequences, although probes to certain introns are also contemplated. A battery of nucleic acid probes may be used to compose a kit for detecting loss of or mutation in the wild-type ECSM4 or ECSM1 gene. The kit allows for hybridization to the entire ECSM4 or ECSM1 gene. The probes may overlap with each other or be contiguous.
If a riboprobe is used to detect mismatches with mRNA, it is complementary to the mRNA of the human ECSM4 or ECSM1 gene. The riboprobe thus is an anti-sense probe in that it does not code for the protein encoded by the ECSM4 or ECSM1 gene because it is of the opposite polarity to the sense strand. The riboprobe generally will be labelled, for example, radioactively labelled which can be accomplished by any means known in the art. If the riboprobe is used to detect mismatches with DNA it can be of either polarity, sense or anti-sense. Similarly, DNA probes also may be used to detect mismatches.
Nucleic acid probes may also be complementary to mutant alleles of the ECSM4 or ECSM1 gene. These are useful to detect similar mutations in other patients on the basis of hybridization rather than mismatches. As mentioned above, the ECSM4 or ECSM1 gene probes can also be used in Southern hybridizations to genomic DNA to detect gross chromosomal changes such as deletions and insertions.
Particularly useful methods of detecting a mutation in the ECSM1 or ECSM4 genes include single strand conformation polymorphism (SSCP), hetero duplex analysis, polymerase chain reaction, using DNA chips and sequencing.
Any sample containing nucleic acid derived from the individual is useful in the methods of the invention. It is preferred if the nucleic acid in the sample is DNA. Thus, samples from cells may be obtained as is well known in the art, for example from blood samples or cheek cells or the like. Where the methods are being used to determine the presence or absence of a mutation in an unborn child, it is preferred if the sample is a maternal sample containing nucleic acid from the unborn child. Suitable maternal samples include the amniotic fluid of the mother, chorionic villus samples and blood samples from which foetal cells can be isolated.
A further aspect of the invention provides a method of reducing the expression of the ECSM4 or ECSM1 polynucleotide in an individual, comprising administering to the individual an agent which selectively prevents expression of ECSM4 or ECSM1.
In a preferred embodiment, the agent which selectively prevents expression of ECSM4 or ECSM1 is an antisense nucleic acid.
Preferably, the antisense nucleic acid is not one (or is not antisense to one) whose sequence consists of the sequence represented by SEQ ID No 18084 or 5096 of EP 1 074 617, SEQ ID No 210 of WO 00/53756 or WO 99/46281, or SEQ ID Nos 22, 23, 96 or 98 of WO 01/23523 or SEQ ID No 31 of WO 99/11293 or their complement, or a nucleic acid sequence which encodes a polypeptide whose amino acid sequence is represented by any one of SEQ ID No 18085 of EP 1 074 617, SEQ ID No 211 of either WO 00/53756 or WO99/46281, SEQ ID Nos 24-27, 29, 30, 33, 34, 38 or 39 of WO 01/23523, or SEQ ID No 86 of WO 99/11293.
A further aspect thereof includes administering an antisense nucleic acid to a cell in order to prevent expression of ECSM4 or ECSM1. Typically, the cell is in the body of an individual in need of prevention of expression of ESCM4 or ECSM1.
The ECSM4 or ECSM1 polynucleotide which is bound by an antisense molecule may be DNA or RNA.
Preferred antisense molecules are as described above.
Diseases which may be treated by reducing ECSM4 or ECSM1 expression include diseases involving aberrant or excessive vascularisation as described above.
Antisense nucleic acids are well known in the art and are typically single-stranded nucleic acids, which can specifically bind to a complementary nucleic acid sequence. By binding to the appropriate target sequence, an RNA-RNA, a DNA-DNA, or RNA-DNA duplex is formed. These nucleic acids are often termed “antisense” because they are complementary to the sense or coding strand of the gene. Recently, formation of a triple helix has proven possible where the oligonucleotide is bound to a DNA duplex. It was found that oligonucleotides could recognise sequences in the major groove of the DNA double helix. A triple helix was formed thereby. This suggests that it is possible to synthesise a sequence-specific molecules which specifically bind double-stranded DNA via recognition of major groove hydrogen binding sites.
By binding to the target nucleic acid, the above oligonucleotides can inhibit the function of the target nucleic acid. This could, for example, be a result of blocking the transcription, processing, poly(A) addition, replication, translation, or promoting inhibitory mechanisms of the cells, such as promoting RNA degradations.
Antisense oligonucleotides are prepared in the laboratory and then introduced into cells, for example by microinjection or uptake from the cell culture medium into the cells, or they are expressed in cells after transfection with plasmids or retroviruses or other vectors carrying an antisense gene. Antisense oligonucleotides were first discovered to inhibit viral replication or expression in cell culture for Rous sarcoma virus, vesicular stomatitis virus, herpes simplex virus type 1, simian virus and influenza virus. Since then, inhibition of mRNA translation by antisense oligonucleotides has been studied extensively in cell-free systems including rabbit reticulocyte lysates and wheat germ extracts. Inhibition of viral function by antisense oligonucleotides has been demonstrated in vitro using oligonucleotides which were complementary to the AIDS HIV retrovirus RNA (Goodchild, J. 1988 “Inhibition of Human Immunodeficiency Virus Replication by Antisense Oligodeoxynucleotides”, Proc. Natl. Acad. Sci . ( USA ) 85(15), 5507-11). The Goodchild study showed that oligonucleotides that were most effective were complementary to the poly(A) signal; also effective were those targeted at the 5N end of the RNA, particularly the cap and 5N untranslated region, next to the primer binding site and at the primer binding site. The cap, 5N untranslated region, and poly(A) signal lie within the sequence repeated at the ends of retrovirus RNA (R region) and the oligonucleotides complementary to these may bind twice to the RNA.
Typically, antisense oligonucleotides are 15 to 35 bases in length. For example, 20-mer oligonucleotides have been shown to inhibit the expression of the epidermal growth factor receptor mRNA (Witters et al, Breast Cancer Res Treat 53:41-50 (1999)) and 25-mer oligonucleotides have been shown to decrease the expression of adrenocorticotropic hormone by greater than 90% (Frankel et al, J Neurosurg 91:261-7 (1999)). However, it is appreciated that it may be desirable to use oligonucleotides with lengths outside this range, for example 10, 11, 12, 13, or 14 bases, or 36, 37, 38, 39 or 40 bases.
Oligonucleotides are subject to being degraded or inactivated by cellular endogenous nucleases. To counter this problem, it is possible to use modified oligonucleotides, eg having altered internucleotide linkages, in which the naturally occurring phosphodiester linkages have been replaced with another linkage. For example, Agrawal et al (1988) Proc. Natl. Acad. Sci. USA 85, 7079-7083 showed increased inhibition in tissue culture of HIV-1 using oligonucleotide phosphoramidates and phosphorothioates. Sarin et al (1988) Proc. Natl. Acad. Sci. USA 85, 7448-7451 demonstrated increased inhibition of HIV-1 using oligonucleotide methylphosphonates. Agrawal et al (1989) Proc. Natl. Acad. Sci. USA 86, 7790-7794 showed inhibition of HIV-1 replication in both early-infected and chronically infected cell cultures, using nucleotide sequence-specific oligonucleotide phosphorothioates. Leither et al (1990) Proc. Natl. Acad. Sci. USA 87, 3430-3434 report inhibition in tissue culture of influenza virus replication by oligonucleotide phosphorothioates.
Oligonucleotides having artificial linkages have been shown to be resistant to degradation in vivo. For example, Shaw et al (1991) in Nucleic Acids Res. 19, 747-750, report that otherwise unmodified oligonucleotides become more resistant to nucleases in vivo when they are blocked at the 3′ end by certain capping structures and that uncapped oligonucleotide phosphorothioates are not degraded in vivo.
A detailed description of the H-phosphonate approach to synthesizing oligonucleoside phosphorothioates is provided in Agrawal and Tang (1990) Tetrahedron Letters 31, 7541-7544, the teachings of which are hereby incorporated herein by reference. Syntheses of oligonucleoside methylphosphonates, phosphorodithioates, phosphoramidates, phosphate esters, bridged phosphoramidates and bridge phosphorothioates are known in the art. See, for example, Agrawal and Goodchild (1987) Tetrahedron Letters 28, 3539; Nielsen et al (1988) Tetrahedron Letters 29, 2911; Jager et al (1988) Biochemistry 27, 7237; Uznanski et al (1987) Tetrahedron Letters 28, 3401; Bannwarth (1988) Helv. Chim. Acta. 71, 1517; Crosstick and Vyle (1989) Tetrahedron Letters 30, 4693; Agrawal et al (1990) Proc. Natl. Acad. Sci. USA 87, 1401-1405, the teachings of which are incorporated herein by reference. Other methods for synthesis or production also are possible. In a preferred embodiment the oligonucleotide is a deoxyribonucleic acid (DNA), although ribonucleic acid (RNA) sequences may also be synthesized and applied.
The oligonucleotides useful in the invention preferably are designed to resist degradation by endogenous nucleolytic enzymes. In vivo degradation of oligonucleotides produces oligonucleotide breakdown products of reduced length. Such breakdown products are more likely to engage in non-specific hybridization and are less likely to be effective, relative to their full-length counterparts. Thus, it is desirable to use oligonucleotides that are resistant to degradation in the body and which are able to reach the targeted cells. The present oligonucleotides can be rendered more resistant to degradation in vivo by substituting one or more internal artificial internucleotide linkages for the native phosphodiester linkages, for example, by replacing phosphate with sulphur in the linkage. Examples of linkages that may be used include phosphorothioates, methylphosphonates, sulphone, sulphate, ketyl, phosphorodithioates, various phosphoramidates, phosphate esters, bridged phosphorothioates and bridged phosphoramidates. Such examples are illustrative, rather than limiting, since other internucleotide linkages are known in the art. See, for example, Cohen, (1990) Trends in Biotechnology . The synthesis of oligonucleotides having one or more of these linkages substituted for the phosphodiester internucleotide linkages is well known in the art, including synthetic pathways for producing oligonucleotides having mixed internucleotide linkages.
Oligonucleotides can be made resistant to extension by endogenous enzymes by “capping” or incorporating similar groups on the 5′ or 3′ terminal nucleotides. A reagent for capping is commercially available as Amino-Link II™ from Applied BioSystems Inc, Foster City, Calif. Methods for capping are described, for example, by Shaw et al (1991) Nucleic Acids Res. 19, 747-750 and Agrawal et al (1991) Proc. Natl. Acad. Sci. USA 88(17), 7595-7599, the teachings of which are hereby incorporated herein by reference.
A further method of making oligonucleotides resistant to nuclease attack is for them to be “self-stabilized” as described by Tang et al (1993) Nucl. Acids Res. 21, 2729-2735 incorporated herein by reference. Self-stabilized oligonucleotides have hairpin loop structures at their 3′ ends, and show increased resistance to degradation by snake venom phosphodiesterase, DNA polymerase I and fetal bovine serum. The self-stabilized region of the oligonucleotide does not interfere in hybridization with complementary nucleic acids, and pharmacokinetic and stability studies in mice have shown increased in vivo persistence of self-stabilized oligonucleotides with respect to their linear counterparts.
In accordance with the invention, the antisense compound may be administered systemically. Alternatively the inherent binding specificity of antisense oligonucleotides characteristic of base pairing is enhanced by limiting the availability of the antisense compound to its intended locus in vivo, permitting lower dosages to be used and minimising systemic effects. Thus, oligonucleotides may be applied locally to achieve the desired effect. The concentration of the oligonucleotides at the desired locus is much higher than if the oligonucleotides were administered systemically, and the therapeutic effect can be achieved using a significantly lower total amount. The local high concentration of oligonucleotides enhances penetration of the targeted cells and effectively blocks translation of the target nucleic acid sequences.
The oligonucleotides can be delivered to the locus by any means appropriate for localised administration of a drug. For example, a solution of the oligonucleotides can be injected directly to the site or can be delivered by infusion using an infusion pump. The oligonucleotides also can be incorporated into an implantable device which when placed at the desired site, permits the oligonucleotides to be released into the surrounding locus.
The oligonucleotides may be administered via a hydrogel material. The hydrogel is non-inflammatory and biodegradable. Many such materials now are known, including those made from natural and synthetic polymers. In a preferred embodiment, the method exploits a hydrogel which is liquid below body temperature but gels to form a shape-retaining semisolid hydrogel at or near body temperature. Preferred hydrogel are polymers of ethylene oxide-propylene oxide repeating units. The properties of the polymer are dependent on the molecular weight of the polymer and the relative percentage of polyethylene oxide and polypropylene oxide in the polymer. Preferred hydrogels contain from about 10% to about 80% by weight ethylene oxide and from about 20% to about 90% by weight propylene oxide. A particularly preferred hydrogel contains about 70% polyethylene oxide and 30% polypropylene oxide. Hydrogels which can be used are available, for example, from BASF Corp., Parsippany, N.J., under the tradename Pluronic®.
In this embodiment, the hydrogel is cooled to a liquid state and the oligonucleotides are admixed into the liquid to a concentration of about 1 mg oligonucleotide per gram of hydrogel. The resulting mixture then is applied onto the surface to be treated, for example by spraying or painting during surgery or using a catheter or endoscopic procedures. As the polymer warms, it solidifies to form a gel, and the oligonucleotides diffuse out of the gel into the surrounding cells over a period of time defined by the exact composition of the gel.
It will be appreciated that the oligonucleotides or other agents may be administered after surgical removal of a tumour, and may be administered to the area from which the tumour has been removed, and surrounding tissue, for example using cytoscopy to guide application of the oligonucleotides or other agents.
The oligonucleotides can be administered by means of other implants that are commercially available or described in the scientific literature, including liposomes, microcapsules and implantable devices. For example, implants made of biodegradable materials such as polyanhydrides, polyorthoesters, polylactic acid and polyglycolic acid and copolymers thereof, collagen, and protein polymers, or non-biodegradable materials such as ethylenevinyl acetate (EVAc), polyvinyl acetate, ethylene vinyl alcohol, and derivatives thereof can be used to locally deliver the oligonucleotides. The oligonucleotides can be incorporated into the material as it is polymerised or solidified, using melt or solvent evaporation techniques, or mechanically mixed with the material. In one embodiment, the oligonucleotides are mixed into or applied onto coatings for implantable devices such as dextran coated silica beads, stents, or catheters.
The dose of oligonucleotides is dependent on the size of the oligonucleotides and the purpose for which is it administered. In general, the range is calculated based on the surface area of tissue to be treated. The effective dose of oligonucleotide is somewhat dependent on the length and chemical composition of the oligonucleotide but is generally in the range of about 30 to 3000 μg per square centimetre of tissue surface area.
The oligonucleotides may be administered to the patient systemically for both therapeutic and prophylactic purposes. The oligonucleotides may be administered by any effective method, for example, parenterally (eg intravenously, subcutaneously, intramuscularly) or by oral, nasal or other means which permit the oligonucleotides to access and circulate in the patient's bloodstream. Oligonucleotides administered systemically preferably are given in addition to locally administered oligonucleotides, but also have utility in the absence of local administration. A dosage in the range of from about 0.1 to about 10 grams per administration to an adult human generally will be effective for this purpose.
It will be appreciated that antisense agents also include larger molecules which bind to said ECSM4 or ECSM1 mRNA or genes and substantially prevent expression of said ECSM4 or ECSM1 mRNA or genes and substantially prevent expression of said ECSM4 or ECSM1 protein. Thus, expression of an antisense molecule which is substantially complementary to said ECSM4 or ECSM1 mRNA is envisaged as part of the invention.
The said larger molecules may be expressed from any suitable genetic construct as is described below and delivered to the patient. Typically, the genetic construct which expresses the antisense molecule comprises at least a portion of the said ECSM4 or ECSM1 cDNA or gene operatively linked to a promoter which can express the antisense molecule in a cell. Promoters that may be active in endothelial cells are described below.
Although the genetic construct can be DNA or RNA it is preferred if it is DNA.
Preferably, the genetic construct is adapted for delivery to a human cell.
Means and methods of introducing a genetic construct into a cell in an animal body are known in the art. For example, the constructs of the invention may be introduced into proliferating endothelial cells by any convenient method, for example methods involving retroviruses, so that the construct is inserted into the genome of the endothelial cell. For example, in Kuriyama et al (1991) Cell Struc. and Func. 16, 503-510 purified retroviruses are administered. Retroviruses provide a potential means of selectively infecting proliferating endothelial cells because they can only integrate into the genome of dividing cells; most endothelial cells are in a quiescent, non-receptive stage of cell growth or, at least, are dividing much less rapidly than angiogenic cells. Retroviral DNA constructs which encode said antisense agents may be made using methods well known in the art. To produce active retrovirus from such a construct it is usual to use an ecotropic psi2 packaging cell line grown in Dulbecco's modified Eagle's medium (DMEM) containing 10% foetal calf serum (FCS). Transfection of the cell line is conveniently by calcium phosphate co-precipitation, and stable transformants are selected by addition of G418 to a final concentration of 1 mg/ml (assuming the retroviral construct contains a neo R gene). Independent colonies are isolated and expanded and the culture supernatant removed, filtered through a 0.45 μm pore-size filter and stored at −70°. For the introduction of the retrovirus into the tumour cells, it is convenient to inject directly retroviral supernatant to which 10 μg/ml Polybrene has been added. For tumours exceeding 10 mm in diameter it is appropriate to inject between 0.1 ml and 1 ml of retroviral supernatant; preferably 0.5 ml.
Alternatively, as described in Culver et al (1992) Science 256, 1550-1552, cells which produce retroviruses are injected into specific tissue. The retrovirus-producing cells so introduced are engineered to actively produce retroviral vector particles so that continuous productions of the vector occurred within the tumour mass in situ. Thus, proliferating endothelial cells can be successfully transduced in vivo if mixed with retroviral vector-producing cells.
Targeted retroviruses are also available for use in the invention; for example, sequences conferring specific binding affinities may be engineered into pre-existing viral env genes (see Miller & Vile (1995) Faseb J 9, 190-199 for a review of this and other targeted vectors for gene therapy).
Other methods involve simple delivery of the construct into the cell for expression therein either for a limited time or, following integration into the genome, for a longer time. An example of the latter approach includes (preferably endothelial-cell-targeted) liposomes (N≅ssander et al (1992) Cancer Res. 52, 646-653).
Immunoliposomes (antibody-directed liposomes) are especially useful in targeting to endothelial cell types which express a cell surface protein for which antibodies are available.
Other methods of delivery include adenoviruses carrying external DNA via an antibody-polylysine bridge (see Curiel Prog. Med. Virol. 40, 1-18) and transferrin-polycation conjugates as carriers (Wagner et al (1990) Proc. Natl. Acad. Sci. USA 87, 3410-3414). In the first of these methods a polycation-antibody complex is formed with the DNA construct or other genetic construct of the invention, wherein the antibody is specific for either wild-type adenovirus or a variant adenovirus in which a new epitope has been introduced which binds the antibody. The polycation moiety binds the DNA via electrostatic interactions with the phosphate backbone. The adenovirus, because it contains unaltered fibre and penton proteins, is internalised into the cell and carries into the cell with it the DNA construct of the invention. It is preferred if the polycation is polylysine.
The DNA may also be delivered by adenovirus wherein it is present within the adenovirus particle, for example, as described below.
In the second of these methods, a high-efficiency nucleic acid delivery system that uses receptor-mediated endocytosis to carry DNA macromolecules into cells is employed. This is accomplished by conjugating the iron-transport protein transferrin to polycations that bind nucleic acids. Human transferrin, or the chicken homologue conalbumin, or combinations thereof is covalently linked to the small DNA-binding protein protamine or to polylysines of various sizes through a disulfide linkage. These modified transferrin molecules maintain their ability to bind their cognate receptor and to mediate efficient iron transport into the cell. The transferrin-polycation molecules form electrophoretically stable complexes with DNA constructs or other genetic constructs of the invention independent of nucleic acid size (from short oligonucleotides to DNA of 21 kilobase pairs). When complexes of transferrin-polycation and the DNA constructs or other genetic constructs of the invention are supplied to the endothelial cells, a high level of expression from the construct in the cells is expected.
High-efficiency receptor-mediated delivery of the DNA constructs or other genetic constructs of the invention using the endosome-disruption activity of defective or chemically inactivated adenovirus particles produced by the methods of Cotten et al (1992) Proc. Natl. Acad. Sci. USA 89, 6094-6098 may also be used. This approach appears to rely on the fact that adenoviruses are adapted to allow release of their DNA from an endosome without passage through the lysosome, and in the presence of, for example transferrin linked to the DNA construct or other genetic construct of the invention, the construct is taken up by the cell by the same route as the adenovirus particle.
This approach has the advantages that there is no need to use complex retroviral constructs; there is no permanent modification of the genome as occurs with retroviral infection; and the targeted expression system is coupled with a targeted delivery system, thus reducing toxicity to other cell types.
It may be desirable to locally perfuse a tumour with the suitable delivery vehicle comprising the genetic construct for a period of time; additionally or alternatively the delivery vehicle or genetic construct can be injected directly into accessible tumours.
It will be appreciated that “naked DNA” and DNA complexed with cationic and neutral lipids may also be useful in introducing the DNA of the invention into cells of the patient to be treated. Non-viral approaches to gene therapy are described in Ledley (1995) Human Gene Therapy 6, 1129-1144.
Alternative targeted delivery systems are also known such as the modified adenovirus system described in WO 94/10323 wherein, typically, the DNA is carried within the adenovirus, or adenovirus-like, particle. Michael et al (1995) Gene Therapy 2, 660-668 describes modification of adenovirus to add a cell-selective moiety into a fibre protein. Mutant adenoviruses which replicate selectively in p53-deficient human tumour cells, such as those described in Bischoff et al (1996) Science 274, 373-376 are also useful for delivering the genetic construct of the invention to a cell. Thus, it will be appreciated that a further aspect of the invention provides a virus or virus-like particle comprising a genetic construct of the invention. Other suitable viruses or virus-like particles include HSV, AAV, vaccinia and parvovirus.
In a further embodiment the agent which selectively prevents the function of ECSM4 or ECSM1 is a ribozyme capable of cleaving targeted ECSM4 or ECSM1 RNA or DNA. A gene expressing said ribozyme may be administered in substantially the same and using substantially the same vehicles as for the antisense molecules.
Ribozymes which may be encoded in the genomes of the viruses or virus-like particles herein disclosed are described in Cech and Herschlag “Site-specific cleavage of single stranded DNA” U.S. Pat. No. 5,180,818; Altman et al “Cleavage of targeted RNA by RNAse P” U.S. Pat. No. 5,168,053, Cantin et al “Ribozyme cleavage of HIV-1 RNA” U.S. Pat. No. 5,149,796; Cech et al “RNA ribozyme restriction endoribonucleases and methods”, U.S. Pat. No. 5,116,742; Been et al “RNA ribozyme polymerases, dephosphorylases, restriction endonucleases and methods”, U.S. Pat. No. 5,093,246; and Been et al “RNA ribozyme polymerases, dephosphorylases, restriction endoribonucleases and methods; cleaves single-stranded RNA at specific site by transesterification”, U.S. Pat. No. 4,987,071, all incorporated herein by reference.
It will be appreciated that it may be desirable that the antisense molecule or ribozyme is expressed from a cell-specific promoter element.
The genetic constructs of the invention can be prepared using methods well known in the art.
A further aspect of the invention is a method of screening for a molecule that binds to ECSM4 or a suitable variant, fragment or fusion thereof, or a fusion of a said fragment or fusion thereof, the method comprising 1) contacting a) the ECSM4 polypeptide with b) a test molecule 2) detecting the presence of a complex containing the ECSM4 polypeptide and a test molecule, and optionally 3) identifying any test molecule bound to the ECSM4 polypeptide.
Preferably the ECSM4 polypeptide is one as described above in respect of the eleventh aspect of the invention.
In a preferred embodiment, the test molecule is a polypeptide.
In a further preferred embodiment, the method is used to identify natural ligands of ECSM4. Thus, in this embodiment the test molecule includes the natural ligand of ECSM4. A particularly useful technique for the identification of natural ligands of polypeptide molecules is the yeast two-hybrid technique. This technique is well known in the art and relies on binding between a molecule and its cognate ligand to bring together two parts of a transcription complex (which are fused one to the molecule in question and other to the test ligand) which, when together, promote transcription of a reporter gene.
Hence, a preferred embodiment of this aspect of the invention comprises use of the screening method, preferably the yeast two-hybrid system, to identify natural ligands of the ECSM4 polypeptide.
A molecule which is identifiable as binding the ECSM4 polypeptide is a further aspect of the invention.
It will be appreciated that a molecule which binds to ESCM4 may modulate the activation of ECSM4.
Suitable peptide ligands that will bind to ECSM4 may be identified using methods known in the art.
One method, disclosed by Scott and Smith (1990) Science 249, 386-390 and Cwirla et al (1990) Proc. Natl. Acad. Sci. USA 87, 6378-6382, involves the screening of a vast library of filamentous bacteriophages, such as M13 or fd, each member of the library having a different peptide fused to a protein on the surface of the bacteriophage. Those members of the library that bind to ECSM4 are selected using an iterative binding protocol, and once the phages that bind most tightly have been purified, the sequence of the peptide ligands may be determined simply by sequencing the DNA encoding the surface protein fusion. Another method that can be used is the NovaTope™ system commercially available from Novagen, Inc., 597 Science Drive, Madison, Wis. 53711. The method is based on the creation of a library of bacterial clones, each of which stably expresses a small peptide derived from a candidate protein in which the ligand is believed to reside. The library is screened by standard lift methods using the antibody or other binding agent as a probe. Positive clones can be analysed directly by DNA sequencing to determine the precise amino acid sequence of the ligand.
Further methods using libraries of beads conjugated to individual species of peptides as disclosed by Lam et al (1991) Nature 354, 82-84 or synthetic peptide combinatorial libraries as disclosed by Houghten et al (1991) Nature 354, 84-86 or matrices of individual synthetic peptide sequences on a solid support as disclosed by Pirrung et al in U.S. Pat. No. 5,143,854 may also be used to identify peptide ligands.
It will be appreciated that screening assays which are capable of high throughput operation will be particularly preferred. Examples may include cell based assays and protein-protein binding assays. An SPA-based (Scintillation Proximity Assay; Amersham International) system may be used. For example, an assay for identifying a compound capable of modulating the activity of a protein kinase may be performed as follows. Beads comprising scintillant and a polypeptide that may be phosphorylated may be prepared. The beads may be mixed with a sample comprising the protein kinase and 32 P-ATP or 33 P-ATP and with the test compound. Conveniently this is done in a 96-well format. The plate is then counted using a suitable scintillation counter, using known parameters for 32 P or 33 P SPA assays. Only 32 P or 33 P that is in proximity to the scintillant, i.e. only that bound to the polypeptide, is detected. Variants of such an assay, for example in which the polypeptide is immobilised on the scintillant beads via binding to an antibody, may also be used.
Other methods of detecting polypeptide/polypeptide interactions include ultrafiltration with ion spray mass spectroscopy/HPLC methods or other physical and analytical methods. Fluorescence Energy Resonance Transfer (FRET) methods, for example, well known to those skilled in the art, may be used, in which binding of two fluorescent labelled entities may be measured by measuring the interaction of the fluorescent labels when in close proximity to each other.
Alternative methods of detecting binding of a polypeptide to macromolecules, for example DNA, RNA, proteins and phospholipids, include a surface plasmon resonance assay, for example as described in Plant et al (1995) Analyt Biochem 226(2), 342-348. Methods may make use of a polypeptide that is labelled, for example with a radioactive or fluorescent label.
A further method of identifying a compound that is capable of binding to the ECSM4 polypeptide is one where the polypeptide is exposed to the compound and any binding of the compound to the said polypeptide is detected and/or measured. The binding constant for the binding of the compound to the polypeptide may be determined. Suitable methods for detecting and/or measuring (quantifying) the binding of a compound to a polypeptide are well known to those skilled in the art and may be performed, for example, using a method capable of high throughput operation, for example a chip-based method. New technology, called VLSIPS™, has enabled the production of extremely small chips that contain hundreds of thousands or more of different molecular probes. These biological chips or arrays have probes arranged in arrays, each probe assigned a specific location. Biological chips have been produced in which each location has a scale of, for example, ten microns. The chips can be used to determine whether target molecules interact with any of the probes on the chip. After exposing the array to target molecules under selected test conditions, scanning devices can examine each location in the array and determine whether a target molecule has interacted with the probe at that location.
Biological chips or arrays are useful in a variety of screening techniques for obtaining information about either the probes or the target molecules. For example, a library of peptides can be used as probes to screen for drugs. The peptides can be exposed to a receptor, and those probes that bind to the receptor can be identified. See U.S. Pat. No. 5,874,219 issued 23 Feb. 1999 to Rava et al.
Another method of targeting proteins that modulate the activity of ECSM4 is the yeast two-hybrid system, where the polypeptides of the invention can be used to “capture” ECSM4 protein binding proteins. The yeast two-hybrid system is described in Fields & Song, Nature 340:245-246 (1989).
It will be understood that it will be desirable to identify compounds that may modulate the activity of the polypeptide in vivo. Thus it will be understood that reagents and conditions used in the method may be chosen such that the interactions between the said and the interacting polypeptide are substantially the same as between a said naturally occurring polypeptide and a naturally occurring interacting polypeptide in vivo.
It will be appreciated that in the method described herein, the ligand may be a drug-like compound or lead compound for the development of a drug-like compound.
The term “drug-like compound” is well known to those skilled in the art, and may include the meaning of a compound that has characteristics that may make it suitable for use in medicine, for example as the active ingredient in a medicament. Thus, for example, a drug-like compound may be a molecule that may be synthesised by the techniques of organic chemistry, less preferably by techniques of molecular biology or biochemistry, and is preferably a small molecule, which may be of less than 5000 daltons and which may be water-soluble. A drug-like compound may additionally exhibit features of selective interaction with a particular protein or proteins and be bioavailable and/or able to penetrate target cellular membranes, but it will be appreciated that these features are not essential.
The term “lead compound” is similarly well known to those skilled in the art, and may include the meaning that the compound, whilst not itself suitable for use as a drug (for example because it is only weakly potent against its intended target, non-selective in its action, unstable, poorly soluble, difficult to synthesise or has poor bioavailability) may provide a starting-point for the design of other compounds that may have more desirable characteristics.
Alternatively, the methods may be used as “library screening” methods, a term well known to those skilled in the art. Thus, for example, the method of the invention may be used to detect (and optionally identify) a polynucleotide capable of expressing a polypeptide activator of ECSM4. Aliquots of an expression library in a suitable vector may be tested for the ability to give the required result.
Hence, an embodiment of this aspect of the invention provides a method of identifying a drug-like compound or lead compound for the development of a drug-like compound that modulates the activity of the polypeptide ECSM4, the method comprising contacting a compound with the polypeptide or a suitable variant, fragment, derivative or fusion thereof or a fusion of a variant, fragment or derivative thereof and determining whether, for example, the enzymic activity of the said polypeptide is changed compared to the activity of the said polypeptide or said variant, fragment, derivative or fusion thereof or a fusion of a variant, fragment or derivative thereof in the absence of said compound.
Preferably, the ECSM4 polypeptide is as described above in respect of the eleventh aspect of the invention.
It will be understood that it will be desirable to identify compounds that may modulate the activity of the polypeptide in vivo. Thus it will be understood that reagents and conditions used in the method may be chosen such that the interactions between the said polypeptide and its substrate are substantially the same as in vivo.
In one embodiment, the compound decreases the activity of said polypeptide. For example, the compound may bind substantially reversibly or substantially irreversibly to the active site of said polypeptide. In a further example, the compound may bind to a portion of said polypeptide that is not the active site so as to interfere with the binding of the said polypeptide to its ligand. In a still further example, the compound may bind to a portion of said polypeptide so as to decrease said polypeptide's activity by an allosteric effect. This allosteric effect may be an allosteric effect that is involved in the natural regulation of the said polypeptide's activity, for example in the activation of the said polypeptide by an “upstream activator”.
A still further aspect of the invention provides a polynucleotide comprising a promoter and/or regulatory portion of any one of the ECSM1 or ECSM4 genes.
By “ECSM1 or ECSM4 genes” we mean the natural genomic sequence which when transcribed is capable of encoding a polypeptide comprising the ECSM1 or ECSM4 polypeptide sequence as defined herein. The natural genomic sequence of the ECSM1 or ECSM4 genes may contain introns.
The polynucleotide of this aspect of the invention is preferably one which has transcriptional promoter activity. A promoter is an expression control element formed by a DNA sequence that permits binding of RNA polymerase and transcription to occur. Preferably the transcriptional promoter activity is present in mammalian cells and more preferably the polynucleotide has transcriptional promoter activity in endothelial cells. In a preferred embodiment, the transcriptional promoter activity is present in endothelial cells and not in other cell types.
Preferably, the promoter and/or regulatory portion is one which can direct endothelial cell selective expression.
Preferably, the promoter or regulatory region of the ECSM4 gene is one which is capable of promoting transcription of an operatively-linked coding sequence in response to hypoxic conditions. More preferably, the level of transcription of the coding sequence is up-regulated in hypoxic conditions compared to the level of transcription in the absence of hypoxia. By “hypoxic conditions” we include the physiological conditions of cancer where the inappropriate cell proliferation deprives surrounding tissue of oxygen, cardiac disease where for example a vessel occlusion may restrict the delivery of oxygen to certain tissues, and tissue necrosis where destruction of vascular tissue cells results in a reduced supply of oxygen to surrounding tissue and the consequent death of that surrounding tissue. Hypoxia is described in more detail in Hockel and Vaupel (2001) J. Nat. Can. Inst. 93: 266-276.
Hence, in a preferred embodiment, the ECSM4 promoter or regulatory region is comprised in a vector suitable for use in gene therapy for driving expression of a therapeutic gene to treat a hypoxic condition. Preferably, the hypoxic condition is cancer or cardiac disease. A “therapeutic gene” may be any gene which provides a desired therapeutic effect.
It will be appreciated that use of the said ECSM4 promoter to treat a hypoxic condition, for example by gene therapy, is included within the scope of the present invention.
Methods for the determination of the sequence of the promoter region of a gene are well known in the art. The presence of a promoter region may be determined by identification of known motifs, and confirmed by mutational analysis of the identified sequence. Preferably, the promoter sequence is located in the region 5 kb upstream of the genomic coding region of ECSM1 or ECSM4. More preferably, it is located in the region 3 kb or 2 kb or 1 kb or 500 bp upstream, and still more preferably it is located within 210 bp of the transcription start site.
Regulatory regions, or transcriptional elements such as enhancers are less predictable than promoters in their location relative to a gene. However, many motifs indicative of regulatory regions are well characterised and such regions affecting the level of transcription of the relevant gene can usually be identified on the basis of these motifs. The function of such a region can be demonstrated by well-known methods such as mutational analysis and in vitro DNA-binding assays including DNA footprinting and gel mobility shift assays.
Regulatory regions influencing the transcription of the ECSM1 or ECSM4 genes are likely to be located within the region 20 kb or 10 kb or 7 kb 5 kb or 3 kb, or more preferably 1 kb 5′ upstream of the relevant genomic coding region or can be located within introns of the gene.
Sequence tagged sites and mapping intervals will be helpful in localising promoter regions, regulatory regions and physical clones.
In a further preferred embodiment, the polynucleotide comprising the promoter and/or regulatory portion is operatively linked to a polynucleotide encoding a polypeptide. Methods for linking promoter polynucleotides to polypeptide coding sequences are well known in the art.
Preferably the polypeptide is a therapeutic polypeptide. A therapeutic polypeptide may be any polypeptide which it is medically useful to express selectively in endothelial cells. Examples of such therapeutic polypeptides include anti-proliferative, immunomodulatory or blood clotting-influencing factors, or anti-proliferative or anti-inflammatory cytokines. They may also comprise anti-cancer polypeptides.
In one embodiment of this aspect of the invention, the polynucleotide is one suitable for use in medicine. Thus, the invention includes the polynucleotide packaged and presented for use in medicine. It will be appreciated that such polynucleotides will be especially useful in gene therapy, especially where it is desirable to express a therapeutic polypeptide selectively an endothelial cell. It is preferred if the polynucleotide is one suitable for use in gene therapy.
Gene therapy may be carried out according to generally accepted methods, for example, as described by Friedman, 1991. A virus or plasmid vector (see further details below), containing a copy of the gene to be expressed linked to expression control elements such as promoters and other regulatory elements influencing transcription of ECSM1 or ECSM4 as described above and capable of replicating inside endothelial cells, is prepared. Suitable vectors are known, such as disclosed in U.S. Pat. No. 5,252,479 and WO 93/07282. The vector is then injected into the patient, either locally or systemically. If the transfected gene is not permanently incorporated into the genome of each of the targeted endothelial cells, the treatment may have to be repeated periodically.
Gene transfer systems known in the art may be useful in the practice of the gene therapy methods of the present invention. These include viral and nonviral transfer methods. A number of viruses have been used as gene transfer vectors, including papovaviruses, eg SV40 (Madzak et al, 1992), adenovirus (Berkner, 1992; Berkner et al, 1988; Gorziglia and Kapikian, 1992; Quantin et al, 1992; Rosenfeld et al, 1992; Wilkinson et al, 1992; Stratford-Perricaudet et al, 1990), vaccinia virus (Moss, 1992), adeno-associated virus (Muzyczka, 1992; Ohi et al, 1990), herpesviruses including HSV and EBV (Margolskee, 1992; Johnson et al, 1992; Fink et al, 1992; Breakfield and Geller, 1987; Freese et al, 1990), and retroviruses of avian (Brandyopadhyay and Temin, 1984; Petropoulos et al., 1992), murine (Miller, 1992; Miller et al, 1985; Sorge et al, 1984; Mann and Baltimore, 1985; Miller et al, 1988), and human origin (Shimada et al, 1991; Helseth et al, 1990; Page et al, 1990; Buchschacher and Panganiban, 1992). To date most human gene therapy protocols have been based on disabled murine retroviruses.
Nonviral gene transfer methods known in the art include chemical techniques such as calcium phosphate coprecipitation (Graham and van der Eb, 1973; Pellicer et al, 1980); mechanical techniques, for example microinjection (Anderson et al, 1980; Gordon et al, 1980; Brinster et al, 1981; Constantini and Lacy, 1981); membrane fusion-mediated transfer via liposomes (Felgner et al, 1987; Wang and Huang, 1989; Kaneda et al, 1989; Stewart et al, 1992; Nabel et al, 1990; Lim et al, 1992); and direct DNA uptake and receptor-mediated DNA transfer (Wolff et al, 1990; Wu et al, 1991; Zenke et al, 1990; Wu et al, 1989b; Wolff et al, 1991; Wagner et al, 1990; Wagner et al, 1991; Cotten et al, 1990; Curiel et al, 1991a; Curiel et al, 1991b).
Other suitable systems include the retroviral-adenoviral hybrid system described by Feng et al (1997) Nature Biotechnology 15, 866-870, or viral systems with targeting ligands such as suitable single chain Fv fragments.
In an approach which combines biological and physical gene transfer methods, plasmid DNA of any size is combined with a polylysine-conjugated antibody specific to the adenovirus hexon protein, and the resulting complex is bound to an adenovirus vector. The trimolecular complex is then used to infect cells. The adenovirus vector permits efficient binding, internalization, and degradation of the endosome before the coupled DNA is damaged.
Liposome/DNA complexes have been shown to be capable of mediating direct in vivo gene transfer. While in standard liposome preparations the gene transfer process is nonspecific, localized in vivo uptake and expression have been reported in tumour deposits, for example, following direct in situ administration (Nabel, 1992).
Gene transfer techniques which target DNA directly to tissues, eg endothelial cells, is preferred. Receptor-mediated gene transfer, for example, is accomplished by the conjugation of DNA (usually in the form of covalently closed supercoiled plasmid) to a protein ligand via polylysine. Ligands are chosen on the basis of the presence of the corresponding ligand receptors on the cell surface of the target cell/tissue type. In the case of endothelial cells, a suitable receptor is ECSM4. These ligand-DNA conjugates can be injected directly into the blood if desired and are directed to the target tissue where receptor binding and internalization of the DNA-protein complex occurs. To overcome the problem of intracellular destruction of DNA, coinfection with adenovirus can be included to disrupt endosome function.
In the case where replacement gene therapy using a functionally wild-type gene is used, it may be useful to monitor the treatment by detecting the presence of replacement gene mRNA or encoded replacement polypeptide, or functional gene product, at various sites in the body, including the endothelial cells, blood serum, and bodily secretions/excretions, for example urine.
A further aspect of the present invention provides a method of treating an individual with cancer, cardiac disease, a hypoxic condition, endometriosis or artherosclerosis comprising administering to the individual a polynucleotide according to the invention, which polynucleotide comprises a promoter or regulatory region of the invention operatively linked to a polynucleotide encoding a therapeutic polypeptide.
A still further aspect of the invention provides a method of modulating angiogenesis in an individual comprising administering to the individual a polynucleotide according to the invention, which polynucleotide comprises a promoter or regulatory region of the invention operatively linked to a polynucleotide encoding a therapeutic polypeptide or a polynucleotide which is capable of expressing ECSM4 or a fragment or variant thereof or which comprises an ECSM4 antisense nucleic acid.
The therapeutic polypeptide may be any therapeutic polypeptide which is useful in treating the individual. Preferably, the therapeutic polypeptide is any one or more of immunomodulatory, anti-cancer, a blood-clotting-influencing factor or an anti-proliferative or anti-inflammatory cytokine.
Antisense nucleic acid is discussed in more detail above. Briefly, the function of an antisense nucleic acid is to inhibit the translation of a specific mRNA to which the antisense nucleic acid is complementary and able to hybridise to within a cell, at least in part. The design of optimal antisense nucleic acid molecules is well known in the art of molecular biology.
The present invention also provides a use of a polynucleotide according to the invention, which polynucleotide comprises a promoter or regulatory region of the invention operatively linked to a polynucleotide encoding a therapeutic polypeptide in the manufacture of a medicament for treating cancer, cardiac disease, a hypoxic condition, endometriosis or artherosclerosis.
The invention will now be described in more detail by reference to the following Examples and Figures herein
FIG. 1 .
Experimental verification by reverse transcription PCR. Candidate endothelial specific genes predicted by the combination of the UniGene/EST screen and xProfiler SAGE differential analysis (Table 8) were checked for expression in three endothelial and nine non-endothelial cell cultures. Endothelial cultures were as follows: HMVEC (human microvascular endothelial cells), HUVEC (human umbilical vein endothelial cells) confluent culture and HUVEC proliferating culture. Non-endothelial cultures were as follows: normal endometrial stromal (NES) cells grown in normoxia and NES grown in hypoxia, MDA 453 and MDA 468 breast carcinoma cell lines, HeLa, FEK4 fibroblasts cultured in normoxia and FEK4 fibroblasts cultured in hypoxia, and SW480, HCT116-two colorectal epithelium cell lines. ECSM1 showed complete endothelial specificity, while magic roundabout/ECSM4 was very strongly preferentially expressed in the endothelium. Interestingly, both these novel genes appear more endothelial specific than the benchmark endothelial specific gene: von Willebrand factor.
FIG. 2 .
Phrap generated contig sequence (SEQ ID NO:21) for ECSM1 and amino acid sequence (SEQ ID NO:22) of the translation product. The ESTs used to generate this contig are shown in Table 10.
FIG. 3 .
ECSM4 in vitro transcription/translation. The cDNA coding for full length ECSM4 was cloned into pBluescript plasmid vector. Circular and HindIII digested plasmid were subjected to in vitro transcription/translation using TNT® T7 Quick Coupled Transcription/Translation System (Promega Corporation) incorporating 35 S Methionine as per manufacturer's instructions. The reaction products were resolved by SDS PAGE and visualised by autoradiography. The Luciferase plasmid was utilised as a positive control for the reaction. The numbers on the left indicate the position of molecular size markers for reference. The size of the band denoting ECSM4 is consistent with the calculated molecular weight of the polypeptide of 118 kDa.
FIG. 4 .
cDNA and computer translation of GenBank AK000805 (human ECSM4/magic roundabout (SEQ ID NOs:23 and 24)).
FIG. 5 .
Phrap generated contig sequence for human ECSM4 (magic roundabout) ESTs (SEQ ID NO:25) and translation of the encoded polypeptide (SEQ ID NO:26). The DNA sequence is shown in the orientation as if it were a cDNA, which is opposite to that in which it was originally generated. The ESTs used to generate the contig are shown in Table 11. Translation start in this sequence is at position 2 of the contig sequence, and translation finish is at position 948.
FIG. 6 .
An alignment of the GenBank Accession No AK000805 (“magic.seq”) (SEQ ID NO:27) and Phrap (“hs. 111518”) generated nucleic acid sequences of human ECSM4 (SEQ ID NO:28) given in FIGS. 4 and 5 .
FIG. 7 .
Mouse ECSM4 contig nucleotide sequence (SEQ ID NO:29) and amino acid sequence (SEQ ID NO:30).
FIG. 8 .
An alignment of the amino acid sequences of the mouse Robo1 protein (“T30805”) (SEQ ID NO:32) and human ECSM4 (“magic.pep”) (SEQ ID NO:31).
FIG. 9 .
An alignment of the amino acid sequences of mouse Robol protein (“T30805”) (SEQ ID NO:33) and mouse ECSM4 (“mousemagic.pep”) (SEQ ID NO:30).
FIG. 10 .
An alignment of the amino acid sequences of human (“magic.pep”) (SEQ ID NO:35) and mouse (“mousemagic.pep”) ECSM4 proteins (SEQ ID NO.34). Residues in bold indicate well conserved sequences. The mouse protein sequence is shown on top and the human sequence is below.
FIG. 11 .
Expression of magic roundabout in vitro. (a) Ribonuclease protection analysis. Top, two probes to different regions (nucleotides 1 to 355 and 3333 to 3679) of magic roundabout were used in the analysis (shown left and right). RNase protection assay was performed with U6 small nuclear RNA as control (shown bottom) (Maxwell et al (1999) Nature 399: 271). Human cell lines and primary isolates: MRC-5, fibroblast cell line, MCF-7, breast carcinoma cell line, Neuro, SY-SH-5Y neuroblastoma cell line, HUVEC, umbilical vein endothelial isolate, HDMEC, dermal microvascular endothelial isolate and HMME2, mammary microvascular endothelial cell line. N, normoxia, H, hypoxia, P. proliferating. (b) Western analysis of cell lysates. A band at ˜110 kD corresponds to MR and was stronger in cells exposed to hypoxia for 18 h. The experiment was repeated twice with similar results. Immunoblotting was carried out as described in Brown et al (2000) Cancer Res. 60: 6298. Polyclonal rabbit anti-sera was raised against the following peptides coupled to keyhole limpet haemocyanin: amino acids 165-181 (LSQSPGAVPQALVAWRA (SEQ ID NO:6)) and 274-288 (DSVLTPEEVALCLEL (SEQ ID NO:7)) (anti-sera 1) or peptides 311-320 (TYGYISVPTA (SEQ ID NO:8)) and 336-351 (KGGVLLCPPRPCLTPT (SEQ ID NO:9)) (anti-sera 2). Both anti-sera gave identical results. For western analysis, anti-sera was affinity purified on a “Hi-Trap NHS-activated HP” column (Amersham) to which the peptides used to raise anti-sera 1 were coupled.
FIG. 12 .
Human ECSM4 full-length cDNA (SEQ ID NO:36) and encoded protein sequence (SEQ ID NO:37).
FIG. 13 .
Mouse ECSM4 full-length cDNA (MuMR.seq) (SEQ ID NOs:38 and 39) and encoded protein sequences (SEQ ID NOs:40-42).
FIG. 14 .
Alignment of human ECSM4 (top) (SEQ ID NO:43) and mouse ECSM4 (bottom) amino acid sequences (SEQ ID NO:48 and SEQ ID NOs:45-47).
FIG. 15 .
Alignment of human ECSM4 (“HuMR.seq”; top (SEQ ID NO:49)) and mouse ECSM4 (“MuMR.seq”; bottom (SEQ ID NO:50)) cDNA sequences.
FIG. 16 .
In situ hybridisation analysis of human placental tissue using ECSM4 as probe. A bright field view of 10× magnification of thin section of placental tissue. The arrow indicates a large blood vessel.
FIG. 17 .
In situ hybridisation analysis of human placental tissue using ECSM4 as probe. A higher magnification of the bright-field view of thin section of placental tissue shown in FIG. 16 , focussing on the blood vessel. The arrow points to endothelial cells lining the lumen of the vessel.
FIG. 18 .
In situ hybridisation analysis of human placental tissue using ECSM4 as probe. A higher magnification of the thin section of placental tissue shown in FIG. 16 , focussing on the blood vessel and shown here in dark-field. The arrow depicts positive staining of endothelial cells lining the lumen of the vessel.
FIG. 19 .
In situ hybridisation analysis of colorectal liver metastatic tissue using ECSM4 as probe. A bright-field view of a section of colorectal liver metastatic tissue magnified with (A) 10× and (B) 20× objective. The area marked by the boundary (encircling * A) depicts the normal liver tissue. The arrow in (B) shows one of the blood vessels within the metastatic tumour tissue.
FIG. 20 .
In situ hybridisation analysis of colorectal liver metastatic tissue using ECSM4 as a probe. This is a dark field view of a section of colorectal liver metastatic tissue magnified with (A) 10× and (B) 20× objective. The area marked by the boundary (encircling *) depicts the normal liver tissue. The arrow in (B) shows one of the blood vessels within the metastatic tumour tissue corresponding to the vessel shown in FIG. 19B . Expression of ECSM4 is restricted to endothelial cells of the tumour blood vessels. Note that there is little expression in the surrounding normal tissue (*).
FIG. 21 .
Western Blot using the rabbit antibody MGO-5 as primary antibody. Dilutions of the peptides ECSM4-derived peptides MR 165, MR 311, MR 366 and the control polypeptide Bovine Serum Albumin (BSA) were resolved by SDS polyacrylamide gel electrophoresis and blotted onto Immobilon P membrane. The blot was probed with MGO-5 antibody and visualised using anti-rabbit antibody coupled with alkaline phosphatase.
FIG. 22 .
Immunostaining of frozen placental section. A frozen thin section of human placenta was analysed by immunohistochemistry without any primary antibody (negative control) and visualised using anti-rabbit antibody coupled with alkaline phosphatase. Little background staining is observed.
FIG. 23 .
Immunostaining of frozen placental section. A frozen thin section of human placenta was analysed by immunohistochemistry using a primary antibody recognising von Willibrand Factor (positive control), and visualised using an anti-rabbit secondary antibody coupled with alkaline phosphatase. The arrows show high levels of expression of vWF restricted to the vascular endothelial cells.
FIG. 24 .
Immunostaining of frozen placental section. A frozen thin section of human placenta was analysed by immunohistochemistry using MGO-5 (a rabbit polyclonal antibody raised against peptide MR 165) as the primary antibody, and visualised using anti-rabbit secondary antibody coupled with alkaline phosphatase. The arrows show high levels of expression of ECSM4 restricted to the vascular endothelial cells. Note that the surrounding tissue shows little staining. Comparison with FIGS. 22 and 23 shows that the expression of ECSM4 colocalises with that of vWF, a known marker for vascular endothelial cells.
FIG. 25 .
Immunohistochemical analysis of HUVEC cells: von Willibrand Factor (VWF). HUVEC cells were immobilised and analysed by immunohistochemistry using an antibody recognising von Willibrand Factor (a marker for endothelial cells) as the primary antibody and visualised using anti-rabbit antibody coupled with alkaline phosphatase. The arrows show expression of vWF in a subset of the HUVEC cells.
FIG. 26 .
Immunohistochemical analysis of HUVEC cells using the antibody MGO-7. HUVEC cells were immobilised and analysed by immunohistochemistry using MGO-7 antibody (a rabbit polyclonal antibody raised against peptides MR 311 and MR 336) as the primary antibody and visualised using anti-rabbit antibody coupled with alkaline phosphatase. The arrows show expression of ECSM4 in a subset of the HUVEC cells. Note that the staining is localised primarily to the cell surface of the cells.
FIG. 27 . Expression of magic roundabout in vivo.
(A) Expression of MR detected by in situ hybridisation in of a placental arteriole (a) and venule (b) (left, light field and right, dark field). (c) Immunohistochemical staining of magic roundabout in a placental arteriole. Left, von Willibrand factor control and right, magic roundabout. (B) Expression of MR in tumour endothelium. Ganglioglioma (a) x20 and (b) x50. Left, light field; right, dark field. Arrows highlight a vessel running diagonally down the section with an erythrocyte within it. Endothelial cells are strongly positive for MR expression. Papillary bladder carcinoma (c) x20 and (d) x50. The vascular core of the papilla of the tumour is strongly positive, particularly the ‘flat’ endothelial cells indicated by arrows. A magic roundabout antisense in situ probe was generated using T3 polymerase from IMAGE EST clone 1912098 (GenBank acc. AI278949). The plasmid was linearised with Eco RI prior to probe synthesis. In situ analysis was then performed as described in Poulsom et al (1998) Eur. J. Histochemistry 42:121-132.
EXAMPLE 1
In Silico Cloning of Novel Endothelial Specific Genes
We describe the use of two independent strategies for differential expression analysis combined with experimental verification to identify genes specifically or preferentially expressed in vascular endothelium.
The first strategy was based the EST cluster expression analysis in the human UniGene gene index (Schuler et al, 1997). Recurrent gapped BLAST searches (Altschul et al, 1997) were performed at very high stringency against expressed sequence tags (ESTs) grouped in two pools. These two pools comprised endothelial cell and non-endothelial cell libraries derived from dbEST (Boguski et al, 1995). The second strategy employed a second datamining tool: SAGEmap xprofiler. XProfiler is a freely available on-line tool, which is a part of the NCBI's Cancer Genome Anatomy Project (CGAP) (Strausberg et al, 1997, Cole et al, 1995). While these two approaches alone were producing a discouragingly high number of false positives, when both strategies were combined, predictions proved exceptionally reliable and two novel candidate endothelial-specific genes have been identified. Full-length cDNAs have been identified in sequence databases. Another gene (EST cluster) corresponds to a partial cDNA sequence from a large-scale cDNA sequencing project and contains a region of similarity to the intracellular domain of human roundabout homologue 1 (ROBO1).
UniGene/EST Gene Index Screen
A pool of endothelial and a pool of non-endothelial sequences were extracted using Sequence Retrieval System (SRS) version 5 from dbEST. The endothelial pool consisted of 11,117 ESTs from nine human endothelial libraries (Table 1). The non-endothelial pool included 173,137 ESTs from 108 human cell lines and microdissected tumour libraries (Table 2). ESTs were extracted from dbEST release April 2000. Multiple FASTA files were transformed into a BLAST searchable database using the pressdb programme. Table 3 shows the expression status of five known endothelial cell-specific genes in these two pools.
Subsequently, the longest, representative sequence in each UniGene cluster (UniGene Build #111 May 2000, multiple FASTA file hs.seq.uniq) was searched using very high stringency BLAST against these two pools. If such representative sequence reported no hits, the rest of the sequences belonging to the cluster (UniGene multiple-FASTA file hs.seq) were used as BLAST queries. Finally, clusters with no hits in the non-endothelial pool and at least one hit in the endothelial pool were selected.
Optimising the BLAST E-value was crucial for the success of BLAST identity-level searches. Too high an E-value would result in gene paralogues being reported. On the other hand, too low (stringent) an E-parameter would result in many false negatives, i.e. true positives would not be reported due to sequencing errors in EST data: ESTs are large-scale low-cost single pass sequences and have high error rate (Aaronson et al, 1996). In this work an E-value of 10e-20 was used in searches against non-endothelial EST pool and a more stringent 10e-30 value in searches against the smaller endothelial pool. These values were deemed optimal after a series of test BLAST searches.
SAGE Data and SAGEmap xProfiler Differential Analysis
Web-based SAGE library subtraction (available at the National Center for Biotechnology Information SAGEmap xProfiler internet site) was utilised as the second datamining strategy for the identification of novel endothelial specific or preferentially endothelial genes. Two endothelial SAGE libraries (SAGE_Duke_HMVEC and SAGE_Duke_HMVEC+VEGF with a total of 110,790 sequences) were compared to twenty-four non-endothelial, cell line libraries (full list in Table 4, total of 733,461 sequences). Table 5 shows the status of expression of five known endothelial specific genes: von Willebrand's factor (vWF), two vascular endothelial growth factor receptors: fms-like tyrosine kinase 1 (flt1) and kinase insert domain receptor (KDR), tyrosine kinase receptor type tie (TIE 1) and tyrosine kinase receptor type tek (TIE2/TEK), in these two SAGE pools.
Combined Data Gives Highly Accurate Predictions
Twenty known genes were selected in the UniGene/EST screen (Table 6). These genes had no hits in the non-endothelial pool and at least one hit in the endothelial pool. The list contained at least four endothelial specific genes: TIE1, TIE2/TEK, LYVE1 and multimerin, indicating ˜20% accuracy of prediction. Other genes on the list, while certainly preferentially expressed in the endothelial cells, might not be endothelial specific. To improve on the prediction accuracy we decided to combine UniGene/EST screen with the xProfiler SAGE analysis. The xProfiler output consisted of a list of genes with a ten times higher number of tags in the endothelial than in the non-endothelial pool sorted according to the certainty of prediction. A 90% certainty threshold was applied to this list. Table 7 shows how data from the two approaches were combined. Identity-level BLAST searches were performed on mRNAs (known genes) or phrap computed contigs (EST clusters representing novel genes) to investigate how these genes were represented in the endothelial and non-endothelial pool. Subsequent experimental verification by RT-PCR ( FIG. 1 ) proved that the combined approach was 100% accurate, i.e. genes on the xProfiler list which had no matches the non-endothelial EST pool and at least one match in the endothelial pool were indeed endothelial specific.
Discussion
There have been several reports of computer analysis of tissue transcriptosomes. Usually an expression profile is constructed, based on the number of tags assigned to a given gene or a class of genes (Bernstein et al, 1996, Welle et al, 1999, Bortoluzzi et al, 2000). An attempt can be made to identify tissue-specific transcripts, for example Vasmatzis et al, (1997) described three novel genes expressed exclusively in the prostate by in silico subtraction of libraries from the dbEST collection. Purpose made cDNA libraries may also be employed. Ten candidate granulocyte-specific genes have been identified by extensive sequence analysis of cDNA libraries derived from granulocytes and eleven other tissue samples, namely a hepatocyte cell line, foetal liver, infant liver, adult liver, subcutaneous fat, visceral fat, lung, colonic mucosa, keratinocytes, cornea and retina (Itoh et al, 1998).
An analysis similar to the dbEST-based approach taken by Vasmatzis et al, is complicated by the fact that endothelial cells are present in all tissues of the body and endothelial-ESTs are contaminating all bulk tissue libraries. To validate this we used three well-known endothelial specific genes: KDR, FLT1, and TIE-2 as queries for BLAST searches against dbEST. Transcripts were present in a wide range of tissues with multiple hits in well vascularised tissues (e.g. placenta, retina), embryonic (liver, spleen) or infant (brain) tissues. Additionally, we found that simple subtraction of endothelial EST libraries against all other dbEST libraries failed to identify any specific genes (data not shown).
Two very different types of expression data resources were used in our datamining efforts. The UniGene/EST screen was based on expressed sequence tag libraries from dbEST. There are 9 human endothelial libraries in the current release of dbEST with a relatively small total number of ESTs: ˜11,117. Some well-known endothelial specific genes are not represented in this dataset (Table 3). This limitation raised our concerns that genes with low levels of expression would be overlooked in our analysis. Therefore, we utilised another type of computable expression data: CGAP SAGE libraries. SAGE tags are sometimes called small ESTs (usually 10-11 bp in length). Their major advantage is that they can be unambiguously located within the cDNA: they are immediately adjacent to the most 3′ NlaIII restriction site. Though, there are only two endothelial CGAP SAGE libraries available at the moment, they contain an impressive total of ˜111,000 tags—an approximately 10 times bigger dataset than the ˜11,117 sequences in the endothelial EST pool. The combined approach proved very accurate (Table 8, FIG. 1 ) when verified by RT-PCR.
We report here identification of two novel highly endothelial specific genes: endothelial cell-specific molecule 1 (ECSM1—UniGene entry Hs.13957) and magic roundabout (UniGene entry Hs. 111518). For a comprehensive summary of data available on these genes see Table 8.
Our combined datamining approach together with experimental verification is a powerful functional genomics tool. This type of analysis can be applied to many cell types not just endothelial cells. The challenge of identifying the function of discovered genes remains, but bioinformatics tools such as structural genomics, or homology and motif searches can offer insights that can then be verified experimentally.
In summary, this screening approach has allowed the identification of novel endothelial cell specific genes and known genes whose expression was not known to be specific to endothelial cells. This identification both advances our understanding of endothelial cell biology and provides new pharmaceutical targets for imaging, diagnosing and treating medical conditions involving the endothelium.
Methods
PERL Scripts
A number of PERL scripts were generated to facilitate large scale sequence retrieval, BLAST search submissions, and automatic BLAST output analysis.
Database Sequence Retrieval
Locally stored UniGene files (Build #111, release date May 2000) were used in the preparation of this report. The UniGene website can be accessed on the National Center for Biotechnology Information internet site, and UniGene files can be downloaded from the ftp repository: ftp://ncbi.nlm.nih.gov/repository/unigene/. Representative sequences for the human subset of UniGene (the longest EST within the cluster) are stored in the file Hs.seq.uniq, while all ESTs belonging to the cluster are stored in a separate file called Hs.seq.
Sequences were extracted from the dbEST database accessed locally at the HGMP centre using the Sequence Retrieval System (SRS version 5) getz command. This was done repeatedly using a PERL script for all the libraries in the endothelial and non-endothelial subsets, and sequences were merged into two multiple-FASTA files.
Selection Criteria for Non-endothelial EST Libraries
Selection of 108 non-endothelial dbEST libraries was largely manual. Initially the list of all available dbEST libraries, which is available at the National Center for Biotechnology Information internet site was searched using the keyword ‘cells’ and the phrase ‘cell line’. While this searched identified most of the libraries, additional keywords had to be added for the list to be full: ‘melanocyte’, ‘macrophage’, ‘HeLa’, ‘fibroblast’. In some cases, detailed library description was consulted to confirm that library is derived from a cell line/primary culture. We also added a number of CGAP microdissected tumour libraries. For that, Library Browser, available at the National Center for Biotechnology Information internet site, was used to search for the keyword ‘microdissected’.
UniGene Gene Index Screen
The UniGene gene transcript index was screened against the EST division of GenBank, dbEST. Both UniGene and dbEST were developed at the National Centre for Biotechnology Information (NCBI). UniGene is a collection of EST clusters corresponding to putative unique genes. It currently consists of four datasets: human, mouse, rat and zebrafish. The human dataset is comprised of approximately 90,000 clusters (UniGene Build #111 May 2000). By means of very high stringency BLAST identity searches, we aimed to identify those UniGene genes that have transcripts in the endothelial and not in the non-endothelial cell-type dbEST libraries. Throughout the project, University of Washington blast2 which is a gapped version was used as BLAST implementation. The E-value was set to 10e-20 in searches against the non-endothelial EST pool and to 10e-30 in searches against the smaller endothelial pool.
While UniGene does not provide consensus sequences for its clusters, the longest sequence within the cluster is identified. Thus, this longest representative sequence (multiple FASTA file Hs.seq.uniq) was searched using very high stringency BLAST against the endothelial and non-endothelial EST pool. If such representative sequence reported no matches, the rest of the sequences belonging to the cluster (UniGene multiple-FASTA file Hs.seq) followed as BLAST queries. Finally, clusters with no matches in the non-endothelial pool and at least one match in the endothelial pool were selected using PERL scripts analysing BLAST textual output.
xProfiler SAGE Subtraction
xProfiler enables an on-line user to perform a differential comparison of any combination of forty seven serial analysis of gene expression (SAGE) libraries with a total of˜2,300,000 SAGE tags using a dedicated statistical algorithm (Chen et al, 1998). xProfiler can be accessed on the National Center for Biotechnology Information internet site SAGE itself is a quantitative expression technology in which genes are identified by typically a 10 or 11 bp sequence tag adjacent to the cDNA's most 3′ NlaIII restriction site (Velculescu et at, 1995).
The two available endothelial cell libraries (SAGE_Duke_HMVEC and SAGE_Duke_HMVEC+VEGF) defined pool A and twenty-four (see Table 4 for list) non-endothelial libraries together built pool B. The approach was verified by establishing the status of expression of the five reference endothelial specific genes in the two SAGE pools (Table 5) using Gene to Tag Mapping, available on the National Center for Biotechnology Information internet site Subsequently, xProfiler was used to select genes differentially expressed between the pools A and B. The xProfiler output consisted of a list of genes with a ten fold difference in the number of tags in the endothelial compared to the non-endothelial pool sorted according to the certainty of prediction. A 90% certainty threshold was applied to this list.
The other CGAP' s on-line differential expression analysis tool, Digital Differential Display (DDD), relies on EST expression data (source library info) instead of using SAGE tags. We attempted to utilise this tool similarly to SAGEmap xProfiler but have been unable to obtain useful results. Five out of nine endothelial and sixty-four out of hundred and eight non-endothelial cell libraries used in our BLAST-oriented approach were available for on-line analysis using DDD, available at the National Center for Biotechnology Information internet site. When such analysis was performed the following were fifteen top scoring genes: annexin A2, actin gamma 1, ribosomal protein large P0, plasminogen activator inhibitor type I, thymosin beta 4, peptidyloprolyl isomerase A, ribosomal protein L13a, laminin receptor 1 (ribosomal protein SA), eukaryotic translation elongation factor 1 alpha 1, vimentin, ferritin heavy polypeptide, ribosomal protein L3, ribosomal protein S18, ribosomal protein L19, tumour protein translationally-controlled 1. This list was rather surprising, did not include any well-known endothelial specific genes, did not have any overlap with SAGE results (Table 8), and contained many genes, that in the literature are reported to be ubiquitously expressed (ribosomal proteins, actin, vimentin, ferritin). A major advantage of our UniGene/EST screen is that instead of relying on source library data and fallible EST clustering algorithms it actually performs identity-level BLAST comparisons in search of transcripts corresponding to a gene.
Mining Data on UniGene Clusters
To quickly access information about UniGene entries (e.g. literature references, STS sites, homologues, references to function) on-line resources were routinely used: NCBI's UniGene and LocusLink interfaces and Online Mendelian Inheritance in Man.
ESTs in UniGene clusters are not assembled into contigs, so before any sequence analysis, contigs were created using phrap assembler (for documentation on phrap see the bozeman.mbt internet site).
To analyse genomic contig AC005795 (44,399) bp containing ECSM1, NIX Internet interface for multi-application analysis of large unknown nucleotide sequences was used. For further information on NIX see the hgmp.mrc internet site. Alignment of ECSM1 against AC005795 was obtained using the NCBI interface to the Human Genome Interface: the NCBI Map Viewer. For further information on the NCBI Map Viewer see the National Center for Biotechnology Information internet site.
To search for possible transmembrane domains and signal sequences in translated nucleotide sequences three Internet based applications were used: DAS (Cserzo et al, 1997), TopPred2 (Heijne 1992), and SignalP (Nielsen et al, 1997).
PERL Scripts
A number of PERL scripts were generated to facilitate large scale sequence retrieval, BLAST search submissions, and automatic BLAST output analysis.
Experimental Verification
To experimentally verify specificity of expression we used the reverse transcription polymerase chain reaction (RT-PCR). RNA was extracted from three endothelial and seven non-endothelial cell types cultured in vitro. Endothelial cultures were as follows: HMVEC (human microvascular endothelial cells), HUVEC (human umbilical vein endothelial cells) confluent culture and HUVEC proliferating culture. Non-endothelial cultures were as follows: normal endometrial stromal (NES) cells grown in normoxia and NES grown in hypoxia, MDA 453 and MDA 468 breast carcinoma cell lines, HeLa, FEK4 fibroblasts cultured in normoxia and FEK4 fibroblasts cultured in hypoxia, and SW480, HCT116—two colorectal epithelium cell lines.
If a sequence tagged site (STS) was available, dbSTS PCR primers were used and cycle conditions suggested in the dbSTS entry followed. Otherwise, primers were designed using the Primer3 programme. Primers are listed in Table 9.
Tissue Culture Media, RNA Extraction and cDNA Synthesis
Cell-lines were cultured in vitro according to standard tissue culture protocols. In particular, endothelial media were supplemented with ECGS (endothelial cell growth supplement—Sigma), and heparin (Sigma) to promote growth. Total RNA was extracted using the RNeasy Minikit (Qiagen) and cDNA synthesised using the Reverse-IT 1 st Strand Synthesis Kit (ABgene).
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TABLE 1
Nine human endothelial libraries from dbEST
Human aortic endothelium, 20 sequences, in vitro culture
Human endothelial cells, 346 sequences, primary isolate
Human endothelial cell (Y. Mitsui), 3 sequences, in vitro culture
Stratagene endothelial cell 937223, 7171 sequences, primary isolate
Aorta endothelial cells, 1245 sequences, primary isolate
Aorta endothelial cells, TNF treated, 1908 sequences, primary isolate
Umbilical vein endothelial cells I, 9 sequences
HDMEC cDNA library, 11 sequences, in vitro culture
Umbilical vein endothelial cells II, 404 sequences
TABLE 2
Non-endothelial dbEST libraries.
1.
Activated T-cells I
2.
Activated T-cells II
3.
Activated T-cells III
4.
Activated T-cells IV
5.
Activated T-cells IX
6.
Activated T-cells V
7.
Activated T-cells VI
8.
Activated T-cells VII
9.
Activated T-cells VIII
10.
Activated T-cells X
11.
Activated T-cells XI
12.
Activated T-cells XII
13.
Activated T-cells XX
14.
CAMA1Ee cell line I
15.
CAMA1Ee cell line II
16.
CCRF-CEM cells, cyclohexamide
treated I
17.
CdnA library of activated B cell line
3D5
18.
Chromosome 7 HeLa cDNA Library
19.
Colon carcinoma (Caco-2) cell line I
20.
Colon carcinoma (Caco-2) cell line II
21.
Colon carcinoma (HCC) cell line
22.
Colon carcinoma (HCC) cell line II
23.
HCC cell line (matastasis to liver in
mouse)
24.
HCC cell line (matastasis to liver in
mouse) II
25.
HeLa cDNA (T. Noma)
26.
HeLa SRIG (Synthetic retinoids
induced genes)
27.
Homo sapiens monocyte-derived
macrophages
28.
HSC172 cells I
29.
HSC172 cells II
30.
Human 23132 gastric carcinoma cell
line
31.
Human breast cancer cell line Bcap
37
32.
Human cell line A431 subclone
33.
Human cell line AGZY-83a
34.
Human cell line PCI-O6A
35.
Human cell line PCI-O6B
36.
Human cell line SK-N-MC
37.
Human cell line TF-1 (D. L. Ma)
38.
Human exocervical cells (CGLee)
39.
Human fibrosarcoma cell line
HT1080
40.
Human fibrosarcoma cell line
HT1080-6TGc5
41.
Human gastric cancer SGC-7901 cell
line
42.
Human GM-CSF-deprived TF-1 cell
line (Liu, Hongtao)
43.
Human HeLa (Y. Wang)
44.
Human HeLa cells (M. Lovett)
45.
Human Jurkat cell line mRNA
(Thiele, K.)
46.
Human K562 erythroleukemic cells
47.
Human lung cancer cell line
A549.A549
48.
Human nasopharyngeal carcinoma
cell line HNE1
49.
Human neuroblastoma SK-ER3 cells
(M. Garnier)
50.
Human newborn melanocytes
(T. Vogt)
51.
Human pancreatic cancer cell line
Patu 8988t
52.
Human primary melanocytes mRNA
(I. M. Eisenbarth)
53.
Human promyelocytic HL60 cell line
(S. Herblot)
54.
Human retina cell line ARPE-19
55.
Human salivary gland cell line HSG
56.
Human White blood cells
57.
Jurkat T-cells I
58.
Jurkat T-cells II
59.
Jurkat T-cells III
60.
Jurkat T-cells V
61.
Jurkat T-cells VI
62.
Liver HepG2 cell line.
63.
LNCAP cells I
64.
Macrophage I
65.
Macrophage II
66.
Macrophage, subtracted (total
CdNA)
67.
MCF7 cell line
68.
Namalwa B cells I
69.
Namalwa B cells II
70.
NCI_CGAP_Br4
71.
NCI_CGAP_Br5
72.
NCI_CGAP_CLL1
73.
NCI_CGAP_GCB0
74.
NCI_CGAP_GCB1
75.
NCI_CGAP_HN1
76.
NCI_CGAP_HN3
77.
NCI_CGAP_HN4
78.
NCI_CGAP_HSC1
79.
NCI_CGAP_Li1
80.
NCI_CGAP_Li2
81.
NCI_CGAP_Ov5
82.
NCI_CGAP_Ov6
83.
NCI_CGAP_Pr1
84.
NCI_CGAP_Pr10
85.
NCI_CGAP_Pr11
86.
NCI_CGAP_Pr16
87.
NCI_CGAP_Pr18
88.
NCI_CGAP_Pr2
89.
NCI_CGAP_Pr20
90.
NCI_CGAP_Pr24
91.
NCI_CGAP_Pr25
92.
NCI_CGAP_Pr3
93.
NCI_CGAP_Pr4
94.
NCI_CGAP_Pr4.1
95.
NCI_CGAP_Pr5
96.
NCI_CGAP_Pr6
97.
NCI_CGAP_Pr7
98.
NCI_CGAP_Pr8
99.
NCI_CGAP_Pr9
100.
Normal Human Trabecular Bone
Cells
101.
Raji cells, cyclohexamide treated I
102.
Retinal pigment epithelium 0041
cell line
103.
Retinoid treated HeLa cells
104.
Soares melanocyte 2NbHM
105.
Soares_senescent_fibroblasts_Nb
HSF
106.
Stratagene HeLa cell s3 937216
107.
Supt cells
108.
T, Human adult
Rhabdomyosarcoma cell-line
TABLE 3
Five genes known to be endothelial specific genes in the dbEST pools.
Known endothelial specific
Hits in the non-
Hits in the
gene
endothelial pool
endothelial pool
von Willebrand factor (vWF)
1
27
flt1 VEGF receptor
—
—
KDR VEGF receptor
1
—
TIE1 tyrosine kinase
—
5
TIE2/TEK tyrosine kinase
—
2
The number of ESTs in the endothelial pool is relatively small (~11,117) and not all known endothelial genes are represented
TABLE 4
Twenty-four non-endothelial cell SAGE-CGAP libraries.
SYMBOL
DESCRIPTION
SAGE_HCT116
Colon, cell line derived from colorectal
carcinoma
SAGE_Caco_2
Colon, colorectal carcinoma cell line
SAGE_Duke_H392
Brain, Duke glioblastoma multiforme cell line
SAGE_SW837
Colon, cancer cell line
SAGE_RKO
Colon, cancer cell line
SAGE_NHA(5th)
Brain, normal human astrocyte cells harvested at
passage 5
SAGE_ES2-1
Ovarian Clear cell carcinoma cell line ES-2,
poorly differentiated
SAGE_OVCA432-2
Ovary, carcinoma cell line OVCA432
SAGE_OV1063-3
Ovary, carcinoma cell line OV1063
SAGE_Duke_mhh-1
Brain, c-myc negative medulloblastoma cell line
mhh-1
SAGE_Duke_H341
Brain, c-myc positive medulloblastoma cell line
H341
SAGE_HOSE_4
Ovary, normal surface epithelium
SAGE_OVP-5
Ovary, pooled cancer cell lines
SAGE_LNCaP
Prostate, cell line. Androgen dependent
SAGE_HMEC-B41
Cell culture HMEC-B41 of normal human
mammary epithelial cells
SAGE_MDA453
Cell line MDA-MB-453 of human breast
carcinoma
SAGE_SKBR3
ATCC cell line SK-BR-3. Human breast
adenocarcinoma
SAGE_A2780-9
Ovary, ovarian cancer cell line A2780
SAGE_Duke_H247_normal
Brain, glioblastoma multiforme cell line, H247
AGE_Duke_H247_Hypoxia
Brain, Duke glioblastoma multiforme cell line,
H247, grown under 1.5% oxygen
SAGE_Duke_post_crisis_fibroblasts
Skin, post-crisis survival fibroblast cell-line
SAGE_Duke_precrisis_fibroblasts
Skin, large T antigen transformed human
fibroblasts clones
SAGE_A
Prostate, cancer cell line. Induced with synthetic
androgen
SAGE_IOSE29-11
Ovary, surface epithelium line
TABLE 5
Five known endothelial specific genes in the CGAP SAGE pools.
Tags in the
Known endothelial
Tags in the non-endothelial
endothelial sage
specific gene
sage libraries
libraries
von Willebrand factor
1 (colon carcinoma cell line)
80
(VWF)
flt1 VEGF receptor
—
—
KDR VEGF receptor
1 (IOSE29 ovarian surface
6
epithelium cell line)
TIE1 tyrosine kinase
17 (ovarian tumour and
27
normal ovarian epithelium
cell lines)
TIE2/TEK tyrosine
4 (ovarian carcinoma and
2
kinase
glioblastoma multiforme cell
lines)
TIE1 and TIE2/TEK have multiple hits in the non-endothelial pool (most in normal or carcinoma cell lines of ovarian origin). vWF is most endothelial specific having 80 hits in the endothelial pool and only one hit in the non-endothelial pool.
TABLE 6
Results of the UniGene/EST screen.
UniGene
Endothelial
Description
ID
hits
TIE1 receptor endothelial tyrosine kinase
Hs.78824
5
Cytosolic phospholipase A2; involved in the
Hs.211587
3
metabolism of eicosanoids
Branched chain alpha-ketoacid dehydrogenase
Hs.1265
2
CGMP-dependent protein kinase; cloned from
Hs.2689
2
aorta cDNA, strongly expressed in well
vascularised tissues like aorta, heart, and uterus
(Tamura et al, 1996)
Lymphatic vessel endothelial hyaluronan
Hs.17917
2
receptor 1-LYVE1 (Banerji et al, 1999)
TRAF interacting protein: TNF signalling
Hs.21254
2
pathway
Multimerin: a very big endothelial specific
Hs.32934
2
protein; binds platelet factor V, can also be
found in platelets (Hayward et al, 1996)
Diubiquitin (a member of the ubiquitin family);
Hs.44532
2
reported in dendrytic and B lymphocyte cells;
involved in antigen processing; this is first
evidence that it is also present in endothelial
cells (Bates et al, 1997)
Beta-transducin family protein; also a homolog
Hs.85570
2
of D. melanogaster gene notchless: a novel
WD40 repeat containing protein that modulates
Notch signalling activity
TIE2/TEK receptor endothelial tyrosine kinase
Hs.89640
2
BCL2 associated X protein (BAX)
Hs.159428
2
Sepiapterin reductase mRNA
Hs.160100
2
Retinoic acid receptor beta (RARB)
Hs.171495
2
ST2 receptor: a homolog of the interleukin 1
Hs.66
1
receptor
Mitogen activated protein kinase 8 (MAPK8)
Hs.859
1
ERG gene related to the ETS oncogene
Hs.45514
1
PP35 similar to E. coli yhdg and R. Capsulatus
Hs.97627
1
nifR3
Interphotoreceptor matrix proteoglycan;
Hs.129882
1
strongly expressed in retina and umbilical cord
vein (Felbor et al, 1998)
Methylmalonate semialdehyde dehydrogenase
Hs.170008
1
gene,
HTLV-I related endogenous retroviral sequence
Hs.247963
1
Twenty known genes were selected in the UniGene/EST screen (no hits in the non-endothelial pool and minimum one hit in the endothelial pool). At least four of these genes are known endothelial specific genes: TIE1, TIE2/TEK, LYVE1 and multimerin, indicating ~ 20% prediction accuracy. Other genes, while certainly preferentially expressed in the endothelial cells, may not be endothelial specific.
TABLE 7
xProfiler differential analysis was combined with data from the
UniGene/EST screen achieving 100% certainty of prediction.
Hits in
X profiler
Hits in
non-
Unigene
prediction
endothelial
endothelial
ID
Gene description
certainty
EST pool
EST pool
Hs.13957
ESTs-ECSM1
97%
4
0
Hs.111518
magic roundabout,
100%
4
0
distant homology to
human roundabout 1
Hs.268107
multimerin
92%
5
0
Hs.155106
calcitonin receptor-
97%
0
0
like receptor activity
modifying protein 2
Hs.233955
ESTs
96%
0
0
Hs.26530
serum deprivation
94%
3
1
response
(phosphatidylserine-
binding protein)
Hs.83213
fatty acid binding
100%
3
1
protein 4
Hs.110802
von Willebrand
100%
25
1
factor
Hs.76206
cadherin 5, VE-
100%
4
1
cadherin (vascular
endothelium)
Hs.2271
endothelin 1
98%
9
2
Hs.119129
collagen, type IV,
100%
4
6
alpha 1
Hs.78146
platelet/endothelial
99%
18
5
cell adhesion
molecule (CD31
antigen)
Hs.76224
EGF-containing
100%
37
9
fibulin-like
extracellular matrix
protein 1
Hs.75511
connective tissue
100%
34
48
growth factor
xProfiler's output lists genes with 10-times higher number of tags in the endothelial than in the non-endothelial pool of SAGE-CGAP libraries. Hits corresponding to these genes in the endothelial and non-endothelial EST pools were identified by identity-level BLAST searches for mRNA (known genes) or phrap computed contig sequences (EST clusters representing novel genes). Genes are sorted according to the number of hits in the non-endothelial EST pool. Known and predicted novel endothelial specific genes are in bold.
TABLE 8
Summary of available information on magic roundabout.
UniGene
cluster ID
Transmembrane
Mapping information
and
Full-length
Longest
segments, signal
Genomic context
size
cDNA
ORF
peptide
Genomic clones
Description
ECSM1
Hs.13957
103 aa
Genomic neighbour:
1100 bp
con-
Tropomyosin
firmed
dbSTS G26129 and G28043
with
Chr. 19 Gene Map 98: Marker
5′RACE
SGC33470, Marker stSG3414,
IntervalD19S425-D19S418
AC005945, AC005795 (partial
identity)
Magic
Hs.111518
Partial cDNA
417 aa
One transmembrane
Genomic neighbour: integral
468 aa region of homology to the
roundabout
2076 bp
FLJ20798 fis,
domain predicted
transmembrane protein 1 (ITM1)
cytoplasmic portion of the roundabout
clone
by TopPred2 and
dbSTS G14646 and G14937
axon guidance protein family: human
ADSU02031
DAS. No signal
Chr. 11, Gene Map 98: Marker
ROBO1, rat ROBO1 and mouse dutt1
(acc.
peptide in the
SHGC-11739, Interval
(E = 1.3e−09)
AK000805)
available 417
D11S1353-D11S93
ORF has no apparent up-stream limit. This
1496 bp
aa ORF (SignalP)
and size comparison to ROBO1 (1651 aa)
however the true
suggests that true protein is very likely to
protein product is
be much larger
very likely to be
Possible alternative polyA sites: the cDNA
larger
clone from adipocyte tissue seems to be
polyadenylated in a different position to
the sequence from the UniGene contig
TABLE 9
List of primers used in RT-PCR reactions.
dbSTS primers were used if a UniGene entry
contained a sequence tagged site (STS).
Otherwise, primers were designed using the
Primer3 programme.
Primers (sequence or GenBank
Gene
Accession for the STS)
ECSM1-Hs.13957
G26129
Magic roundabout-
G14937
Hs.111518
calcitonin
G26129
receptor-like
receptor activity
modifying 2
Hs.233955
G21261
fatty acid
5′-TGC AGC TTC CTT CTC ACC TT-3′
binding protein 4
(SEQ ID NO: 15)
5′-TCA CAT CCC CAT TCA CAC TG-3′
(SEQ ID NO: 16)
von Willebrand
5′-TGT ACC ATG AGG TTC TCA ATG C-
factor
3′
(SEQ ID NO: 17)
5′-TTA TTG TGG GCT CAG AAG GG-3′
(SEQ ID NO: 18)
serum deprivation
G21528
response protein
collagen, type
G07125
IV, alpha 1
EGF-containing
G06992
fibulin-like
extracellular
matrix protein 1
connective tissue
5′-CAA ATG CTT CCA GGT GAA AAA-
growth factor
3′
(SEQ ID NO: 19)
5′-CGT TCA AAG CAT GAA ATG GA-3′
(SEQ ID NO: 20)
TABLE 10
ESTs belonging to ECSM1 contig sequence are as follows:
EST SEQUENCES(30)
AI540508, cDNAcloneIMAGE: 2209821, Uterus, 3′read, 2.1 kb
AI870175, cDNAcloneIMAGE: 2424998, Uterus, 3′read, 1.7 kb
AI978643, cDNAcloneIMAGE: 2491824, Uterus, 3′read, 1.3 kb
AI473856, cDNAcloneIMAGE: 2044374, Lymph, 3′read
AI037900, cDNAcloneIMAGE: 1657707, Wholeembryo, 3′read, 1.2 kb
AI417620, cDNAcloneIMAGE: 2115082, 3′read, 1.0 kb
AA147817, cDNAcloneIMAGE: 590062, 3′read
AA968592, cDNAcloneIMAGE: 1578323, 3′read, 0.7 kb
AW474729, cDNAcloneIMAGE: 2853635, Uterus, 3′read
R02352, cDNAcloneIMAGE: 124282, 3′read, 0.7 kb
R01889, cDNAcloneIMAGE: 124485, 5′read, 0.7 kb
AA446606, cDNAcloneIMAGE: 783693, Wholeembryo, 3′read
R02456, cDNAcloneIMAGE: 124282, 5′read, 0.7 kb
T72705, cDNAcloneIMAGE: 108686, 5′read, 0.7 kb
R01890, cDNAcloneIMAGE: 124485, 3′read, 0.7 kb
AA147925, cDNAcloneIMAGE: 590014, 5′read
AI131471, cDNAcloneIMAGE: 1709098, Heart, 3′read, 0.6 kb
AA733177, cDNAclone399421, Heart, 3′read
AI039489, cDNAcloneIMAGE: 1658903, Wholeembryo, 3′read, 0.6 kb
AI128585, cDNAcloneIMAGE: 1691245, Heart, 3′read, 0.6 kb
AI540506, cDNAcloneIMAGE: 2209817, Uterus, 3′read, 0.6 kb
AA894832, cDNAcloneIMAGE: 1502815, Kidney, 3′read, 0.5 kb
AW057578, cDNAcloneIMAGE: 2553014, Pooled, 3′read, 0.3 kb
AA729975, cDNAcloneIMAGE: 1257976, GermCell, 0.3 kb
AI131016, cDNAcloneIMAGE: 1706622, Heart, 3′read, 0.2 kb
AA147965, cDNAcloneIMAGE: 590062, 5′read
AA446735, cDNAcloneIMAGE: 783693, Wholeembryo, 5′read
AA147867, cDNAcloneIMAGE: 590014, 3′read
AI497866, cDNAcloneIMAGE: 2125892, Pooled, 3′read
T72636, cDNAcloneIMAGE: 108686, 3′read, 0.7 kb
TABLE 11
ESTs within the magic roundabout sequence:
EST sequences in magic roundabout (55):
AI803963, cDNAcloneIMAGE: 2069520, 3′read, 0.9 kb
W88669, cDNAcloneIMAGE: 417844, 3′read, 0.7 kb
AI184863, cDNAcloneIMAGE: 1565500, Pooled, 3′read, 0.6 kb
AA011319, cDNAcloneIMAGE: 359779, Heart, 3′read, 0.6 kb
AA302765, cDNAcloneATCC: 194652, Adipose, 3′read
AI278949, cDNAcloneIMAGE: 1912098, Colon, 3′read, 0.7 kb
AI265775, cDNAcloneIMAGE: 2006542, Ovary, 3′read
AA746200, cDNAcloneIMAGE: 1324396, Kidney, 0.5 kb
N78762, cDNAcloneIMAGE: 301290, Lung, 3′read
AI352263, cDNAcloneIMAGE: 1940638, Wholeembryo, 3′read, 0.6 kb
AA630260, cDNAcloneIMAGE: 854855, Lung, 3′read, 0.5 kb
C20950, cDNAclone(no-name), 3′read
W88875, cDNAcloneIMAGE: 417844, 5′read, 0.7 kb
AA156022, cDNAcloneIMAGE: 590120, 3′read
N93972, cDNAcloneIMAGE: 309369, Lung, 3′read, 1.7 kb
AI217602, cDNAcloneIMAGE: 1732380, Heart, 3′read, 0.5 kb
AW294276, cDNAcloneIMAGE: 2726′347, 3′read
AA010931, cDNAcloneIMAGE: 359779, Heart, 5′read, 0.6 kb
AA303624, cDNAcloneATCC: 115215, Aorta, 5′read
AI366745, cDNAcloneIMAGE: 1935056, 3′read, 0.5 kb
AA327257, cDNAcloneATCC: 127927, Colon, 5′read
C06489, cDNAclonehbc5849, Pancreas
BE218677, cDNAcloneIMAGE: 3176164, lung, 3′read
AA335675, cDNAcloneATCC: 137498, Testis, 5′read
R84975, cDNAcloneIMAGE: 180552, Brain, 3′read, 2.1 kb
AI926445, cDNAcloneIMAGE: 2459442, Stomach, 3′read, 1.9 kb
H61208, cDNAcloneIMAGE: 236318, Ovary, 3′read, 1.9 kb
AA335358, cDNAcloneATCC: 137019, Testis, 5′read
AI129190, cDNAcloneIMAGE: 1509564, Pooled, 3′read, 0.8 kb
T59188, cDNAcloneIMAGE: 74634, Spleen, 5′read, 0.8 kb
T59150, cDNAcloneIMAGE: 74634, Spleen, 3′read, 0.8 kb
R53174, cDNAcloneIMAGE: 154350, Breast, 5′read, 0.8 kb
AA156150, cDNAcloneIMAGE: 590120, 5′read
AA302509, cDNAcloneATCC: 114727, Aorta, 5′read
R99429, cDNAcloneIMAGE: 201985, 5′read, 2.4 kb
AI813787, cDNAcloneIMAGE: 2421627, Pancreas, 3′read, 1.2 kb
H62113, cDNAcloneIMAGE: 236316, Ovary, 5′read, 1.0 kb
R16422, cDNAcloneIMAGE: 129313, 5′read, 0.7 kb
T48993, cDNAcloneIMAGE: 70531, Placenta, 5′read, 0.6 kb
T05694, cDNAcloneHFBDF13, Brain
R84531, cDNAcloneIMAGE: 180104, Brain, 5′read, 2.2 kb
AI903080, cDNAclone(no-name), breast
AI903083, cDNAclone(no-name), breast
AA302764, cDNAcloneATCC: 194652, Adipose, 5′read
AA341407, cDNAcloneATCC: 143064, Kidney, 5′read
W16503, cDNAcloneIMAGE: 301194, Lung, 5′read
AW801246, cDNAclone(no-name), uterus
AW959183, cDNAclone(no-name)
R85924, cDNAcloneIMAGE: 180104, Brain, 3′read, 2.2 kb
AA358843, cDNAcloneATCC: 162953, Lung, 5′read
BE161769, cDNAclone(no-name), head-neck
W40341, cDNAcloneIMAGE: 309369, Lung, 5′read, 1.7 kb
AA876225, cDNAcloneIMAGE: 1257188, GermCell, 3′read
R99441, cDNAcloneIMAGE: 202009, 5′read, 2.3 kb
W76132, cDNAcloneIMAGE: 344982, Heart, 5′read, 1.4 kb,
TABLE 12
110 ESTs in the mouse magic roundabout cluster (Mm.27782)
AI427548, cDNAcloneIMAGE: 521115, Muscle, 3′read
AV022394, cDNAclone1190026N09, 3′read
BB219221, cDNAcloneA530053H04, 3′read
AI604803, cDNAcloneIMAGE: 388336, Embryo, 3′read
AI504730, cDNAcloneIMAGE: 964027, Mammarygland, 3′read
AI430395, cDNAcloneIMAGE: 388336, Embryo, 5′read
AI181963, cDNAcloneIMAGE: 1451626, Liver, 3′read
AV020471, cDNAclone1190017N14, 3′read
BB219225, cDNAcloneA530053H12, 3′read
BB224304, cDNAcloneA530086A21, 3′read
BB527740, cDNAcloneD930042M18, 3′read
W66614, cDNAcloneIMAGE: 388336, Embryo, 5′read
BB097630, cDNAclone9430060E21, 3′read
AI152731, cDNAcloneIMAGE: 1478154, Uterus, 5′read
AW742708, cDNAcloneIMAGE: 2780289, innerear, 170pooled, 3′read
BB118169, cDNAclone9530064M17, 3′read
AI839154, cDNAcloneUI-M-AO0-ach-e-11-0-UI, 3′read
BB206388, cDNAcloneA430075J10, 3′read
BB381670, cDNAcloneC230015E01, 3′read
BB199721, cDNAcloneA430017A19, 3′read
AI593217, cDNAcloneIMAGE: 1177959, Mammarygland, 3′read
BB219411, cDNAcloneA530054L01, 3′read
BB220744, cDNAcloneA530061M19, 3′read
BB220944, cDNAcloneA530062O22, 3′read
BB390078, cDNAcloneC230066L23, 3′read
BB220730, cDNAcloneA530061L13, 3′read
AI615527, cDNAcloneIMAGE: 964027, Mammarygland, 5′read
AI882477, cDNAcloneIMAGE: 1396822, Mammarygland, 5′read
AV025281, cDNAclone1200012D01, 3′read
BB470462, cDNAcloneD230033L23, 3′read
BB247620, cDNAcloneA730020G03, 3′read
BB555377, cDNAcloneE330019B13, 3′read
BB512960, cDNAcloneD730043I21
BB400157, cDNAcloneC330017F17, 3′read
BB320465, cDNAcloneB230385O10, 3′read
BB105670, cDNAclone9430096H10, 3′read
BB441462, cDNAcloneD030027B11, 3′read
BB137530, cDNAclone9830142O07, 3′read
AA553155, cDNAcloneIMAGE: 964027, Mammarygland, 5′read
BB319763, cDNAcloneB230382G07, 3′read
BB451051, cDNAcloneD130007I05, 3′read
BB504672, cDNAcloneD630049J11, 3′read
AI429453, cDNAcloneIMAGE: 569122, Embryo, 3′read
BB190585, cDNAcloneA330062J23, 3′read
BB257082, cDNAcloneA730076M18, 3′read
BB386699, cDNAcloneC230047P06, 3′read
BB295814, cDNAcloneB130042A09, 3′read
BB450972, cDNAcloneD130007A22, 3′read
AA718562, cDNAcloneIMAGE: 1177959, Mammarygland, 5′read
BB223775, cDNAcloneA530083K18, 3′read
AV020555, cDNAclone1190018G05, 3′read
BB226083, cDNAcloneA530095K11, 3′read
BB482105, cDNAcloneD430007O19, 3′read
BB381671, cDNAcloneC230015E02, 3′read
BB383758, cDNAcloneC230030C02, 3′read
BB257519, cDNAcloneA730080D13, 3′read
BB265667, cDNAcloneA830021I17, 3′read
BB254777, cDNAcloneA730063K20, 3′read
AV240775, cDNAclone4732443F15, 3′read
BB315010, cDNAcloneB230352H04, 3′read
BB390074, cDNAcloneC230066L16, 3′read
BB517605, cDNAcloneD830025B17, 3′read
BB484410, cDNAcloneD430025H01, 3′read
BB357583, cDNAcloneC030022J01, 3′read
AV225639, cDNAclone3830431D12, 3′read
BB554921, cDNAcloneE330016A12, 3′read
BB161650, cDNAcloneA130061H21, 3′read
BB106720, cDNAclone9530002M22, 3′read
BB535465, cDNAcloneE030043P14, 3′read
BB357738, cDNAcloneC030024B10, 3′read
AV285588, cDNAclone5031411M12
BB188339, cDNAcloneA330048H22, 3′read
AV337749, cDNAclone6430404F19, 3′read
BB065281, cDNAclone8030443H10, 3′read
BB148059, cDNAclone9930104N19, 3′read
AV252251, cDNAclone4833438P20, 3′read
BB184506, cDNAcloneA330012J24, 3′read
BB522445, cDNAcloneD930007M08, 3′read
BB520366, cDNAcloneD830041K23, 3′read
AV127290, cDNAclone2700047J01, 3′read
BB248651, cDNAcloneA730027F04, 3′read
BB008452, cDNAclone4732482M24, 3′read
BB550719, cDNAcloneE230024C07, 3′read
BB182033, cDNAcloneA230095N14, 3′read
BB480258, cDNAcloneD330045D17, 3′read
BB004855, cDNAclone4732463E03, 3′read
AV379748, cDNAclone9230013A19, 3′read
BB552137, cDNAcloneE230035B12, 3′read
BB288263, cDNAcloneIMAGE: 3490042, mammary, 5′read
BB215681, cDNAcloneA530026M11, 3′read
BB251356, cDNAcloneA730046B16, 3′read
BB503441, cDNAcloneD630043F10, 3′read
BB500571, cDNAcloneD630029E03, 3′read
BB199833, cDNAcloneA430017K13, 3′read
BB533549, cDNAcloneE030030K03, 3′read
BB098399, cDNAclone9430063L18, 3′read
BB213310, cDNAcloneA530009E09, 3′read
BB240699, cDNAcloneA630083B14, 3′read
BB217106, cDNAcloneA530040N24, 3′read
BB057432, cDNAclone7120459H22, 3′read
BB214645, cDNAcloneA530021N22, 3′read
BB218254, cDNAcloneA530048K12, 3′read
BB319841, cDNAcloneB230382O06, 3′read
BB459759, cDNAcloneD130063G22, 3′read
BB485618, cDNAcloneD430032M09, 3′read
BB517699, cDNAcloneD830025J18, 3′read
BB535595, cDNAcloneE030044M09, 3′read
BB536291, cDNAcloneE030049D17, 3′read
BB552689, cDNAcloneE330001A16, 3′read
BB552709, cDNAcloneE33C001C16, 3′read
EXAMPLE 2
ECSM4 Expression is Restricted to Endothelial Cells
In situ hybridisation (ISH) of tumour and normal tissues showed that the expression of ECSM4 is restricted to vascular endothelial cells in adult angiogenic vessels only. Analysis of normal tissues showed that expression of ECSM4 is detected in human placenta and umbilical cord foetal tissue 10.8 weeks menstrual age. As shown in FIG. 16 , ECSM4 expression is highly specific for the vascular endothelial cells of the blood vessel in placenta. Furthermore, expression was absent throughout a number of other normal tissues that were analysed, including adult liver, brain cerebrum and large vessels, prostate, colon, small bowel, heart, eye (choroid and sclera), ovary, stomach, breast and foetal bladder, testis, kidney (15.8 weeks) and foetal heart, kidney, adrenal, intestine (11.3 weeks) foetal brain (10.6 weeks) and foetal eye (16.5 weeks) (data not shown).
ISH analysis of colorectal liver metastasis biopsies showed that expression of ECSM4 was restricted to vascular endothelial cells of the tumour vessels only ( FIGS. 17 and 18 ). No expression was detected in the surrounding normal tissue. Furthermore the enhanced expression in the vicinity of the necrotic tissues ( FIG. 18 , necrotic tissue is indicated by the bright signal labelled *) is indicative and consistent with induction of ECSM4 expression by hypoxia. As such, ECSM4 may be a novel hypoxia regulated gene.
The highly restricted expression pattern of ECSM4 in angiogenic vessels in normal and tumour tissues in adult is entirely consistent with the endothelial cell selective pattern of expression determined by the in silico analysis described in Example 1.
Methods
Blocks of formalin-fixed, paraffin-embedded tissues and tumours were obtained from the archives of the Imperial Cancer Research Fund Breast Pathology Group at Guys Hospital, London, UK. An antisense riboprobe to ECSM4 cDNA was prepared for specific localisation of the ECSM4 mRNA by in situ hybridisation. The methods for pretreatment, hybridisation, washing, and dipping of slides in Ilford K5 for autoradiography has been described previously (Poulsom, R., Longcroft, J. M., Jeffrey, R. E., Rogers, L., and Steel, J. H. (1998) Eur. J. Histochem. 42, 121-132). Films were exposed for 7 to 15 days before developing in Kodak D19 and counterstaining with Giemsa. Sections were examined under conventional or reflected light dark-field conditions (Olympus BH2 with epi-illumination) under a x5, x10 or x20 objective that allowed individual auto-radiographic silver grains to be seen as bright objects on a dark background.
EXAMPLE 3
ECSM4 Polypeptide is Detected Only in Endothelial Cells
Antibodies capable of selectively binding the ECSM4 polypeptide were generated and used in immunohistochemistry to demonstrate the presence of ECSM4 polypeptide in a range of cell types ( FIGS. 21 to 26 ). Tissue samples were prepared by standard techniques in the art of immunohistochemistry.
Generation of Antibodies Recognising ECSM4.
The peptides MR 165, MR 311 and MR 336 were fused to Keyhole Limpet Haemocyanin (KLH) before immunisation of rabbits for production of polyclonal antibodies. The antibody MGO-5 was derived from rabbits immunised with the peptide MR 165, whereas MGO-7 was derived from rabbits immunised with a mixture of MR 311 and MR 336. The sequence of the peptides used to generated the polyclonal antibodies is shown below with their reference within the amino acid sequence of full length human ECSM4 as shown in FIG. 12 .
MR 165 =
LSQSPGAVPQALVAWRA
(681-697)
(SEQ ID NO: 6)
MR 274 =
DSVLTPEEVALCLEL
(790-804)
(SEQ ID NO: 7)
MR 311 =
TYGYISVPTA
(827-836)
(SEQ ID NO: 8)
MR 336 =
KGGVLLCPPRPCLTPT
(852-867)
(SEQ ID NQ: 9)
EXAMPLE 4
The magic roundabout EST sequence identified in the bioinformatics search for endothelial specific transcripts was used to isolate a cDNA of 3800 base pairs in length from a human heart cDNA library. A screen using gene specific primers showed the gene to be present in libraries from heart, adult and foetal brain, liver, lung, kidney, muscle, placenta and small intestine but absent from peripheral blood leukocytes, spleen and testis. Highest expression was in the placental library. Comparison of the magic roundabout sequence to that of roundabout revealed a transmembrane protein with homology throughout but absence of some extracellular domains. Thus, MR has two immunoglobulin and two fibronectin domains in the extracellular domain compared to five immunoglobulin and two fibronectin domains in the extracellular domains of the neuronal specific roundabouts. A transmembrane domain was identified by (i) using the transmembrane predicting software PRED-TMR and (ii) using an alignment between human MR and human ROBO1 peptide sequences. Both methods identified the same residues as the transmembrane region of human MR as amino acids 468-490. Thus, aa 1-467 are extracellular and aa 491-1007 are intracellular. The intracellular domain contains a putative proline rich region that is homologous to those in roundabout that are thought to couple to c-abl (Bashaw et al (2000) Cell 101: 703-715).
Human SHGC-11739 (GenBank acc. G14646) sequence tagged site (STS) was mapped to magic roundabout mRNA in a BLAST dbSTS search. This STSmaps to chromosome 11 on the Stanford G3 physical map (region 5647.00 cR10000 LOD 1.09 bin 129). Nevertheless, much sequence is missing and the genomic structure is not known. Search of the RIKEN database identified murine magic roundabout. The predicted molecular weight for the peptide core of human MR was 107,457 kDa. This was confirmed by in vitro translation ( FIG. 3 ).
EXAMPLE 5
ECSM4 Expression is Detectable in Tumours
In situ hybridisation was used to characterise expression of ECSM4 in vivo. Expression of ECSM4 was found to be very restricted (Table 13), with no signal detectable in many tissues including neuronal tissue. In contrast, strong expression was detected in pacenta and a range of tumours including those of the brain, bladder and colonic metastasis to the liver ( FIG. 27 ). Expression within tumours was restricted to the tumour vasculature. Immuno-histochemical staining of placenta confirmed endothelial specific expression of the protein.
A search of CGAP SAGE libraries for ECSM4 detected it only in endothelial and tumour libraries (Table 14). This was consistent with in situ hybridisation results in the adult showing that expression was restricted to tumour vessels (colon metastasis to liver, ganglioglioma, bladder and breast carcinoma).
TABLE 13
Expression of magic roundabout in human tissue in vivo.
Expression detected
Placenta and umbilical cord foetal tissue (10.8 weeks menstrual age)
Vessels in colorectal liver metastasis, ganglioglioma, bladder and breast
carcinoma.
Expression not detected
Adult liver, brain cerebrum and large vessels, prostate, colon, small bowel,
heart, eye choroid and sclera, ovary, stomach, breast
TABLE 14
CGAP SAGE libraries in which magic roundabout was found
on the basis of gene to tag mapping
Library
Tags/million Tags
HDMEC
171
HDMEC + VEGF
224
Medulloblastoma
102
Glioblastoma multiforme
85
Ovary, serous adenocarcinoma
59
Glioblastoma multiforme, pooled
48
HDMEC, human dermal microvascular endothelial cells;
VEGF, vascular endothelial growth factor.
EXAMPLE 6
Induction of ECSM4 in Hypoxic Endothelial Cells
Initial RT-PCR detected ECSM4 expression in endothelial but not other cell lines such as fibroblasts (normal endometial and FEK4), colon carcinoma (SW480 and HCT116), breast carcinoma (MDA453 and MDA468) and HeLa cells. Ribonuclease protection analysis has confirmed and extended this ( FIG. 11 a ). ECSM4 expression was seen to be restricted to endothelium (three different isolates) and absent from fibroblast, carcinoma and neuronal cells. Induction of ECSM4 in hypoxia in endothelial (but not non-endothelial cells) was seen when expression of ECSM4 was analysed using two different RNase protection probes. Expression was on average 5.5 and 2.6 fold higher in hypoxia for HUVEC and HDMEC respectively. Western analysis identified a weak band of 110 kD in human dermal microvascular endothelial cells (HDMEC) but absent from the non-endothelial cells types ( FIG. 11 b ). The band was more intense when the HDMEC cells were epxosed to 18 h hyposia, consistent with ECSM4 being a hypoxically regulated gene. | The present invention relates to endothelial cell-specific genes and encoded polypeptides and materials and uses thereof in the imaging, diagnosis and treatment of conditions involving the vascular endothelium. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of co-pending application Ser. No. 342,182, filed Jan. 25, 1982 entitled "Unitized Stair Tread With Adjustable Hangers", now abandoned.
TECHNICAL FIELD
The present invention relates to modular apparatus used in constructing stair treads, and more particularly discloses a prefabricated modular carrier for stair treads which is adapted to be used between pairs of unnotched stringers disposed at a predetermined angle between a first surface and a second surface.
BACKGROUND OF THE INVENTION
During the last decade, the cost of housing in the United States, and in some of the other industrialized countries of the world, has risen tremendously. In the United States in particular interest rates which were unheard of, and illegal, ten years ago are now commonplace. The 1970s saw interest rates in excess of 20% on mortgage money. This has led to a situation in which many middle class people have been unable to purchase single family dwellings.
Partly in response to this situation, lower cost methods of construction of housing have been developed. A number of prefabricated housing units are available in the market and have become quite popular in recent years due to the increase in quality of such units and their relatively low cost. Such units often include a number of standardized components which may be used in more than one particular house of the manufacturer, thus reducing the manufacturer's cost of inventory, and the need to employ skilled labor to fabricate custom components for a house.
As anyone who has ever attempted it knows, the construction of staircases in the conventional manner requires a fair degree of skill and precision measuring and cutting. In the conventional manner, a pair of parallel boards are disposed between a lower surface and an upper surface, normally first and second floors, to form a pair of stringers. When the location and length of the stringers are determined, perpendicular rectilinear cuts are made on the stringers at regular intervals. The horizontal portions of these cuts support the treads and the risers are attached to the vertical portions of the cuts during normal stair construction.
It is most desirable in constructing a staircase to make sure that stairs are regularly spaced and that the distance between the top stair and the second floor and the bottom stair and the first floor be commensurate with the distance between treads on the balance of the staircase. This is important for both aesthetic and safety reasons. Since people often walk down stairs at night, without the aid of light, or early in the morning when they are not fully awake, a discontinuity in the distance between adjacent treads, or a tread and a floor surface can give rise to an unpleasant surprise and often injury to the ankle or knee of a person who encounters such a discontinuity and is not prepared for it.
Many makers of prefabricated houses have adopted standard staircases as components of such housing and thus a large number of stringers wih the same cuts can be fabricated by the manufacturer and used in a variety of different units. However, the prior art has not provided an inexpensive and efficient apparatus which may be used to construct stairs between floors separated by a variety of distances which will still provide the desirable even spacing between adjacent treads, the top and bottom treads, and the floor surfaces.
Several prior art arrangements for providing prefabricated metal stairs have been made. For example, the method described in U.S. Pat. No. 3,839,840 shows an arrangement for constructing metal stairs where the stringers are provided with the flanges of a conventional "I-beam". A prefabricated cason for use in constructing metal staircases is also shown in British Pat. No. 1,082,462.
However, neither of these arrangements are satisfactory, or applicable to the more commonly encountered situation of constructing staircases in homes and other buildings in which wooden stringers are normally used.
SUMMARY OF THE PRESENT INVENTION
The present invention provides a modular carrier for stair treads which is particularly designed to overcome the above noted shortcomings in the prior art. In particular, the present invention provides a modular carrier designed to be used on an otherwise conventional stringer which may be cut and secured in place, without the need for notching the stringers for risers and treads.
Furthermore, the present invention provides a modular carrier for stair treads which allows the user to cut the ends of the stringers so that they fit between floor levels in a conventional fashion, and then simply put them in place in the same manner as they would be placed had the conventional notches been cut. Thus, conventional methods of measuring, cutting and securing stringers can be used without the requirement that the time consuming step of providing rectilinear cuts for treads and risers be made.
The present invention provides such an apparatus by having a surface for supporting a stair tread, which can include an integral stair tread thereon, and having a pair of spaced apart vertical side walls extending above the tread surface. The side walls include a top edge which is tilted with respect to the plane of the tread at a predetermined angle. The predetermined angle is equal to the angle at which the stringers are placed with respect to the horizontal, assuming that the treads are to be horizontal, in the resultant staircase.
Attached to the top edge of each of side walls is a mounting plate which is adapted to be laid over the upper surface of the stringers. Thus, the present invention provides an arrangement wherby, once the stringers are set at a predetermined angle, the integral, tread, side wall, and mounting plate may simply be laid over the stringers and secured thereto.
The present invention further provides a plurality of notches and/or score lines for fitting adjacent modular carriers together so that the resultant staircase includes the proper number of stair treads, spaced properly with respect to each other.
In the method of the present invention the user need only determine the height between the two levels to be connected by the staircase and the number of steps desired on the case. From this, the distance along the mounting surface for each modular carrier is unambiguously determined. In constructing the staircase, the user need only overlap portions of the mounting surface of the next adjacent lower carrier over the lower end of the mounting surface of each carrier at a predetermined position determined by the above-referenced calculation. In the preferred form of the present invention, indicia corresponding to the results of the above-noted calculation are provided so that the staircase may be quickly assembled without error.
In another form of the present invention, an extended portion of each mounting surface is provided and score lines are provided on the extended portion. The extended portion is made of a frangible material, such as relatively thin fiberglass, so that parts of the extended portions of the mounting surfaces may be broken off at the appropriate places and the stairs may be constructed by simply abutting the remaining portions of the mounting plates. Alternately, the carriers according to the present invention may be constructed of metal, and the appropriate part of each extended portion may be cut off prior to assembly of the staircase.
Thus, by providing a plurality of embodiments of the present invention with several respective predetermined angles between the horizontal tread and the slope of the mounting surfaces, a wide variety of staircases, suitable for virtually any application, may be constructed.
Thus, it is an object of the present invention to provide a modular carrier for a stair tread which is readily adapted to be used in connection with conventional wooden stringers which do not have to be cut along their lengths extending between two floor levels.
It is a further object of the present invention to provide a modular stair carrier designed to be used on stringers set at a predetermined angle with respect to the horizontal for which the number of stairs in a given staircase may be varied according to the desired spatial relationship between adjacent treads.
It is a further object of the present invention to provide an improved method of stair step construction using modular carriers for the stair treads which is quick, efficient, and can be dependably implemented by relatively unskilled labor.
It is a further object of the present invention to provide prefabricated modular carriers for stairs which may be made from a variety of materials including stamped metal and molded fiberglass.
That the present invention accomplishes these objects, and overcomes the above-noted drawbacks of the present invention will become apparent from the detailed description below.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a pictorial view of a first preferred embodiment of the present invention.
FIG. 2 is a pictorial view of a plurality of the preferred embodiment of FIG. 1 set on a pair of stringers.
FIG. 3 is an end elevational view of the preferred embodiment of FIG. 1 showing the geometric relationship between the parts.
FIG. 4, consisting of FIGS. 4A and 4B, shows alternate arrangements for joining adjacent modular carriers according to the present invention.
FIG. 5 is a pictorial view of an alternate embodiment of the present invention.
FIG. 6A is a side elevational view of a third embodiment of the present invention and FIG. 6B is a pictorial view of the embodiment of FIG. 6A.
DETAILED DESCRIPTION
Turning first to FIG. 1, a pictorial view of the first preferred embodiment of the present invention is shown. The first preferred embodiment is one for which a pair of side walls and a tread of predetermined width are integrally formed. As may be seen in FIG. 1, a bottom tread, or tread, 15 is provided. Extending vertically from each end of the bottom tread is a pair of side walls, 16 and 16'. Each of side walls 16 and 16' includes a top edge shown, respectively, as 17 and 17'.
As may be seen in FIG. 1, the top edge 17 forms a predetermined angle, shown as φ with respect to the plane of bottom tread 15. Connected to each of the top edges 17 is a mounting plate 18. Mounting plate 18 intersects side walls 16 at a right angle and lies in a plane which is parallel to top edge 17 and tilted at the predetermined angle φ with respect to the plane of the upper surface of bottom tread 15.
Each of mounting surfaces 18 includes a lower scored or notched surface 19 and an upper scored or notched surface 20 extending above a respective upper end point 21 of top edge 17.
As is explained hereinbelow, portions 19 and 20 are notched in the preferred form so that the upper surface of portion 20 will engage the lower surface of portion 19 when lapped thereover during use of the preferred embodiment. Alternately, scoring or notching of lower surface 19 is omitted and extended portion 20 on mounting plate 18 is scored so that predetermined increments of the extended portion of the mounting surface may be broken off or cut off during use.
Turning next to FIG. 2, an example of two of the embodiments of FIG. 1 as used in a portion of an assembled staircase are shown. In FIG. 2, the modular carriers for the present invention are disposed between a pair of stringers 25 and 25'. Dashed line 26 shows a horizontal line parallel to the horizontal upper surface of bottom tread 15.
As may be seen in FIG. 2, stringers 25 and 25' are disposed at the same predetermined angle φ with respect to the horizontal as top edge 17 forms with bottom tread 15. Mounting plates 18 are laid over the upper support surfaces 27 and 27' of stringers 25 and 25'. Note that in the present example the predetermined angle φ is shown with respect to the bottom edge of stringer 25. This assumes the common convention of having upper support surface 27 of stringer 25 parallel to the bottom surface. However, it will be readily apparent that the important factor is that the upper support surface 27 form the predetermined angle φ with the horizontal, irrespective of the geometry of the lower surface of the stringers.
Also shown on FIG. 2 are a plurality of holes 28 and 28' in mounting plates 18 and 18'. Likewise, a plurality of holes 29 are shown in side walls 16 These are provided so that screws, nails or the like may be used to secure side walls 16 and mounting plates 18 to stringers 25.
Turning for a moment to the intersection between the two carriers shown atop stringer 25, one aspect of the preferred method of using embodiments of the present invention will be described. Upper end point 21 of top edge 17 is visible in FIG. 2. Thus, a part of extended portion 20 is uncovered, as shown in the drawing figure. In this arrangement, notches appearing on the top side of extended portion 20 of mounting surface 18 are covered and engaged by corresponding notches (not shown) on the lower surface of mounting plate 18 for the immediately adjacent carrier above extended portion 20. It is within the scope of the present invention that upper and lower surfaces overlap in either sense (upper over lower or lower over upper), but FIG. 2 shows the preferred arrangement so that remaining free ends of extending portions 20 of the carriers will not be exposed.
Turning next to FIG. 3, a side elevational view is shown to demonstrate the geometry of the present invention. As in the previously described drawing figures, top edge 17 forms a predetermined angle φ with respect to bottom tread 15. Notch means 32 appear on the lower surface of mounting plate 18 and corresponding notch means 35 appear on the upper surface of extended portion 20 of mounting plate 18.
The exemplary preferred embodiment shown in FIG. 3 is one in which length dimension L is 12 inches. The total height between the surface of tread 15 and the extreme end of extended portion 20 is shown by dimension line 36 and is preferably 71/2 inches. The vertical projection of extended portion 20 is indicated by dimension line 37 which is 1 inch in the preferred embodiment. Thus, the vertical height between tread 15 and upper end point 21, shown by dimension line 38, is equal to 61/2 inches. From this, simple trigonometry indicates that predetermined angle φ in the preferred embodiment is 32° since it is readily determined as the arctangent of seven and one-half inches divided by 12 inches.
From this, it is apparent that the length of extended portion 20 is approximately 1.89 inches (1/SIN 32°). Thus, if the notches of notch means 32 and 35 are equally spaced at 1/8 inch intervals, fifteen 1/8 inch notch intervals are provided in the preferred embodiment.
The preferred forms of the method of the present invention are executed as follows. It is first assumed that either the stringers will be disposed at predetermined angle φ, determined by a single available embodiment of the present invention, or that two or more embodiments of the present invention are available to the user characterized by two distinct angles φ. The user selects the appropriate angle φ, and set the stringers accordingly.
The total vertical distance between the two floors to be connected is designated as H. Next, the user selects a number n to represent the number of steps desired between the two floors. H/n is defined as h, the height between adjacent treads. An arbitrary example is shown as h in FIG. 3.
Alternately, the distance h between adjacent treads may be most important to the user and a first approximation of this number can be selected first. This number can then be divided into H to determine a first approximation for the number n. n must then be rounded to an appropriate integer value to provide evenly spaced stairs. It will be readily apparent that for any given embodiment of the present invention, and any given distance H between two adjacent stories, the possible range of values for n may be determined by taking the integer part of H divided by the minimum value for h (the length of dimension line 38) and dividing H by the maximum value for h (the length of dimension line 36).
However it is arrived at, the value of h determines the value of distance d along mounting plate 18 as shown in FIG. 3. Thus, first step of the method may be considered calculating distance d.
As shown in the example of FIG. 3, d extends between the lower end of mounting plate 18 and a point indicated at 40 on extended portion 20. In the preferred form, indicia are provided next to notches 35 on extended portion 20 which are calibrated in values of h. Thus, in placing the modular carriers on the stringers, adjacent carriers need to be disposed so that lower end point 41 of mounting plate 18 engages point 40 in the next contiguous carrier below and the stairs will be properly and evenly spaced.
In an alternate method, referred to above, extended portion 20 is made of frangible material and provided with score lines corresponding to notch means 32 and thus part of extended portion 20 extending above point 40 may be broken off. In using this method, point 40 is merely butted against point 41 for adjacent carriers. Alternately, the carrier of the present invention may be constructed from metal and extended portion 20 may simply be cut off at point 40.
It should further be apparent to those skilled in the art that (n-2) carriers according to the present invention will be needed in the above recited example since the significance of the number n is the number of equally spaced increments of height h between the floors. Naturally, one of these increments will be met by the space h between the topmost tread of the staircase and the second floor itself, and another will be met by the space between the bottommost tread and the first floor surface. Thus, it should be understood that the reference to n means that n-2 carriers will actually need to be provided.
Turning next to FIGS. 4A and 4B, an alternate arrangement for notch means 32 and 35 are shown as 32' and 35'. In this arrangement, the notches on extended portion 20 are downward facing and are thus shown as 35' to suggest that they correspond to notch means 35 shown on FIG. 3 but are distinct therefrom. Similarly, notch means 32 near lower end point 41 are shown as 32'.
FIG. 4B shows an example of the indicia 45 and score lines 46 on extended portion 20. The example shown on FIG. 4 corresponds to the above description in which indicia 45 are denominated in values for h. It will be appreciated from viewing the indicia shown on FIG. 4B that the values for h extend between the 61/2 inches and 71/2 inches described hereinabove in increments of 1/8 inch. Of course, other increments may be used and it is also possible to use indicia calibrated in terms of distance d, where desired
From the foregoing, it will be readily appreciated that while the preferred form of the invention is to have extended portion 20 be present above upper end point 21 of top edge 17, that fully equivalent embodiments of the present invention may be constructed wherein the extended portion lies below point 41 and thus, the particular end from which the extended portion is provided is not considered cirtical. Likewise, structures corresponding to the extended portions 20 may be provided separately and used as spacers.
FIG. 5 shows an alternative arrangement for the present invention in which like parts of the first preferred embodiment are numbered with like reference numerals. The embodiment of FIG. 5 differs from the embodiment of FIG. 1 in that a bottom plate 48 is provided for carrying a tread but no tread is integrally formed with this embodiment. A plurality of holes 49 are provided as means for attaching a tread to the bottom plate which, naturally, will be used in connection with screws, nails, or the like. The embodiment of FIG. 5 is one which allows use of the present invention with stairs characterized by treads of variable width. From the foregoing, it will be readily apparent that a mirror image of the embodiment of FIG. 5 must be used in connection with the embodiment shown and that these two are used in pairs to construct a staircase according to the present invention.
FIGS. 6A and 6B shown an alternate embodiment of the present for which only a single specific embodiment of the present invention must be provided for the construction of a staircase. This particular embodiment is limited to use in construction of staircases with stringers extending at 45° to the horizontal.
As is shown in FIG. 6A, predetermined angle φ equals 45°. From inspection of FIG. 6, it will be apparent that the embodiment shown therein is bilaterally symmetrical with respect to a line shown as 55 bisecting the right angle at the corner of vertical side wall 16. Thus, the 45° angle shown at the upper corner of the embodiment of FIG. 6A is also designated as φ, and is equal to 45°. Similarly, two extended portions 51 are provided between end points 50 in this embodiment. In the preferred form of the embodiment of FIG. 6A, score lines 52 are provided at each of extended portions 51 and extended portions 51 are constructed of frangible material so that it may be readily broken or cut along the score lines. As may be seen in FIG. 6, a pair of bottom plates 48 are provided on each edge of vertical side wall 16.
Due to the symmetry of the embodiment of FIG. 6, it will be readily understood that mounting plate 18 may be laid over either the right or left hand stringer (with the stringers set at 45°) and one or the other of bottom plates 48 will be horizontal, ready to support a stair tread. In using this embodiment, it is preferable to break off the entirety of an apropriate one of extended portions 51 to correspond to the lower end point of mounting plate 18 shown in the previously described embodiment, and to break off an appropriate portion of the other of extended portions 51 to set the carriers for appropriate tread-to-tread spacing.
From the foregoing description, it will be apparent that the present invention accomplishes the objects set forth above and overcomes the cited drawbacks of the prior art. In view of the foregoing description of several embodiments of the invention, other embodiments will suggest themselves to those skilled in the art and the scope of the present invention is to be limited only by the claims below. | A modular carrier for stair treads (15) is provided so that treads may be evenly spaced and hung between a pair of stringers (25, 25'). A pair of vertical side walls (16, 16') extend above the tread and have a mounting plate connected thereto lying in a plane which intersects the plane of the tread at a predetermined angle (φ). With the stringer set at this angle with respect to the horizontal, the treads lay in proper horizontal orientation. The plurality of notches or score lines are provided at the ends of the mounting plate (19, 20) which may be broken off, or overlapped, facilitating easy construction of evenly spaced stairs. Alternately, the left and right hand carriers are provided as separate units having a bottom plate 48 so that treads of varying widths may be used with the device. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is a continuation of U.S. patent application Ser. No. 09/848,052, filed May 3, 2001, which claims the benefit of the filing date of U.S. Provisional Patent Application Ser. No. 60/202,147, filed May 5, 2000 and entitled “PERFORMANCE ANALYSIS TOOL FOR LOCATION SYSTEMS”, the entire contents of which are hereby expressly incorporated by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to a system and method for wireless location systems. More specifically, the invention relates to a performance analysis software tool designed to predict the performance and geographical coverage of wireless location systems.
BACKGROUND OF THE INVENTION
[0003] Various location determining systems (LDS) are used to determine the location of a mobile user. For example, a Global Positioning System (GPS) typically uses a set of twenty-four orbiting satellites to allow ground-based users to determine their locations. These systems provide the user with location information based on LDS such as GPS data. Some location systems include LDS elements integrated into a cellular phone, while others have equipment added to the wireless infrastructure.
[0004] Designing a location system has been cumbersome and involves manipulation and analysis of a variety of information. Location sensor density and geometry are extremely important to obtaining acceptable location data. For example, Angle of Arrival (AOA) techniques require sensor information from a minimum of two sites to obtain a location, three to estimate the quality of a location and a minimum of four to identify and reject severely corrupted (multipath) data from one site. Time Difference of Arrival (TDOA) techniques (both at the sites and in the handsets) require sensor information from a minimum of three, four, and five sites for the same capabilities. Factors such as the type of service area to be covered (rural vs. urban) or the characteristics of the wireless network (existing cell site densities, geometry of cell sites with respect to each other and areas to be covered, restrictions on antenna placement, availability at cell sites, etc.) are all factors affecting location performance and are incorporated in this software platform.
[0005] The geometry of the site infrastructure has a major impact on the quality of the locations. Geometric Dilution Of Precision (GDOP) plays an important role which must be considered. An extreme example of poor geometry is found along (relatively) straight highways between major cities. In these cases, cell sites are often located in a string near the highways providing cellular/PCS coverage only to the highway. An AOA location system with sensors located only at the sites will only be able to locate a mobile set as being between two highway sites. TDOA systems will only be able to locate the mobile set along a hyperbola intersecting the highway. This is at least better information if one can assume that the mobile set is on the highway and not on a nearby farm-to- market road. Even this would require a unique algorithm for use only in these areas. Note that a combined AOA/TDOA system would be able to provide location services under these circumstances.
[0006] Location systems have coverage requirements that conflict with those of Cellular/PCS networks. For example, an objective of a cellular/PCS design is to limit the radio coverage of a given base station. A location system, on the other hand, requires that each receiver site “see” (i.e., receive a useful signal) well beyond the limits of a single base station. A location system or technique generally operates the best, i.e., it offers the best accuracy for the highest percentage of the time, when it has an abundance of sites that receive the signal from the phone. This means that the higher the number of receiver sites that “see” the mobile unit the better the performance.
[0007] As explained above, because of the divergent requirements of wireless communication and wireless location systems, a specialized design and analysis software tool is required for proper design of a location system. There are a number of Cellular/PCS coverage design tools available on the market but none provide the utility to predict a location system coverage.
[0008] Therefore, there is a need for a software tool for analyzing wireless location systems with a user friendly graphical user interface (GUI).
SUMMARY OF THE INVENTION
[0009] The software of the present invention predicts the availability and accuracy of locations determined by a variety of different techniques such as Angle of Arrival (AOA), Time of Arrival (TOA), Time Difference of Arrival (TDOA), and hybrid variations of these angle and time of arrival as well as signal strength based techniques. The tool is capable of performance analysis whether the pertinent measurements are performed in fixed sensors associated with the network infrastructure, or in the handset. The tool can also determine if the deployed location sensors meet, exceed, or fall short of providing the expected coverage and performance. The tool allows the location system designer to eliminate redundancies if not all sensors are needed and propose additional sites where location coverage holes are present. The software tool offers similar capabilities to location and monitoring services (LMS) networks.
[0010] In one aspect the present invention describes a method for analyzing performance of a wireless location system. The method includes the steps of storing data related to location equipment, wireless infrastructure, handsets, terrain map, and morphology map; generating a site radial file for path loss and time/angle error based on the stored terrain and morphology maps; computing a multi-site forward and reverse link signal strength map for determining coverage of the location system; generating a multi-site margin/error map from the computed multi-site forward and reverse link signal strength map and the stored data; and generating an error estimate map for the location system.
[0011] In another aspect, the present invention discloses a system for performance analysis of a location system comprising: means for generating a radial model and a radial map including a plurality of radial paths for a site from a stored raster map; means for selecting a propagation model from a stored plurality of propagation models for predicting a path loss along each radial path; at each point along a radial path, means for predicting accumulated angular errors and time delay errors; and means for generating an error estimate from the path loss and the accumulated angular errors and time delay errors.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The objects, advantages and features of this invention will become more apparent from a consideration of the following detailed description and the drawings, in which:
[0013] FIG. 1 is a simplified process flow, according to one embodiment of the present invention;
[0014] FIG. 2 is a simplified process flow related to FIG. 1 , according to one embodiment of the present invention;
[0015] FIG. 3 is a picture providing an example screen of a GUI, according to one embodiment of the present invention;
[0016] FIG. 4 is an exemplary window within the GUI of FIG. 3 ;
[0017] FIG. 5 is a simplified process flow for generating site radial maps for terrain and land use, according to one embodiment of the present invention;
[0018] FIG. 6 is a simplified process flow for generating site radial maps for path loss and time/angle error, according to one embodiment of the present invention;
[0019] FIG. 7 is a simplified process flow for generating rectangular maps from radial maps, according to one embodiment of the present invention;
[0020] FIG. 8 is a simplified process flow for generating a cluster map, according to one embodiment of the present invention;
[0021] FIG. 9 is a simplified process flow for generating forward and reverse link signal strengths, according to one embodiment of the present invention;
[0022] FIG. 10 is a simplified process flow for generating mobile unit transmit power, according to one embodiment of the present invention;
[0023] FIG. 11 is a simplified process flow for generating a multi-site time/angle error map, according to one embodiment of the present invention;
[0024] FIG. 12 is a simplified process flow for generating a location error map, according to one embodiment of the present invention;
[0025] FIG. 13 is an exemplary picture showing location error in a metropolitan area, according to one embodiment of the present invention;
[0026] FIG. 14 is an exemplary picture showing number of location sensors receiving useful signal from a handset, according to one embodiment of the present invention; and
[0027] FIG. 15 is an exemplary block diagram of a software tool, according to one embodiment of the present invention.
DETAILED DESCRIPTION
[0028] The present invention is a performance analysis software tool designed to predict the performance and geographical coverage of a wide array of wireless location systems. The tool applies to both network-based and handset based location technologies. These location techniques find broad application in Cellular and PCS networks, as well as in other wireless networks, including those for LMS. The software tool of the present invention is designed to work as a stand alone package or as a value added adjunct to wireless communication network design tools.
[0029] In one embodiment, the software tool of the present invention provides a windows based user interface that is fairly simple to use by a radio or design engineer. It also provides outputs in the forms of graphs, tables and reports for display and/or printing. In one embodiment, the tool runs on a Pentium-based, IBM-PC compatible machine running Windows NT 4.0. However, hosting on other platforms with a variety of different operating systems such as Linux or UNIX are also provided. The tool is modular in its structure to allow the gradual inclusion of capabilities and features, as well as to support on-going refinements. The typical user does not need to perform any programming, although hooks are made available to add modules by authorized technical users. Such development could be initiated based on the users' unique needs and requests.
[0030] The accuracy of the location determination is described by the expected location determination error (based on the mean square error). There are two widely used definitions for availability, and both capabilities are provided by the tool. In one, availability is determined by whether location determination is feasible at all or not. This relates directly to the minimum number of location sites (sensors) that “cover” a specific point under consideration on the map. (The minimum number of sites required to yield a location varies from one technique to another and is described briefly below for the different techniques.) In the second definition, availability is whether a location system statistically provides a location accuracy that meets a pre-selected accuracy threshold for example, 100 m over 67% of a given area.
[0031] In the family of network or infrastructure based location techniques, the position determination is performed by means of sensors that are placed at fixed locations, most typically co-located with the wireless cell sites.
[0032] For example, AOA sensors include specially designed antennas mounted at cell sites or other propitious locations to measure the angle of arrival of the mobile signal. Because the wave front arrives at the differently positioned antenna elements at slightly different times, the phase measured at each element relative to the others is different. Angle of arrival is calculated from these differing phase measurements using a specially designed receiver and is delivered to the location determining system controlling element as azimuth from true north (or other fixed directional reference).
[0033] The intersection of the rays formed by the reported azimuths provide the location of the caller. A major advantage of AOA position finding is that only two sites are required to obtain a position. Continuous system calibration is also unnecessary. AOA systems, however, are particularly sensitive to wave reflections caused by multipath in the urban environment. Their accuracy degrades also as the distance between the transmitter (e.g., the handset) and the AOA sensor increases.
[0034] In TDOA, the difference in the arrival times at multiple receiver sites of a signal emitted from a transmitter is used to calculate the position of that transmitter. An advantage of the TDOA approach is that special antennas are not required—current site antennas may be used. The sensor typically contains the functions of reception (filtering, down-conversion), signal sampling and storage, demodulation of certain signals, and calibration. Continuous calibration or control of system timing accurate to 10's of nanoseconds is required to achieve the required time measurement accuracy.
[0035] A closely related technique to TDOA is TOA, which applies when the transmitter and receiver are tightly time synchronized. In this case, the differential time alignment in TDOA is not required, and it is possible to measure the round trip propagation delay between a sensor and a handset, hence infer the range (distance) to the handset. TOA is normally used in conjunction with AOA or TDOA to broaden their applicability or enhance performance.
[0036] In hybrid angle and time techniques, the location system attempts to combine the performance advantages of AOA with those of TOA or TDOA, enabling, in theory, using only one or two sensors to detect the position of the transmitter (e.g., the caller's handset), even when poor geometry renders pure AOA systems ineffective. These hybrid systems also promise improved performance (location accuracy and coverage). The drawback is the increased complexity at each hybrid site and in system control.
[0037] Multipath pattern recognition is an approach which is not immediately related to TDOA, however it is often combined with AOA to improve its performance. Multipath pattern recognition entails comparing the signature of the signal received at various sensor sites with the that stored in a substantial data base containing the signatures created during extensive calibration runs spanning the area. Pattern recognition and classification algorithms are used to obtain the best match and the location. This technique is better suited to long calls or mobile calls where a significant amount of filtering can be applied to discard erroneous matches.
[0038] In handset based approaches, the handset plays an active role in performing measurements and optionally computing the location. Systems pertaining to this family can be divided into the following three broad classes.
[0039] Enhanced Observed Time Difference (E-OTD) technique is essentially TDOA but with the measurements performed at the handset. The times of arrival of signals from the serving as well as neighboring cell sites are observed at the handset. This technique also entails the broadcast by the network of the differences between the actual time bases at the different cell sites in the area. This information is used by the handset to enhance the location computation if it is performed there. Alternately, the information on the OTD measurements performed at the handset could be transmitted back to the network where the location is computed. In either case, from a location determination stand point, the technique is similar in its performance to TDOA, but with distinct parameters relating to its implementation particulars. E-OTD has been the technique of choice for a number of GSM operators and infrastructure vendors.
[0040] Forward Link Triangulation (FLT) technique is essentially TDOA at the handset. This flavor of TDOA is most commonly applied to CDMA networks because of the tight timing constraints maintained on the pilot transmitted from each CDMA cell site. FLT generally uses these pilots from the serving and neighboring sites to perform a TDOA computation at the handset. Analogous to E-OTD, some calibration of the time base accuracies at the cell sites is performed and is disseminated over the air to the handsets.
[0041] GPS Based Location techniques rely on the presence of a GPS receiver or sensor in the handset. Pseudo ranges from GPS satellites are measured and used to obtain the location. The computation is performed either in the handset or at a server on the network side if the measurement information is transmitted back to the network. So called assistance data may also be transmitted from the network to aid the performance of the GPS measurements performed in the handset.
[0042] The tool of the present invention obtains the geographic coverage and performance of AOA and TDOA based location systems including their variations and hybrids, whether the measurements are performed at fixed sensor sites or at the handset. As such, traditional network-based AOA and TDOA, network-based hybrid AOA/TDOA, and E-OTD and FLT are all techniques whose performance is predicted by the tool. Techniques that apply to a CDMA network, such as FLT, require special handling in the program to account for CDMA's unique radio coverage prediction, but as far as location performance prediction, the same procedures and algorithms described in detail below are applied.
[0043] Although the detailed algorithms discussed above do not explicitly depict the case of GPS measurement in the handset, because GPS is a TDOA system with the transmitters in the sky, the same methodology described below is readily applied to predict the performance of those systems as well. Straight-forward extensions to the propagation, geometry and signal models used with terrestrial transmitters are applied in obtaining the performance for the GPS case.
[0044] FIG. 15 is an exemplary simplified block diagram of some components included in one embodiment of the tool of the present invention. As shown in FIG. 15 , in this embodiment, the software tool of the present invention includes the following components: infrastructure technologies and environment databases 1502 , model & algorithm packages 1504 , and interfaces 1506 . Databases 1502 includes wireless infrastructure databases 1508 , location system deployment databases 1510 , geographic databases, and databases for multipath profiles 1524 . geographic databases include information for: terrain 1518 , morphology/land use 1514 , roads 1516 , salient features 1520 (e.g., large towers or obstacles), and population 1522 .
[0045] Model & algorithm packages 1504 include multipath profile generation/characterization algorithms and multipath profile databases 1530 , location technology databases and location system performance models 1532 , propagation algorithm databases 1526 , and reverse link adjustments 1528 .
[0046] Interfaces 1506 include GUI 1538 , printing module & interface 1540 , LAN interface 1542 , and outside system interface 1544 . System administration utility module 1534 handles the system functions controlled by a system administrator, such as system access control using a password system. System Controller 1536 provide a variety of system control functions.
[0047] In one embodiment, the software tool supports the entry, reading, or importing of the specifics of a target cellular or PCS infrastructure. This wireless infrastructure data includes:
air interface type; cell site locations (latitude and longitude); site elevation AMSL (maybe computed automatically from terrain); sector height (above surrounding terrain); number of sectors; antenna gain; TX and RX pattern propagation model type; downtilt; number of channels; transmit powers; and power control window upper and lower limits.
[0049] The default mode of data entry is the keyboard/GUI. However, other modes of data entry are possible. In one embodiment, each cell site of an infrastructure is assigned a number and each of its sectors is assigned another number to distinguish antennas that may be physically separate (e.g., on different sides of a building). In one embodiment, the tool includes separate databases for each target cellular/PCS infrastructure.
[0050] In one embodiment, the software tool supports entering, reading, or importing of the location system infrastructure deployment information. The information pertaining to the location system deployment includes: location system type or name; unit type (if multiple receiver types or configurations are available); location receivers' antenna category (same as wireless network or not); location system antenna locations (latitude and longitude or cell site number if same antenna); antenna type (if not same as cellular); number of antenna units at a given installation; location system antenna elevation; location system antenna height; and cabling losses. In one embodiment, the tool includes separate databases for each location system deployment. Information pertaining to a given location technology that is not deployment (placement) specific is maintained in another database called the Location Technologies database.
[0051] In one embodiment, the tool reads and maintains database with parameters specific to various location technologies. Each databases contains information specific to one location technology or one release version of it that is under investigation. This non-placement specific information is retained in the location infrastructure database. Some of these parameters include: type of technology; antenna types (gains and/or patterns); receivers' sensitivities and noise data; receiver bandwidth; integration time(s); known receiver biases; any known or estimated receiver jitter; quality indicators of receiver or receiver type; and quality indicators computation (if available).
[0052] The tool contains location system performance algorithm packages to enable predicting system performance. For every location technology identified above, performance computation algorithms are developed using both theoretical and empirical formulas. Distinct modules within each package are possible to compute the effects of specific phenomena on the subject technology, for example, GDOP. The user is able to adjust certain parameters in the equations to support “what if” and sensitivity analyses. These algorithms typically take inputs from multiple databases, including: infrastructure, geographic, multipath profile, and location technology. They also exercise or cause the execution of the propagation package and wireless control algorithms. The outputs of the performance algorithms are expressed in several ways, including: average and RMS errors, probability of missed detection, number and identity of location receivers observing a mobile at given thresholds, and coverage availability (assuming these thresholds). In one embodiment, the results are made available in tabular formats, graphical formats using data layers, and in summary reports.
[0053] The tool also supports the entry, reading, or importing of the specifics of mobile units. This data is primarily the unit type and model. For a number of models, default characteristics are initially read and then maintained into the database. The characteristics include: peak transmit power; power control range; support of discontinuous transmission; speech specification (analog or speech coding rate); and support of data services, if any.
[0054] The tool has the ability to read and store the terrain information for a certain area determined by its corner latitude and longitude coordinates. The tool is also able to display this information as a raster data layer. Maps from the USGS or other private sources conforming to standard formats are supported. For example, both one degree and 7.5 minute arc maps are supported. 300 m and 100 m terrain maps, among others, are also supported. The tool also has the ability to read, store and display morphology type maps. One such source is the USGS Land Use Land Cover (LULC) data maps. The tool also makes it possible to edit and design custom morphology maps. It displays this information as a raster data layer.
[0055] The GUI allows simple entry of many information elements through dialogue windows. However, some elements may also be obtainable from sources other than the GUI, e.g., an external system like a switch or a CD-ROM. Preferably, each database has a set of menu-driven dialogue windows that enable entering and/or editing, as appropriate, their information elements. For example, nominal transmit power, receiver site coordinates, antenna height, receiver noise figure, land use/morphology category, and so on. The dialogue windows enable the creation of a new wireless or location site and the entry of its parameters into the appropriate databases. Preferably, each model within a package has associated with it a dialogue window to specify, enter parameter into, or edit (as appropriate) the model. Certain core parts of the models require administrator access for modification.
[0056] Prior to performance prediction, two distinct types of site sectors are defined in a project within the tool: (1) wireless sectors (e.g., Cellular, PCS, ESMR), and (2) geolocation (or simply location) sectors. Sites may be comprised of either wireless sectors, geolocation sectors, or both. A unique graphical user interface (GUI) allows the user to define the project, enter and edit the particulars of both the wireless and location sites, and otherwise input and manipulate all the information that the program may need to provide the predictions sought by the user. A picture providing an example screen of this GUI is shown in FIG. 3 . An exemplary window within this layered GUI, called the Site Editor, is shown in FIG. 4 . The Site Editor provides a mechanism for the user to input, edit and select wireless and geolocation site information.
[0057] Furthermore, the tool is able to read, store and display interstate, major and secondary roads. This data may be stored as line or curve rather than raster data. It is possible to display and/or overlay this information with/on other data layers. The tool is capable of distinguishing between Interstate highways and other roads. The tool reads, maintains and displays population density raster maps. In one embodiment, data based on US census information is used. Also, it is possible to read or define information elements that specify certain salient features in the area under investigation. Examples include large transmitters, tanks, obstructions, airports, etc.
[0058] The software tool of the present invention begins with wireless (e.g., cellular) site or area coverage prediction methods, and adds considerable new modeling to arrive at a prediction of geolocation network performance. An exemplary process is illustrated at a top level in the flow charts depicted in FIG. 1 and FIG. 2 . These charts show eight major “boxes” or steps culminating in obtaining the desired location error map. The description below will follow these top level charts and will elaborate on the eight main steps, providing details on their algorithmic contents with a more detailed flow chart for each step.
[0059] FIGS. 1 and 2 are exemplary process flows according to one embodiment of the present invention. In block 102 of FIG. 1 , site radial maps for terrain and land use are generated. This entails developing a radial model and a radial map, centered on the site, for the terrain and morphology (land use) from common raster maps. The details of this process are shown in the exemplary flow process of FIG. 5 .
[0060] At each point along a radial path, a combination of accumulated angular errors and time delay errors (for AOA, TDOA, their hybrid location techniques) are predicted. The combined path loss and accumulated error radial maps are then converted to square raster maps, one for each cellular site and each geolocation site, as shown in block 104 . The details of this process are shown in the exemplary flow processes of FIGS. 6 and 7 .
[0061] A cluster of sites of fairly arbitrary size is also defined. The maps calculated for the individual sites are then combined into a single, combined raster map for the cluster in block 106 . These maps contain at each point, the path loss for the best wireless server and the error data for the geolocation sites with the highest received signals. Up to N geolocation sites can be included, where N is currently 8 by default but can be changed. Details of the steps of block 106 are further described in FIG. 8 .
[0062] In block 108 (explained further in FIG. 9 ), both forward and reverse link signal strength maps are computed for the cellular network to determine the presence of cellular coverage. From these maps, a map of actual cell phone transmit power is calculated. The receive power margins are then computed for the geolocation sites (up to N as described above) in block 202 (explained further in FIG. 10 ).
[0063] In block 204 , a multi-site receive power map, containing the signal margins at each map point, is then constructed for these location sites. The additional angle and/or delay noise at each point due to geolocation sensors receive noise are then estimated. These errors are combined with the noise previously estimated from the terrain/land use environment and already available in the cluster raster map in block 206 (explained further in FIG. 11 ).
[0064] In block 208 , at each map point, an error covariance matrix is then generated from the up to N angle and/or time error estimates. The semi-major axis of the error ellipse is derived from this matrix, to determine the error estimate, as shown in block 210 (explained further in FIG. 12 ).
[0065] The error results are then output in the form of a display map covering the cluster or metropolitan area. Color coding is keyed to the size of the estimated error. Alternately, the estimated probability that the error will meet a specified criterion is displayed. The tool is interactive in nature and allows the user to conduct a number of what-if scenarios, to optimize location site placement and location system performance.
[0066] Referring now to FIG. 5 , the number of radials required to adequately represent the site's signal propagation is calculated in block 502 . This number is based on the resolution of the original terrain file data and the (entered) calculation radius for the site. The resolution along each radial is typically the same as the resolution of the terrain file data. Next, the latitude and longitude are calculated in block 512 for each point (block 508 ) on each radial (block 504 ). This requires the sine and cosine of the azimuth of the radial (block 506 to calculate the horizontal and vertical distances from the site (center) to the point on the radial, shown in block 510 .
[0067] From these distances, the local radius of the earth, and the site's coordinates, the longitude and latitude of a point on the radial are determined in block 512 . The terrain altitude for the point (defined by its latitude and longitude) is obtained in block 514 from the original terrain file 516 , and a morphology code is obtained in block 520 from the original morphology files 518 . The morphology code is an index into a table that contains an effective height, loss, and effective obstruction width for each type of land usage (urban, light suburban, forest, open land, etc.). This information is then stored together in radial format. This process is repeated for the next point (blocks 522 and 524 ) and the next radial (blocks 526 and 528 ).
[0068] The second major step for the top level exemplary process flow of FIG. 1 is to generate the radial files for path loss and for the time and/or angle error, as shown in block 104 . In one embodiment, the tool includes a set of propagation models that can be selected by the user for the purpose of computing the path loss. The selection may be based on a sector, or larger areas. The following models are some examples of the propagation model selections: Okumura-Hata (cellular band), Cost 231 (PCS band), Line of Site, Lee's model with effective antenna height, Fresnel zone corrections for paths partially obstructed by terrain. Other propagation models may be easily added to the tool. The user has the ability to override key default parameter values in the model selected.; for example, the intercept of the Hata model (as seen on a log-log scale).
[0069] Furthermore, the design of the propagation module enables importing measurement data in a standard file format to perform least square fit type computations. The results of these computations are used to adjust the parameters of the selected propagation model over a certain application region to be defined by the user. Another capability of the tool is to automatically select a permissible combination of models (e.g., O-H and LOS) on a per-pixel, per site basis. For each propagation model made available on the forward wireless link, a set of adjustments are implemented to allow its use for predicting the reverse link path loss. The details of this multi-faceted process are depicted in the exemplary process flow of FIG. 6 .
[0070] Referring now to FIG. 6 , several salient sub-steps are shown including: spherical ( 4 / 3 ) earth computation (block 606 ); propagation model computation to generate the path loss including the effects of diffraction and antenna height (blocks 628 and 630 ); computation of loss due to antenna pattern (block 638 ); computation of the angle errors (block 662 ) or time errors (block 660 ) that result along the radial paths in an AOA or TDOA based system, respectively.
[0071] For each entry along each radial route, the total number of obstructions is determined and the characteristics of each path leg from site to obstruction to other obstruction(s) to mobile unit are determined in block 620 , and the accumulated diffraction loss is calculated for each obstruction in block 628 . Diffraction loss is calculated similar to the method described in “The Mobile Radio Propagation Channel, Parsons, Halsted Press, 1992, pp 48-49,” the contents of which are expressly incorporated by reference herein, following the “The Epstein-Peterson method”. For each point (block 616 ), the number of path legs are obtained in block 620 . For each path leg (block 626 ), the diffraction loss is calculated and summed, as shown in block 628 . From the last path leg, and the average slope of the land just before the mobile unit, the effective height of the site antenna is calculated in block 630 . Both the ray from the mobile and the slope of the land just before the mobile are projected back along the last leg to the site antenna position and the difference in altitude is used as the effective antenna height. From this and the total distance to the mobile unit, the nominal path loss is determined in block 632 from a selected propagation model 634 (e.g. Hata, Cost 231).
[0072] A host of standard propagation models are made available to the user to predict the path loss along each radial. Hybrid variations of these models are also permissible in the tool. For example, Okumura-Hata (O-H) is one typical model widely used for urban or suburban propagation. The O-H model includes parameters that could be adjusted and selected by an expert user to adapt it specifically to certain propagation environments, e.g., an unusually open area. The tool's user friendly GUI permits the user to select and edit these detailed parameters of the propagation model. Other models that are more appropriate for specialized propagation environments, e.g., for very high sites, can be used, at the user's option, instead of a standard O-H model.
[0073] This propagation model is then modified by the morphology loss at all points where the ray penetrates the morphology. Using the azimuth of the current radial and the elevation to mobile unit or first obstruction, if any; the stored antenna pattern 636 ; and the antenna's azimuth and tilt, the antenna pattern loss is determined in block 638 . This loss is added for the total modeled path loss in block 640 .
[0074] At each point along a radial path (blocks 644 and 646 ), a combination of accumulated angular errors or time delay errors are computed as applicable (for AOA, TDOA, and hybrid location techniques). The angular measurement error is accumulated along the propagation path below the morphology (clutter) height based on an equivalent obstruction size, an equivalent obstruction density, and the distance from the sensor antenna. The steps in blocks 648 and 650 are used to determine whether or not each of the rays is impacted by the clutter. The type of the algorithm to be used for the analysis is determined in blocks 652 and 654 .
[0075] In block 656 , individual AOA errors are calculated by calculating the angular error from the antenna caused by the path diffracting around the obstruction (or reflecting off an adjacent obstruction). In block 658 , TDOA errors are calculated by subtracting the direct path from the site from the path around the obstruction to the mobile unit. Each error is squared for accumulation as a variance in blocks 660 for TDOA/EOTD and block 662 for AOA.
[0076] The equivalent obstruction sizes and densities are abstract terms arrived at through integrating field measurements into the model and are different for each morphology (land use) type. The resolution along the radial path remains consistent with the terrain/morphology database. Next point and next leg is selected in blocks 664 and 668 , respectively. If the end of loop is not reached (block 676 ), next point is selected in block 616 . If the end of loop is reached, next radial is selected for analysis in block 610 .
[0077] The next major step in FIG. 1 is to convert the combined path loss and accumulated error radial maps to square raster maps, one for each cellular site and each geolocation site. In one embodiment, the details of these conversions are performed as shown in FIG. 7 . In FIG. 7 , first, the box map dimensions are determined to fit the radial signal file and the box map is set to the same resolution as the radial distance resolution, as shown in block 702 . From here, a signal map entry is obtained (block 708 ) for each latitude and longitude (blocks 704 and 706 ) in the box map. The signal data (path loss and error) is then stored in the box map's raster format, as shown in block 712 .
[0078] It is quite common for radio engineering and location system planners to focus their analysis on a subset of the sites that have been initially entered into the project prior to processing. This is, for example, to examine in more detail a specific area or section of a city, or to conduct what-if analyses. The cluster size is fairly arbitrary. The rectangular maps calculated in the previous step for the individual sites are now combined into a single, combined raster map for the cluster. The details of this procedure are depicted in the exemplary process flow of FIG. 8 . The cluster maps contain at each point the path loss for up to N sites as their coverage usually overlaps.
[0079] Referring to FIG. 8 , based on the user's input, the boundaries (latitude and longitude) of the overall cluster are determined from the site box map 805 sizes and positions, as shown in block 802 . Then, the box map is aligned with the cluster map in box loop of block 804 . This is done by obtaining the box map's upper left coordinate (latitude and longitude) in block 806 and determining where this position is in the Cluster map, as shown in block 808 . Inserting the box data into the cluster map starts at this point. At each point in the cluster map (blocks 820 and 822 ), the signal is extracted from the box map 805 in block 824 and is inserted into the cluster map in block 828 . In this process, the site signals are ordered by received signal strength, the best wireless server being first in the list. These are the sites with the highest signal levels received from the handset (or vise-versa at the handset). The default value for the number of sites N is 8, but can be changed and selected differently by a user. The resolution of the cluster maps is user selectable but is typically the same as the original terrain maps.
[0080] Referring back to the high level exemplary process flow of FIG. 1 , the next step is computing the forward and reverse link signal strength maps for the best server in the cellular network, as shown in block 108 . This is to determine the presence of cellular coverage. (This implies that the tool also determines the likely/best server for a given mobile's location.)
[0081] As shown in FIG. 9 , for each line in the cluster map (block 902 ) a signal strength is obtained. The path loss is subtracted from the effective radiated power (ERP) of the best server site to obtain the forward signal strength. Alternatively, the path loss is subtracted from the maximum ERP of the mobile unit to obtain the reverse signal strength, as shown in block 912 . The ERP of the cellular sites are obtained from the Site Data database 908 and the maximum ERP of the mobile unit from the mobile unit data database 910 .
[0082] Full use of most of the propagation models for path loss computation requires the availability of terrain information. Nevertheless, In one embodiment, the tool has two modes: a no terrain mode and a full terrain mode. When no terrain information is available the user enters a height for the mobile manually. The overall heights of the cell sites is computed from manual input of site elevation AMSL plus manual input of an antenna height. When terrain data is available and accessible, the tool automatically computes the site and mobile user elevation from the coordinates manually provided and the antenna height entered.
[0083] From the forward and reverse link signal maps (block 108 ), a map of actual cell phone transmit power is calculated in block 202 . The details of this steps are shown in FIG. 10 . For each cluster line (block 1010 ) and cluster column (block 1012 ), forward signal margins and return signal margins are calculated in blocks 1024 and 1028 , respectively. From the forward signal map 1014 and mobile unit data 1016 , path loss and mobile unit receive sensitivity is subtracted from the ERP of the best server site to obtain forward signal margin, as shown in block 1024 . If this margin is positive (block 1026 ), from return signal map 1018 and site data 1020 , path loss and site receive sensitivity is subtracted from the ERP of the mobile unit to obtain the return signal margin, as shown in block 1028 .
[0084] In block 1030 , the mobile unit power is calculated as the minimum power necessary to maintain the reverse link so long as both the forward and reverse margins are positive. Mobile unit power never goes below the minimum mobile unit power entered into the program. The computation takes into account the power control implemented in the wireless network and followed by the handset. Again, the particular parameters of the mobile unit are obtained from the mobile unit data database 1022 .
[0085] As depicted in block 204 of FIG. 2 , the receiver powers are now computed. The receiver power margins are also computed as described in the previous paragraph for the pertinent geolocation sites (up to N as described above). As shown in block 206 , a multi-site margin/error map, containing the signal margins at each map point, is then constructed for the N location sites. This map is essentially identical to the cluster map discussed previously, except that the location sensor sites are used instead of the cell sites and the error data is recorded in addition to the signal margin data. Using algorithm database 126 the propagation algorithms 128 , and the time/angle error algorithms 130 , a computation is performed at this stage to include the additional angle and/or delay noise at each point due to geolocation sensors receive noise. These are based on sensor characteristics and signal margins. The details for these algorithmic steps are shown in FIG. 11 .
[0086] Similar to the exemplary process of FIG. 8 , the boundaries (latitude and longitude) of the overall cluster are determined from the site box map sizes and positions using the location signal box maps 1104 , as shown in block 1102 of FIG. 11 . Then, the box maps within the overall cluster map are aligned with it. This is done by obtaining the box map's upper left coordinate (latitude and longitude) in blocks 1110 and 1114 . Next, for each location in each box map (block 1126 and 1128 ), latitude and longitude are determined in block 1130 . The latitude and longitude are then converted to the line/column coordinates used in the mobile unit power map, as shown in block 1132 . The mobile unit power is then obtained in block 1133 , similar to the process of FIG. 10 .
[0087] Depending on whether the mobile unit is transmitting (because it has positive cellular link margins), then the signal margin to the location sensor (forward or reverse) is determined in blocks 1158 or 1154 , respectively. If the margin is positive, then the appropriate error is added to the position by insertion sort in blocks 1168 or 1166 depending on the type of the location algorithm used (blocks 1162 and 1164 ). These location sensor related errors are combined with the errors previously estimated from the terrain/land use environment and already available in the cluster raster map.
[0088] The final computational step in FIG. 2 is to obtain at each map point an error covariance matrix from up to N angle and/or time error estimates, as shown in block 208 . The semi-major axis of the error ellipse is derived from this matrix. This is the error estimate at any given point on the map. The detail of this step is shown in exemplary process flow of FIG. 12 .
[0089] Referring now to FIG. 12 , for each line and each column (blocks 1202 and 1204 ), using the Multi-site Error map 1210 , the inverse of the covariance matrix is calculated in block 1208 . The inverted matrix 1212 is then used to calculate the semi-major axis of the error ellipse in block 1214 .
[0090] The covariance matrix for AOA is:
P = [ ∑ ( - Δ y k d k * υ k ) 2 ∑ ( - Δ y k d k * υ k ) * ( Δ x k d k * υ k ) ∑ ( - Δ y k d k * υ k ) * ( Δ x k d k * υ k ) ∑ ( Δ x k d k * υ k ) 2 ] - 1 = [ σ x 2 p 12 p 21 σ y 2 ]
where: Δγ k =vertical component of distance from position to site k. Δx k =horizontal component of distance from position to site k. d k =distance to site k. υ k =variance of measurement k.
[0095] For TDOA, the covariance matrix is:
P = [ ∑ ( Δ x k d k * υ k ) 2 ∑ ( Δ y k d k * υ k ) * ( Δ x k d k * υ k ) ∑ ( Δ x k d k * υ k ) ∑ ( Δ y k d k * υ k ) * ( Δ x k d k * υ k ) ∑ ( Δ y k d k * υ k ) 2 ∑ ( Δ y k d k * υ k ) ∑ ( Δ x k d k * υ k ) ∑ ( Δ y k d k * υ k ) ∑ ( 1 υ k ) ] - 1 = [ σ x 2 p 12 p 13 p 21 σ y 2 p 23 p 31 p 32 σ b 2 ]
where: Δγ k =vertical component of distance from position to site k. Δx k =horizontal component of distance from position to site k. d k =distance to site k. υ k =variance of measurement k.
[0100] For combined AOA-TDOA, the first matrix is added to the upper left rows and columns of the second matrix and then the resulting matrix is inverted to yield the desired covariance matrix.
[0101] In all three cases, the semi-major axis of the error ellipse is:
σ = 1 2 [ σ x 2 + σ y 2 + ( σ x 2 - σ y 2 ) 2 + 4 P 12 2 ]
[0102] The error results are then output in the form of a display map covering the cluster or metropolitan area. Color-coding is keyed to the size of the estimated error. An example of this output is shown in FIG. 13 . Alternately, the estimated probability that the error will meet a specified criterion is displayed. A host of intermediate results such as forward and reverse link margins and Cellular best server can also be displayed in support of location system planning activities. Another very useful output plot is the number of location sensors “seeing”; i.e., receiving a useful signal above sensitivity floor, from a handset. An example of this type of plot is shown in FIG. 14 . Outputs as those shown in FIG. 13 and FIG. 14 provide clear graphical representations of location system accuracy and availability.
[0103] Default outputs in many cases are graphical; e.g., location error contours, GDOP contours, coverage areas, color coded regions to indicate the number of observing receivers above a certain threshold., and so on. However, the user has the option to display certain outputs in other formats, e.g., tables.
[0104] Printing dialogue windows are user friendly, permitting the user to use both map scale specifications as well as mouse movements to select the printable area. Different icons are used to signify different site categories. For example, existing, proposed, what-if, and neighboring are possible categories that have somewhat different icons to assist the user in the analysis.
[0105] The user is able to select the colors for the color-coded displayed categories through dialogue windows under an “Options” menu entry. Preferably, certain color components, e.g., terrain shading gradations, water bodies, morphology categories, highways, etc., may be available for selection by the user. The graphical outputs are of sufficiently high resolution and the refresh speed of the screen is maintained high enough to provide the user with a good work environment.
[0106] Moreover, the tool supports common business-quality inkjet color printers. Varying paper sizes are supported by the tool as well. Black and white report and table printing are also supported. In one embodiment, printing control is performed through menu selection. Printer selection and feature control are provided through printer setup dialogue windows. Print item or area selection are provided through dialogue windows. Both keyboard entry of print object size as well as mouse-based specification of an area on the display are possible. Both direct connection to the printer and connection through networks such as a LAN are supported.
[0107] The tool also supports interfacing to certain outside systems. It is convenient at times to import database information from outside sources. This, at times, is the only way a database can be maintained current with a dynamic deployment. For example, the cell site database may be maintained in the mobile switching center (MSC) or connected to it and has up to date information on the wireless systems' cells, channel assignments, powers, etc. This information may also be imported by the tool.
[0108] The tool also provides data base and system security. Preferably, user created data used in an analysis session cannot be deleted except by its owner or by the system administrator. Also, a user may save the data used in a session for subsequent use. The system includes password access control for using the tool.
[0109] With its user friendly GUI, structured menus, and various intermediate and final output options, the tool is a flexible, interactive tool that offers the wireless location system planner a host of powerful design capabilities. Not only does it enable the user to determine location system performance, it also enables him or her to conduct exercises to optimize location site placement, and to perform various coverage and cost-benefit tradeoffs.
[0110] It will be recognized by those skilled in the art that various modifications may be made to the illustrated and other embodiments of the invention described above, without departing from the broad inventive scope thereof. It will be understood therefore that the invention is not limited to the particular embodiments or arrangements disclosed, but is rather intended to cover any changes, adaptations or modifications which are within the scope and spirit of the invention as defined by the appended claims. | The software of the present invention predicts the performance of a wireless location system, including its accuracy, availability, and coverage. The tool can determine if the deployed location sensors meet, exceed, or fall short of providing the expected coverage and performance. The tool allows the location system designer to eliminate redundancies if not all sensors are needed and propose additional sites where coverage holes are present. The software tool includes a graphical user interface for ease of use. | 7 |
FIELD OF THE INVENTION
This invention relates to compositions and methods for repelling pests, such as insects, arthopods (spiders, ticks, etc.), and other undesired non-human species. More specifically it relates to a repellent composition containing only naturally occurring ingredients.
BACKGROUND AND PRIOR ART
Repellents have been used for as long as history has been recorded, to prevent insects, arthropods, etc., from harming or annoying subject hosts such as humans, pets and other domesticated animals, and so forth. In addition, repellents have been used to prevent harm from pests such as insects and arthropods on inanimate materials, such as clothing, furniture, foodstuffs, etc. Examples of such materials are well known, including moth balls, and citronella candles. In the 20th century, very powerful, and very toxic chemicals have been developed which either repel or kill the aforementioned pests. Examples of these include "DDT" and "DEET". (Only acronyms are given, because these compounds are extremely well known to the artisan).
The noted toxicity of the aforementioned materials has been shown to not be restricted to the pests against which they are directed. Rachel Carson, in Silent Spring, documented the effect of DDT on the environment. Recently, DEET has been implicated as a toxin and potential carcinogen. Thus, there is an interest in safe, non-toxic chemicals which are also useful as pest repellents.
Safety to the user is not the only concern with respect to these repellents. As Silent Spring and other works have shown, repellents and other toxic chemicals persist in the environment for surprisingly long periods of time. Many repellents are used outdoors, generally in pristine areas which are not exposed to toxins. These persist, generally with harmful and damaging consequences. Further, those repellents which are toxic impact the natural ecosystems to which they are released, affecting complex, evolved systems of the native fauna. As an example of this, generally dragonflies are not considered an insect pest. They breed however, in wetlands which also habituate other insects, such as mosquitoes, which are considered pests. Application of a toxic repellent to ward off mosquitoes can also harm dragonflies, especially in the larvae, or nymph phase, where food is ingested in soluble form via gills. The resulting damage to the dragonfly population results in an increase in the population of their natural prey--including mosquitoes--which can lead to increases in the spread of diseases borne by the mosquitoes.
The foregoing example is just one of a number which could be cited to show the effect of pesticides and repellents on natural systems. Given the complex interrelationships that define nature, there is much that is unknown, and much that can be disturbed, sometimes permanently.
It is thus perhaps not surprising that there is interest in repellents which are not synthetics, and which may not be toxic.
An early example of a specific repellent, i.e., one directed against a particular type of insect, may be seen in U.S. Pat. No. 173,945, to Hall et al. This patent describes a moth repellent suitable for use on articles such as furs, woolen goods and pictures. The composition contains alcohol, turpentine, tar, camphor, mirbane essence (nitrobenzene), camphor spirits, citronella essence, bitter almond essence, and cedar extract. This liquid is brushed, or sprinkled on the area to be protected.
It will be understood from the disclosure that this composition is clearly unsuited for topical application to skin or other body areas of humans or domesticated animals, as many of the items are themselves toxic or noxious.
U.S. Pat. No. 351,897 is to the same effect in that it teaches a repellent composition suitable for application to paper. The composition contains tar, petroleum, oils of cedar, pennyroyal, sassafras and citronella, as well as creosole, carbolic acid, and sulphur. This composition is incorporated in, rather than applied to the paper, as it is added during the pulping process, or impregnated therein
Bishopp et al., J. Econ. Entomol 18: 776 (1925) discusses the results of "test jar" experiments In these, a meat sample is coated with the material to be tested and is placed in a jar After a given period of time, the meat is studied for insect reaction. The reference states that some of the "essential oils", e.g., Oils culled from the essences of various plants and plant parts, show promise. Citronella, fennel, camphor (crude), clove bud oil and clove powder are mentioned.
In an extensive study, Parman et al., Technical Bulletin No. 80 (September 1928, U.S. Dept. of Agriculture) studied various substances to determine if they were effective against blow flies. The goal was to find prospective wound treating agents. In Table 9 of this reference, various essential oils were tested. Of 26 of these, three of the oils of the invention, i.e., citronella oil, pennyroyal oil, and camphor oil, were ranked 15th, 19th and 20th in terms of efficacy. Camphor oil, in fact, attracted insects of one species.
U.S. Pat. No. 2,041,264 describes various emulsions, one of which may contain citronella oil. Such emulsions are said to have insect repellent properties, although no empirical evidence supports this, at least in the cited patent.
By 1957, one sees a turning away from natural insecticides as Hall et al., Insect Repellents and Attractants 5(9): 663 (Sept. 1957) espouse the use of DDT and state that oil of citronella, pennyroyal, cedar, and camphor are "obsolete" because while they have a certain efficacy and limited repellency toward mosquitoes, this is "short lived". Indeed, this turning away from the essential oils is continued in U.S. Pat. No. 2,302,159, to Wasum, who says that citronella has a "strong unpleasant odor" and that some of the essential oils are annoying and possibly harmful against tender or sunburned skin.
In U.S. Pat. No. 4,193,986, a flea treatment composition is described. The vast majority of the composition (93-98%) is inert. The remaining, active fraction contains pennyroyal (10-40 parts), eucalyptus oil (5-20 parts), cedar oil (3-10 parts) citronella oil (5-10 parts), and oil of rue (1-2 parts). The preferred composition is 17-32 parts pennyroyal, 8-16 parts eucalyptus, 5-8 parts cedar, 5-8 parts citronella, and 1.25-1.75 parts rue. This material is designed for use on animals previously infected with fleas.
The ubiquitous citronella is used again in U.S. Pat. No. 4,320,112, where it is combined with naphthalene to form a pest repellent for garbage bags and the like.
U.S. Pat. No. 4,671,960 teaches a flea repellent. A collar device is taught and contains both plant solids (pennyroyal, eucalyptus, camomile), and small amounts of the oils of pennyroyal, eucalyptus and citronella.
This survey of the art shows that there is no teaching of the invention, which is a topical composition useful as a pest repellent, this composition comprising equal parts of the natural oils of citronella, cedar and wintergreen in a non-toxic carrier. It has been found, surprisingly in view of the art, that these compositions are effective when applied to human subjects. Further, by using an oil base, it has been found that a surprisingly large amount of effect ingredient, i.e., anywhere from 15-40 parts of the total composition, may be the active mixture. In tests in the field, the compositions of the invention not only performed effectively but did not aggravate the skin of subjects who were exposed to extremes of heat and humidity.
The invention is described in more detail in the description which follows.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
As described herein, the invention is a composition, suitable for use as a topical for humans, which has pest repellent properties. "Pest" as used herein is not limited to insects, as the material has been found to repel arthropods as well, such as ticks. A benefit of the composition is that it is a repellent, but is not toxic, so the various "pests", which are only pests when a host is introduced, are not themselves harmed.
The inventive compositions contain equal amounts of the natural oils of citronella, cedar and wintergreen. These natural oils are combined in a non-toxic, oil based carrier, such as oleic acids (i.e., olive oil).
"Natural" as a modifier of the word "oil" is an important descriptive. It is generally known that even under the most stringent conditions of purity, "natural" substances are not 100% uniform. In developing this invention, it was found that while every formulation of natural oils was effective, regardless of source, synthetic materials were not.
While citronella, cedar and wintergreen oils are required in the pest repellent compositions, they may also contain natural oil of pennyroyal.
The required oils comprise from about 15 to about 33 percent, or parts, of the entire composition, i.e., each oil is present in from about 5 to about 11 parts of the total composition. When pennyroyal oil is added, the amounts of the three can be reduced. Additionally, natural oils of eucalyptus and camphor can be added, in small amounts.
In a particularly preferred embodiments, and the one used in the experiments which follow, the constituents of the repellent composition are as follows:
______________________________________Citronella 6.9 partsCedar 6.9 partsWintergreen 6.9 partsPennyroyal 10.3 partsOlive oil 69.0 partsComposition 100 parts______________________________________
All materials are readily available from, e.g., health food stores, and formulation of the compositions simply involves mixing the recited oils together.
A composition in accordance with the above formulation was tested in the following case studies.
CASE STUDIES--TEST 1
A group of fifteen volunteers applied the composition described above during a wilderness trek in the Midwest, during which time the activities included mountain climbing, wilderness walking, etc. The subjects were asked to record what insects they observed. While responses varied, nearly all reported chiggers, horseflies, blackflies, ticks, and mosquitoes. Some also reported wasps, horseflies, fleas and gnats. These descriptions are consistent with insect populations in the Oklahoma Flatlands, which is where the test took place. The subjects were asked to apply the composition to the exposed parts of their bodies--arms, legs, face, etc., in the morning before the day's activities, and in the evening before retiring. Some also applied it at midday as well. Approximately half of the respondents reported that they experienced no insect bites or stings. Two subjects reported a few ticks, but only one received any tick bites. The efficacy of the composition was good for about 7 hours, at which time a second application was desirable.
CASE STUDIES--TEST 2
A study was carried out in May, 1990 over an approximately two week period. Six volunteers, travelling in the New Jersey Pine Barrens observed heavy populations of ticks, mosquitoes, and blackflies. The composition referred to supra was applied 2-4 times a day. The volunteers experienced no mosquito bites and there were reports of observing ticks lighting on exposed but protected skin, and leaving without biting or attachment. In addition, volunteer subjects reported that exposed areas which had not been protected were bitten by mosquitoes and other insects.
CASE STUDIES--TEST 3
A test was carried out in Eastern Kansas, at a National Wildlife refuge. At the time of the test, the area was experiencing heavy infestation of "flood mosquitoes", which are a large, and aggressive variety.
The composition was applied anywhere from 1-4 times a day, and no bites from mosquitoes were reported. In addition, it was observed that chigger bites were experienced on unprotected skin at night.
CASE STUDIES--TEST 4
Smaller group of volunteers tested formulations in South Central Pennsylvania, the Eastern region of North Carolina, Maine, and the Virginia coastal marshes. Gnats, biting flies, ticks, mosquitoes, horseflies, and blackflies were observed, although all insects were observed in all areas. The volunteers applied the formulation once, and found that this was generally sufficient to repel the insects and ticks.
The foregoing case studies show that the composition described herein is generally effective against all insects present as well as arthropod fleas and ticks. In nearly every case, the subjects were completely satisfied with the product, which either eliminated or drastically reduced the frequency of insect and tick attack.
Thus, the compositions described above are useful as topicals for repelling pests, such as insects and ticks. The fact that it is effective on humans would had the skilled artisan to conclude that efficacy would be expected with domestic animals, including pets. Hence, a method for repelling pests is taught, wherein the above compositions are used by applying them to the exposed skin or other areas of the body. "Other areas" includes, e.g., hair, foot soles, and unexposed body parts.
As efficacy on a living subject is less predictable than is efficacy on inanimate material, the foregoing results suggest that the composition is also effective as a repellent for inanimate material, such as clothing, furniture, and so forth. In addition, it suggests that the material may be effective as an environmental repellent, when used in the form of a fogger, non-aerosol spray, and so forth.
The material can be used in the oil based form, described supra. and also as a cream, lotion, spray, roll-on, or other conventional form of repellent. These need not be described herein, as they are readily known to the skilled artisan.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, it being recognized that various modifications are possible within the scope of the invention. | An environmentally safe, topical pest repellent is described. The repellent action is attributable to a mixture of natural oils of citronella, cedar, and wintergreen. These natural oils, mixed in equal amounts, are combined in a non-toxic base, such as olive oil. The mixture is effective against diverse species, including mosquitoes and ticks. | 8 |
FIELD OF THE INVENTION
[0001] The present invention relates to a solvent composition as well as to its use to remove deposits and incrustations. In particular, this invention describes a solvent composition free of or with a low content of aromatics, and high biodegradability for solubilizing asphaltenes and paraffins and other oil-derived organic deposits, and its use to remove said deposits in the oil industry.
BACKGROUND OF THE INVENTION
[0002] The deposition of organic materials originating from crude oil, such as asphaltenes and paraffins, is deemed to compromise satisfactory exploration and production of oil. Records show that severe asphaltene deposits can stop oil production, requiring the use of mechanical processes and, in some cases, even well re-drilling (Kelland, 2014). The deposition of organic materials can occur at various points from extraction from the reservoir, which may cause obstruction in rock pores, affecting significantly the production of the well, to pipes and equipment during transport of crude oil and fluids, such as pipes, valves and pumps in both platforms and refineries, and can cause pressure drops in lines, favor other deposits, the formation of sites favorable to corrosion and, in the worst cases, prevent runoff.
[0003] Several techniques are employed in the oil industry to tackle this problem. The most common preventive technique is the use of paraffin and asphaltene inhibitors in which chemicals are injected to ensure that such organic compounds remain stable in suspension in crude oil. Another technique is the use of dispersants, which are chemicals added to break the paraffin deposits in smaller particles, so that they can be reintegrated into the oil stream. However, inhibitors and dispersants are designed to operate within specific runoff conditions, and possible disturbances can cause destabilization of the system and inefficiency of the inhibitor or dispersant, resulting in the precipitation of organic deposits. Therefore, although the industry has been employing increasingly the use of such inhibitors and dispersants, in many cases the non-definitive nature of these solutions will make the use of remediation techniques necessary, the main one being the treatment with paraffin and asphaltene dissolvers or solubilizers.
[0004] In the past, a widely-used technique was the introduction of heated crude oil above the melting point of paraffins and asphaltenes and the recirculation in the well annulus between injectors and producers. This method is extremely expensive as it requires heating large quantities of crude oil, and poses risks of fire and explosion risks in the reservoirs where the oil has a low flash point (US 2014/0121137).
[0005] Other techniques consist in an adaptation of the above solution in which crude oil is replaced by other heated fluid systems, which may contain acid, water, and aromatic solvents. U.S. Pat. No. 3,930,539 provides a reactive treatment method of organic deposits, in which the heat released by the reaction between the hydrochloric acid and phosphoric acid with ammonia allows solubilizing the paraffin while disintegrating the rock formation. Not only does this solution pose risk to the well operator, but it does not even address the issue of asphaltene deposits. U.S. Pat. No. 4,836,283, U.S. Pat. No. 6,592,279, and U.S. Pat. No. 7,296,627 also propose techniques that directly or indirectly use heat, acid, or electrolytic methods to solve the problem. U.S. Pat. No. 4,813,482, U.S. Pat. No. 5,909,774 and U.S. Pat. No. 6,112,814 relate, in turn, to complex solutions for the treatment of organic deposits where fluids are injected in defined sequences, or contain surfactants in their compositions. Such complexity explains, in part, the industry preference to use aromatic solvents, mainly xylene, and mixtures thereof, in the solubilizing processes of asphaltenic and paraffinic deposits. However, given the questionable toxicological profile of elements such as benzene, toluene, ethylbenzene and xylene (products commonly referred to as BTEX), the use of such components has been increasingly avoided by companies seeking responsible performance and reducing their employees' level of exposure to these solvents, and such trend has also been observed with the service companies of the oil and gas exploration and production industry.
[0006] Furthermore, most of the used fluid leaves the reservoir hydrophobic, which is detrimental to subsequent acidification treatments (using aqueous acid solutions). U.S. Pat. No. 4,278,129 provides elementary examples of tertiary stimulation treatments that can be applied in oil wells after primary and secondary recovery, in which aqueous solutions of anionic surfactants, such as alkoxylated and phosphates esters, are used to change the wettability of the rock, and thus increase oil mobility during formation. Such tertiary recovery methods have become increasingly common, thus being a general interest of the industry the existence of treatments for cleaning and solubilizing asphaltenic and paraffinic deposits which are capable to provide hydrophilic character to the rock.
[0007] The evolution of the theme towards friendlier formulations has been shown in U.S. Pat. No. 8,695,707, which proposes a method for removing organic deposits using at least two polar solvents and an apolar one, which may contain asphaltene inhibitors. This patent (U.S. Pat. No. 8,695,707) explores the theme based on the polar or apolar character of solvents to ensure satisfactory solubilization of different organic solutes. However, U.S. Pat. No. 8,695,707 is limited to an at least ternary solvent system, and, this patent clearly does not enable the achievement of a solution free of aromatics and containing biodegradable components providing the desired performance, since it uses solvents such as cyclohexanone or N-methyl-2-pyrrolidone (NMP) and kerosene, the latter being an oil fraction that typically contains 15 to 20% of free aromatic such as BTEX in its composition.
[0008] Considering the state of the art, it is clear the industry still needs compositions for treating deposits and incrustations that involve low thermal or mechanic energy consumption, that are acid free, compatible with aqueous system and fluids for treating secondary recovery and, mainly, compositions of biodegradable and with low content fluids of questionable toxicological profile, in particular free of aromatic hydrocarbons such as BTEX. Within this context, the present invention aims to address these matters, proposing compositions having low complexity and best toxicological and environmental characteristics.
SUMMARY OF THE INVENTION
[0009] The present invention relates to a solvent composition for the solubilization of deposits and incrustations, including, but not limited to, asphaltenes and paraffins. The solvents used in this invention exhibit a high power to solubilize the molecules of asphaltenes and paraffins, forming sufficiently fluid and stable solutions that allow the use of this composition to remove the organic deposit in the oil industry, such as well cleaning by the process of injecting the fluid containing the cited solvents, solubilization and deposit removal. Due to the good technical performance and. above all, to the biodegradability and toxicological profile of the used solvents, the composition formulated according to this invention will find application in the place of compositions containing benzene, toluene, ethylbenzene and xylene (products commonly known as BTEX), diesel, kerosene or other solvents and complex formulations used in the industry.
DETAILED DESCRIPTION OF THE INVENTION
[0010] For purposes of interpretation in the present invention, for ‘aromatic solvents’ we mean all the solvents that have at least one aromatic ring in their structure. Free aromatic solvents designate solvents or solvents compositions that contain at least one of the compounds benzene, toluene, ethyl-benzene or xylene (products commonly designated as BTEX). As ‘oxygenated solvents’ we mean all the solvents that have at least one oxygen atom in their molecule. Treatment fluids are used in the industry in a remediation manner, aiming at solubilizing deposits and incrustations and, more specifically, oil-derived organic deposit, such as paraffins and asphaltenes.
Solubilization of Asphaltenes, Paraffins and Other Organic Deposits
[0011] In the exploration and handling of crude oil, organic materials naturally present in petroleum can precipitate, depositing in pores of rocks, pipes, and equipment. The main organic deposits referred to in this invention include asphaltenes and paraffins. Asphaltene has a complex and non-homogeneous molecular structure containing aromatic rings, heteroatoms and aliphatic chains combined to form various types of molecular structures. Paraffins are saturated aliphatic compounds having chains higher than C 20 , which may or may not contain branching.
[0012] When attempting to replace the apolar solvents and especially the aromatic solvents traditionally used to solubilize these organic deposits, there is a challenge for the determination of the most effective solvents and their optimal concentration in the composition of an effective treatment fluid.
[0013] The present invention proposes the inclusion of oxygenated solvents and its combinations as candidates for solving the problem of organic deposits. Solvents and formulations traditionally containing free aromatics (BTEX) are then replaced by compositions comprising BTEX-free polar solvents, or substituted by compositions comprising at least one apolar solvent with low aromatic content or free of aromatics and a BTEX-free polar solvent, such combinations being chosen and determined according to the concepts of solvency power and compatibility.
[0014] Polar solvents according to the present invention that will provide the composition with solubility properties that are acceptable and comparable with the ones of compositions commonly found in the industry, are preferably oxygenated solvents, that is, characterized by containing at least one oxygen atom in their molecules. Preferably, the polar solvent has physico-chemical characteristics according to the data of Table 1.
[0000]
TABLE 1
Physico-chemical properties of the oxygenated solvents
Propriety
Value
Boiling Point (° C.)
112-300° C.
Density (20/20° C.)
0.9-1.3
Solubility in water @ 20° C. (% by weight)
0.9-100
Flash point (closed vessel, ° C.)
30-140
[0015] The information provided in Table 1, when interpreted alone, are not enough to suggest that the oxygenated solvents can be used alone or in combination with any apolar solvent with low aromatic content or free of aromatics, in compositions for the solubilization of deposits and incrustations in the oil industry, in place of the traditionally-used aromatic solvents. Moreover, the molecular structure of this solvent family clearly differs from the one of xylene and of the other solvents commonly used for this application. Thus, the finding that the oxygenated solvents exhibit suitable properties and, in preferred embodiments of the invention, provide surprisingly superior performance in the application described in this invention is an advance in the art.
[0016] The oxygenated solvents used in this invention are not listed as carcinogenic by several environmental agencies, such as IARC (International Agency for Research on Cancer), NTP (National Toxicology Program—USA), OSHA (Occupational Safety and Health Administration—USA) and ACGIH (American Conference of Governmental Industrial Hygienists). Therefore, the use of solvents belonging to the family of oxygenated solvents to replace BTEX in applications for deposit and incrustation solubilization in the oil industry enables safer levels of workers' exposure to treatment fluids, which is, thus, a significant advance in health, safety, and environmental conditions.
[0017] The composition described in this invention meets corrosion standards and is compatible with materials commonly used in the oil industry. Such solution showed satisfactory results in the solubilization of asphaltenes and paraffins when compared to commonly used aromatic solvent-based fluids, and superior performance with respect to ternary solvent compositions containing aromatics. Finally, the solvents used in the present invention have conferred upon said fluids additional characteristics that improve the performance of the compositions and assist in the application of the technique, such as (i) increasing the hydrophilic character of the compositions if compared with the use of aromatic compositions, enabling better compatibility in the intervention processes of subsequent well that require the rock to have a hydrophilic character, (ii) reducing or eliminating aromatic components in the compositions, making handling and storage possible with more safety and less exposure to compounds of questionable toxicological profile such as BTEX, (iii) increasing the composition biodegradability by using solvents containing functional groups with higher biodegradability than that of aromatic solvents, such as esters.
Composition Free of Free Aromatics Containing Polar Solvents
[0018] The composition according to this invention is free of free aromatics (that is, BTEX), and can solubilize deposits, incrustations, asphaltenes and paraffins typically found in the oil industry in a number of steps, such as, but not limited to: drilling, stimulation, fracturing, completing and cementing of wells, production, transportation, refining and storage of oil and derivatives.
[0019] In a detailed description of the invention, the composition has the following characteristics:
[0020] a) it contains at least one polar solvent;
[0021] b) it is free of apolar solvents;
[0022] c) it has aromatic solvents (solvents that have at least one aromatic ring in their structure), in a content from 0% to 40% by weight of the total composition;
[0023] D) it is free of free aromatics (that is, BTEX); and,
[0024] d) it is free of water and/or acids.
[0025] In a detailed description of the invention, at least one of the used polar solvents is preferably an oxygenated solvent (that is, a solvent characterized in that it contains at least one oxygen atom in its molecule).
[0026] In a detailed description of the invention, the oxygenated solvent is characterized in that it preferably contains at least one ester group, or an ether group, or a ketone group in its molecule, according to Formula 1:
[0000] R 1 —X 1 —(R 2 —X 2 ) m —R 3 (Formula 1)
where: R 1 is independently an aliphatic chain or cyclic chain C 1-18 , which may contain at least one hydroxyl or carboxyl group R 3 is independently a hydrogen atom, an aliphatic or cyclic chain C 1-18 , which may contain at least one hydroxyl or carboxyl group X 1 and/or X 2 are independently an ether, ester, ketone, or an oxygen atom R 2 is an aliphatic or cyclic chain C 1-18 m≧0
[0033] In a preferred description of the invention, the oxygenated solvent according to Formula 1 is an ester obtained from alcohols whose carbon chain contains from 2 to 18 carbon atoms, and thus R 1 is a chain C 1-18 , X 1 an ester bond, m=0, and R 3 an aliphatic chain C 2-18 .
[0034] In a preferred description of the invention, the oxygenated solvent according to Formula 1 is an ester obtained characterized by being obtained from alcohols whose carbon chain contains from 2 to 18 carbon atoms, characterized in that the alcohol has at least one branch in its structure, and therefore, R 1 is a chain C 1-18 , X 1 is an ester bond, m=0, and R 3 is a branched aliphatic chain derived from alcohols such as, but not limited to, isopropyl alcohols, isobutyl alcohols, sec-butyl alcohol, isoamyl alcohols.
[0035] In another preferred description of the invention, the oxygenated solvent according to Formula 1 is an ether obtained from alcohols whose chain contains from 2 to 6 carbon atoms and, therefore, X 1 is an ether bond, R 1 a chain derived from alcohols such as, but not limited to, ethanol, propanol, butanol, or phenol.
[0036] In a detailed description of the invention, the oxygenated solvent according to Formula 1 is a glycol ether characterized in that it is obtained from the reaction of alcohols with one to three molecules of ethylene, propylene or butylene oxides, and therefore, X 1 is an ether bond, R 1 a chain derived from alcohols such as, but not limited to, ethanol, propanol, butanol, or phenol, R 2 a saturated aliphatic chain C 2-4 , X 2 an oxygen atom, 1<m<3, and R 3 an hydrogen atom.
Composition Free of or with Low Content of Free Aromatics Containing a Polar Solvent and Apolar Solvents
[0037] In another detailed description of the invention, the composition has the following characteristics:
[0038] a) contains a polar solvent;
[0039] a) contains at least one apolar solvent;
[0040] c) has aromatic solvents (solvents that have at least one aromatic ring in their structure), in a content from 0% to 40% by weight of the total composition;
[0041] d) is free of water and/or acids.
[0042] In a first preferred description of the invention, the used polar solvent is preferably an oxygenated solvent (that is, a solvent characterized by containing at least one oxygen atom in its molecule).
[0043] In a detailed description of the invention, the oxygenated solvent is characterized in that it preferably contains at least one ester group, or an ether group, or a ketone group in its molecule, according to Formula 2:
[0000] R 1 —X 1 —(R 2 —X 2 ) m —R 3 (Formula 2)
where: R 1 is independently an aliphatic chain or cyclic chain C 1-18 , which may contain at least one hydroxyl or carboxyl group R 3 is independently a hydrogen atom, an aliphatic or cyclic chain C 1-18 , which may contain at least one hydroxyl or carboxyl group X 1 and/or X 2 are independently an ether, ester, ketone or an oxygen atom R 2 is an aliphatic or cyclic chain C 1-18 m≧0
[0050] In a detailed description of the invention, the oxygenated solvent according to Formula 2 is an ester obtained from alcohols whose carbon chain contains from 2 to 18 carbon atoms, and thus R 1 is a chain C 1-18 , X 1 an ester bond, m=0, and R 3 an aliphatic chain C 2-18 .
[0051] In a detailed description of the invention, the oxygenated solvent according to Formula 2 is an ester obtained from alcohols whose carbon chain contains from 2 to 18 carbon atoms, characterized in that the alcohol has at least one branch in its structure, and therefore, R 1 is a chain C 1-18 , X 1 is an ester bond, m=0, and R 3 is a branched aliphatic chain derived from alcohols such as, but not limited to, isopropyl alcohols, isobutyl alcohols, sec-butyl alcohol, isoamyl alcohols.
[0052] In a second preferred description of the invention, the oxygenated solvent according to Formula 2 is preferably an ether obtained from alcohols whose chain contains from 2 to 6 carbon atoms and, therefore, X 1 is an ether bond, R 1 a chain derived from alcohols such as, but not limited to, ethanol, propanol, butanol, or phenol.
[0053] In a detailed description of the invention, the oxygenated solvent according to Formula 2 is a glycol ether characterized in that it is obtained from the reaction of alcohols with one to three molecules of ethylene, propylene or butylene oxides, and therefore, X 1 is an ether bond, R 1 a chain derived from alcohols such as, but not limited to, ethanol, propanol, butanol, or phenol, R 2 a saturated aliphatic chain C 2-4 , X 2 an oxygen atom, 1<m<3, and R 3 and hydrogen atom.
[0054] The hybrid character of the composition, which uses solvents of different polarities, allows the achievement of solubility results similar to the typical values found for apolar solvents or commonly used ternary mixtures.
[0055] In a detailed description of the invention, apolar solvents suitable for the proper functioning of the invention preferably include the ones obtained from fractions from the distillation of petroleum with boiling point between 20° C. and 400° C., preferably naphtha, kerosene, and derivatives thereof, such as, but not limited to turpentine, paraffin aliphatic hydrocarbons, olefinic aliphatic hydrocarbons, aromatic hydrocarbons, and mixtures thereof. The apolar solvent used is preferably a purified fraction of the above fractions in which the aromatic hydrocarbon content ranges from 0% to 40% by weight of the total weight of the apolar solvent. The used solvent has a flash point above 61° C.
[0056] Alternatively, other apolar solvents suitable for the proper functioning of the present invention may include those obtained preferably from natural extracts, such as, but not limited to, terpenes or essential oils, such as, but not limited to, lemon terpenes, such as, but not limited to, d-limonene and 1-limonene, as well as mixtures thereof.
[0057] In a preferred form of this invention, both apolar solvents and the polar solvent are used as major components of the dissolving composition comprising from 20 to 80% by weight relative to the total composition thereof.
[0058] The composition containing two or more low-aromatic content and biodegradable solvents described in this invention can solubilize asphaltenes, paraffins and organic deposits typically found in the oil industry in a number of steps, such as, but not limited to: well drilling, stimulation, fracturing and completion, production, transportation, refining and storage of oil and by-products.
EXAMPLES OF ORGANIC DEPOSIT SOLUBILIZATION
[0059] The invention is now described based on the examples, which are simply illustrative and should not be meant as limiting its scope.
Example 1—Asphaltene Solubilization Test
[0060] Solvent compositions have been formulated according to the disclosure of the present invention. Oxygenated solvents belonging to the family of pure monoesters, glycol ethers and diesters were tested in combination with each other and in combinations with apolar solvents such as kerosene and d-limonene. Such compositions have been compared with traditionally employed formulas such as xylene, kerosene, and ternary mixtures containing solvents such as n-2-methylpyrrolidone (NMP). The dissolution test used to compare the formulations was performed according to the procedure described below using, as a representative material of the asphaltene family, gilsonite—a resinous rock made of a complex combination of hydrocarbons:
[0061] 1) 100 ml of the composition to be tested was bath-heated until the composition reached the temperature of 66° C.;
[0062] 2) an envelope of impermeable and resistant fabric was weighed (m c ) and the approximate amount of 1 g of gilsonite was inserted inside it. The envelope was closed, the weight of the set (m i ) being later measured and recorded;
[0063] 3) the set was inserted in the solvent composition to be testes, and the temperature is kept at 66° C.;
[0064] 4) the sample was kept immersed for 1 h;
[0065] 5) Upon immersion, the sample was withdrawn from the solution, placed in an oven for 30 minutes at 30° C. to allow solvent evaporation, and then its final mass was measured (m f );
[0066] 6) the solubilization rate was then calculated from the Formula below:
[0000] S= 100×( m i −m f )/ m i
[0067] The compositions used in each test, as well as the respective obtained dissolution rates S are listed in Table 2. The prefix B indicates typical formulations of the industry, while the prefix A indexes the proposed compositions within the scope of the present invention.
[0000]
TABLE 2
Solubilization of asphaltenes with different formulations at 66° C.
Glycolic
Aromatic
Apolar
Polar
Test
S (%)
D-limonene
Kerosene
Xylene
NMP
Diesel
Butylglycol
Monoester
Ether
Diester
character
solvents
solvents
B1
100.0
100
BTEX
1
0
B3
100.0
50
50
BTEX
2
0
B6
100.0
50
45
5
BTEX < 40
2
1
B5
100.0
85
5
10
BTEX
2
1
A13
100.0
50
50
BTEX < 40
1
1
A1
95.2
50
50
Free of
1
1
B2
94.6
100
BTEX
1
A11
94.2
20
80
Free of
1
1
A4
89.0
80
20
Free of
1
1
B4
86.6
80
20
BTEX
2
A6
85.6
80
20
BTEX < 40
1
1
A5
84.9
80
20
BTEX < 40
1
1
A8
84.8
20
80
BTEX < 40
1
1
A2
84.1
50
50
BTEX = 0
1
1
A7
82.5
80
20
BTEX < 40
1
1
A14
73.5
100
Free of
1
0
A3
7.1
50
50
Free of
1
1
[0068] The results of Table 2 clearly show that, with the exception of A3, all the compositions proposed in the present invention can dissolve the organic deposits of asphaltic nature at rates higher than 70%, a minimum limit compatible with the general requirement of the oil industry, wherein, among the formulations that made possible the total dissolution of the deposits (B1, B3, B6, B5 e A13), A13 is the only formulation characterized in that it is a binary formulation with an aromatic content of less than 40% by weight.
[0069] Upon comparing the results of formulations A11, and A4, it is evident the superior effect of the monoester solubilization in relation to d-limonene, since the formulation with 80% of ester shows a rate 5.2% higher in relation to the inverse formulation containing 80% of d-limonene. The formulation A11 showed a rate only 0.4% lower than formulation B2 which is formed by pure kerosene. Furthermore, all monoester and d-limonene combinations exhibited rates higher than the solubility rate of the kerosene and diesel mixture (B4), typically used in the industry.
[0070] Upon comparing the results of A5 and A8, we have verified the ester ability to perform solubilization equivalent to that of kerosene.
[0071] Formulation A14, consisting of pure monoester, although exhibited a rate 21.1% lower than the rate of pure kerosene (B2), still showed adequate performance for the purposes of treatment fluid composition since it can solubilize more than 70% of the initial deposit. A14 still has the advantage of being a composition of only one solvent, free of any aromatic solvents. Such a finding that it is possible to select an oxygenated solvent capable of composing a solution free of aromatic solvents and which is capable of solubilizing organic deposits of asphaltenic nature represents an advance in the state of the art.
[0072] Formulations A6 and A2 indicate the promising character of the glycol ether in solubilizing asphaltenes, its performance being more synergistic with kerosene than with d-limonene.
[0073] The diester did not exhibit intrinsically-favorable characteristics for solubilization, however, A7 reveals that the solvent can be included in traditional compositions without significantly compromising the performance thereof.
[0074] Compositions A1, A11 and A4 provide the advantage of being binary compositions, free of aromatic solvents, being able to dissolve the asphaltic deposits at rates higher than the dissolution rates obtained for the typical aromatic formulations such as B4. A1 further provides an advantage in relation to the use of pure kerosene (B2).
[0075] Another advantage of the proposed compositions is the fact that they contain oxygenated solvents, which are products obtained by industrial processes and at higher scale than terpenes and essential oils. Moreover, said ester is, by its nature, more biodegradable than the traditional BTEX compounds used.
Example 2—Paraffin Solubility Test
[0076] Solvent compositions have been formulated according to the disclosure of the present invention. Oxygenated solvents belonging to the family of pure monoesters, glycol ethers and diesters were tested in combination with each other and in combinations with apolar solvents such as kerosene and d-limonene. Such compositions have been compared with traditionally employed formulas such as xylene, kerosene, and ternary mixtures containing solvents such as n-2-methylpyrrolidone (NMP). The dissolution test used to compare the formulations was performed according to the procedure described below, using paraffin wax with a melting point between 60° C. and 80° C., a material representative of the paraffins commonly found in petroleum industry operations. To characterize the solvency power of each formulation, separating it from thermophysical aspects, the tests were carried out at a temperature below the paraffin melting point, as detailed below:
[0077] 1) 100 ml of the composition to be tested was bath-heated until the composition reached the temperature of 38° C.;
[0078] 2) an envelope of impermeable and resistant fabric was weighed (m c ) and the approximate amount of 1 g of paraffin wax was inserted inside it. The envelope was closed, the weight of the set (m i ) being later measured and recorded;
[0079] 3) the set was inserted in the solvent composition to be testes, and the temperature is kept at 38° C.;
[0080] 4) the sample was kept immersed for 1 h;
[0081] 5) Upon immersion, the sample was withdrawn from the solution, placed in an oven for 30 minutes at 30° C. to allow solvent evaporation, and then its final mass was measured (m f );
[0082] 6) the solubilization rate was then calculated from the Formula below:
[0000] S= 100×( m i −m f )/ m i
[0083] The compositions used in each test, as well as the respective obtained dissolution rates S are listed in Table 3. The prefix B indicates typical formulations of the industry, while the prefix A indexes the proposed compositions within the scope of the present invention.
[0000]
TABLE 3
Solubilization of paraffins with different formulations at 38° C.
Glycolic
Aromatic
Apolar
Polar
Test
S (%)
D-limonene
Kerosene
Xylene
NMP
Diesel
Butylglycol
Monoester
Ether
Diester
character
solvents
solvents
B1
99.0
100
BTEX
1
0
B5
76.1
85
5
10
BTEX
2
1
A1
65.1
50
50
Free of
1
1
B3
62.6
50
50
BTEX
2
0
B4
61.7
80
20
BTEX
2
0
B2
61.3
100
BTEX
1
0
A5
60.9
80
20
BTEX < 40
1
1
A12
57.7
50
50
Free of
1
1
B6
56.4
50
45
5
BTEX < 40
2
1
A13
51.2
50
50
BTEX < 40
1
1
A7
49.2
80
20
BTEX < 40
1
1
A6
45.0
80
20
BTEX < 40
1
1
A4
43.5
80
20
Free of
1
1
A2
40.0
50
50
Free of
1
1
A11
36.7
20
80
Free of
1
1
A14
36.4
100
Free of
0
1
A8
33.0
20
80
BTEX < 40
1
1
A3
22.2
50
50
Free of
1
1
[0084] The results of compositions B1, B5 and A1 show that composition A1 shows the dissolving power closest to the aromatic formulations typically used in the industry, with the advantage that A1 is an aromatic-free binary composition in its formulation. Furthermore, A1 exhibits an improved performance when compared with the mixtures of kerosene and xylene (B3 and B4), and also when compared with pure kerosene (B2).
[0085] By comparing the solubilization results of A5 with the results of B6, the ability of the monoester to act synergistically with the apolar solvent kerosene to solubilize paraffinic deposits, surprisingly, shows a better performance than that of a ternary formulation of aromatic content lower than 40% (B6), thus allowing a binary formulation with an aromatic content of less than 40% (A5). Such a finding that it is possible to select an oxygenated solvent capable of composing a binary solution with 0 to 40% by weight of aromatic solvents and which is capable of solubilizing organic deposits of paraffinic nature represents an advance in the state of the art.
[0086] In addition, by comparing A1 solubilization results with B6 and A4 results, the fact that formulation A1 exhibits a dissolution rate of 8.7% and 21.6% higher than B6 and A4 rates, respectively, reveals the ability of the oxygenated monoester solvent to act synergistically in the solubilization of paraffins to achieve superior performance than a ternary mixture containing d-limonene (B6) or binary composition with 80% d-limonene (A4).
[0087] Formulations A6 and A2 indicate that there is potential for glycol ether to compose paraffin solubilization fluids, and its performance is more synergistic with kerosene than with d-limonene.
[0088] Formulation A7 indicates the promising character of the diester in solubilizing paraffins, however, there is a technical barrier when attempting to formulate compositions with higher ester contents by weight, combined with aliphatic solvents, since the solubility of the diester in apolar solvents is low.
[0089] Another advantage of the proposed compositions is the fact that they contain oxygenated solvents, which are products obtained by industrial processes and at higher scale than terpenes and essential oils. Moreover, said ester is, by its nature, more biodegradable than the traditional BTEX compounds used.
[0090] Therefore, the findings of Examples 1 and 2 allow us to conclude that the present invention can provide a solution to the problem of solubilization of deposits and incrustations, preferably asphaltenic and paraffinic organic deposits, proposing formulations free of BTEX and with an aromatic content lower than 40% of the total weight of its composition, consisting of at least one polar solvent, wherein the polar solvent is preferably an oxygenated solvent, the oxygenated solvent being preferably a monoester. Furthermore, the examples support the fact that the present invention can propose a composition having an aromatic content of less than 40% of the total weight of its composition, containing a polar solvent and at least one apolar solvent, the polar solvent being preferably an oxygenated solvent, so that the proposed composition exhibits a solubility power equivalent to the power of solutions typically found in the art such as xylene, kerosene and ternary formulations containing d-limonene and solvents such as N-2-methyl pyrrolidone. | The deposition of organic materials originating from crude oil, such as asphaltenes and paraffins, is deemed to compromise satisfactory oil exploration and production, because it clogs pores and equipment, compromising the operation performance. This problem may arise at various points during the operations of drilling, stimulating, fracturing, completing and cementing wells, production, transportation, refining and storage of oil and derivatives, including the use of the fluid in treatments for oil wells and reservoirs, well tubing and annuli, tubing, equipment, and tanks used in treatment processes, transportation and refining of oil and derivatives thereof. The present invention relates to a solvent composition to solubilize such deposits and incrustations. The solvents used in the present invention have a high capacity to solubilize the molecules of asphaltenes and paraffins, forming sufficiently fluid and stable solutions, which allow the use of this composition for the removal of organic deposits in the oil industry. Due to its good performance in the solubilization of deposits and incrustations and, especially, due to the biodegradable nature and superior toxicological profile, the alternatives described in the present invention can replace compositions containing benzene, toluene, ethylbenzene, and xylene (products commonly denoted as “BTEX”), diesel, kerosene, or other solvents and complex formulations used in the oil industry. | 4 |
FIELD OF THE INVENTION
This invention relates to aircraft disk braking systems and, more particularly to an improved disk braking system for aircraft that dampens vibration found associated with brakes upon brake application.
Background
Modern aircraft employ a disc braking system, whose structure is described in the literature, including the patent literature, such as U.S. Pat. Nos. 5,437,352 to Harker; 5,323,881 to Machen et al; 5,255,761 to Zaremsky; 5,205,832 to Edminsten; 5,107,968 to Delpassand; 5,062,503 to Black et al; 4,944,370 to Chambers et al; 4,383,594 to Correll et al; 4,290,505 to Kramer and 3,977,631 to Jenny.
During braking of the aircraft, the stator and rotor discs are pressed into frictional sliding contact with each other, converting the forward momentum of the aircraft into heat, bringing the aircraft to a halt. Until recent years, those discs were constructed primarily of steel material.
Carbon disc aircraft brakes were developed in recent years and became the brakes of choice for many aircraft. Carbon disc brakes offered considerable advantage. They were longer lasting and thereby reduced brake maintenance cost and they were much lighter in weight than the steel disk brakes. That substitution reduced aircraft weight, improving the aircraft's payload/range and/or reducing the aircraft's operational fuel consumption.
Enjoying the benefits of that important technological development, with experience, it was discovered that some landing gear and wheel brake assembly components became damaged and required replacement prematurely. Initially unexplainable, after lengthy investigation it was found that upon landing and initial braking of the aircraft, a very large vibration developed in the wheel brake assembly, and continued for but a small fraction of a second and that high frequency vibration caused the damage. As example, wheel heat shields became twisted, carbon disks were cracking, wheel speed transducers were failing, hydraulic piping was breaking and landing gear components were failing to the extent that brakes were becoming inoperable, creating a safety hazard.
Investigation ultimately showed that such vibration was attributed to the carbon brake assembly in an unknown vibrational mode. Although vibration was always present somewhat in steel brakes, that vibration did not produce nearly the amount of damage caused with the carbon brakes.
What existed as a relatively minor vibration problem with the prior steel disk brakes had grown to a more substantial problem, a problem faced by airframe manufacturers, brake manufacturers and air carriers worldwide. The effects of the problem range from cabin noise and passenger discomfort to structural damage and failure of landing gear and rolling assembly components. Those effects directly impact passenger safety, comfort, aircraft servicabiblity, dispatch reliability and hardware replacement costs. The foregoing circumstances provided strong incentive to seek the cure offered by the present invention.
Prior techniques of suppressing brake vibration include placement of orifices with the hydraulic passages of the brake housing; placement of dampers within the brake rotors and stators; change in composition of the brake friction material; attachment of turnbuckles to load the brake against the landing gear; and stiffening of brake structural components. Of the foregoing techniques, the only one that appeared to hold promise is the turnbuckle arrangement that loaded the brake assembly. However, turnbuckles have the operational problems of adjustment, load retention and potential yielding.
Accordingly, an object of the present invention therefore is to provide a new brake installation for aircraft brakes.
A further object of the invention is to minimize and/or eliminate significant vibration in aircraft landing gear and wheel brake assemblies upon aircraft brake application.
A still further object of the present invention is to suppress brake vibration in aircraft brake systems that employ carbon disc brakes and also in those that employ steel disc brakes, and to dampen such brake vibration with greater effectiveness than available with vibration dampening systems that employ turnbuckles to effect dampening.
An additional object of the invention is to provide a vibration suppressing brake structure that does not require the use of turnbuckles, that does not require adjustment and that does not require large axle nut torquing levels.
SUMMARY
In accordance with the foregoing objects an improved multiple disk aircraft wheel brake assembly of the type which includes disc rotors and stators in a conventional assembly and containing a torque tube and torque tube foot is improved by inclusion of a restraining means to clamp or restrict movement of the torque tube foot against lateral movement axial of the wheel axle and also serves to restrain rotational movement. The foregoing structure substantially eliminates the unwanted high frequency vibration as reflected by the reduction and/or elimination of the kinds of damage earlier experienced with carbon brakes. The foregoing should also serve to eliminate even the relatively minor damage, cabin noise and passenger discomfort experienced with steel disc brakes.
The present invention minimizes free-play. It also maximizes energy dissipation through coulomb damping. The invention introduces significantly higher levels of damping than the known prior techniques. By restraining or clamping the movement of the brake torque tube foot relative to the axle, high levels of vibration energy are found to be effectively dissipated and the impulse forces are minimized. This in turn dampens brake and rolling assembly vibration.
In accordance with an embodiment of the invention, the restraint is provided by positioning a barrier alongside the torque tube foot, the barrier being axially fixed in position. In brake installations in which the torque tube foot may move axially in both directions, a like barrier is placed on the other side of the torque tube foot as well. In accordance with another embodiment of the invention the restraining means is accomplished by a flange integrally formed on the wheel axle sleeve and positioned on one side of the torque tube foot and a wheel spacer mounted to the axle that is located on the other side of the torque tube foot. Each of those elements serves as a barrier to foot movement in the direction of such respective elements.
The foregoing and additional objects and advantages of the invention together with the structure characteristic thereof and the various embodiments thereof, which was only briefly summarized in the foregoing passages, becomes more apparent to those skilled in the art upon reading the detailed description of the various embodiments, which follows in this specification, taken together with the illustrations thereof presented in the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
FIG. 1 is a fragmentary partial cross-section view of a brake assembly embodying the invention as mounted on an aircraft installation;
FIG. 2 is an enlarged partial cross section view of the torque tube foot and the associated components for restraining axial movement of the foot end found in the embodiment of FIG. 1;
FIG. 3 is an enlarged scale section view of the outboard rim member integrally formed in the outboard end of the axle tube sleeve in the embodiment of FIG. 1;
FIG. 4 is a enlarged partial section view of the inboard end of the embodiment of FIG. 1 illustrating the inboard end of an axle sleeve member;
FIG. 5 is a partial section view of an alternative torque tube foot construction that may be substituted for the corresponding element in the embodiment of FIG. 1
FIG. 6 is a fragmentary partial section view of an alternative embodiment of the torque tube foot restraint of the aircraft brake system;
FIG. 7 is a fragmentary partial section view of a further alternative embodiment of the torque tube foot restraint of the aircraft brake system;
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The improvement modifies an existing aircraft brake installation and is best understood in the context of that brake system in connection with which the invention is hereafter described. Referring to the drawings, wherein like reference numerals designate like or corresponding parts throughout the several views, there is shown in FIG. 1 a friction brake mechanism 10 for use with a cylindrical wheel 11 having matching wheel sections 12 and 13. Each of the wheel sections 12 and 13 has a rim or flange, 14 and 15, web 16 and 17, and hub 18 and 19, respectively. The wheel sections 12 and 13 are fastened together by suitable bolts disposed in aligned bores within webs 16 and 17 to form an integral unit herewith to which a conventional pnuematic rubber aircraft tire, not illustrated, is mounted. The hubs 18 and 19 are supported for rotation on bearings, suitably roller bearings 21 and 22, which are mounted on a nonrotatable axle means or axle 23, having a central axis, the latter of which forms part of the aircraft's landing gear assembly.
The extending portions of axle 23 are covered by hollow removable sleeve 25, the latter described in greater detail, located to the left in the figure, and removable sleeve 26, located to the right in the figure, which are shrink fit over the axle during during assembly of the landing gear. These sleeves protect the axle, a very expensive component, from physical damage as could be caused from periodic maintenance of the wheel and/or brake assembly, which are periodically removed and replaced during the operational life of the aircraft, and from damage as could be caused by the high temperatures generated by the brakes during braking. Sleeve 25 serves an additional function in this embodiment, which is described later herein in greater detail.
As those skilled in the art recognize, when it is stated herein that one part or another is mounted to the axle, such reference is made in a generic sense, since such part may be mounted to the sleeve which overlies the axle, and/or is mounted to a bushing and/or such sleeve, as is apparent from the illustrations. But it is the axle which is the principal load bearing support.
A carrier 27, customarily referred to as a piston housing or a piston support member, is mounted on axle 23, with an intervening cylindrical bushing 28. Carrier 27 contains an inner hub or rim portion 29, a radially extending lug portion 31 and a plurality of cylinders or cylinder housings 33, distributed about the circumference of the housing and only one of which is visible in this view.
The piston housing contains a plurality of circumferentially spaced bores, not illustrated, for securing the piston housing to an annular hub 34 of a cylindrical torque tube member or torque tube 35. A plurality of bolts and nuts, not illustrated, are placed in the circumferentially spaced bores to secure the piston housing to torque tube 35.
Torque tube 35 also contains an annular and radially outwardly extending reaction plate or, as variously termed, end plate 36. The reaction plate 36 may be formed integral with torque tube 35 or may be made as a separate annular piece that is suitably connected to the torque tube 35. A plurality of circumferentially spaced pressure pads 37, generally disc shaped, is attached to the left hand side of reaction plate 36. The pressure pads 37 react the force of the back plate 47, an annular disc located to the left of the pressure pads 37. As is also conventional, torque tube 35 contains a plurality of circumferentially spaced splines 38, which are axially extending. Wheel section 12 contains a plurality of circumferentially spaced ribs or splines 39 on its inner peripheral surface. Such ribs or splines are typically cast therein during manufacture of the component or are machined to provide an integral type rib or spline for the brake assembly.
A temperature sensor 9 is connected to piston housing 27 and through a passage through the latter extends into an extended passage in the torque tube, allowing the torque tube temperature to be monitored by appropriate monitoring equipment in the aircraft.
Spline members or ribs 38 on the torque tube 35 support an axially nonrotatable pressure plate or end disc 40 and inner nonrotatable discs, 41, 42, 43, 44, 45, and 46. All of such stators contain slotted openings at circumferentially spaced locations on the inner periphery for captive engagement by the spline members 38 as is old and well known in the art. Such discs 41, 42, 43, 44, 45, and 46 constitute the stators for friction brake 10. An annular disc or back plate element 47 is suitably connected to the pressure pads 37 and acts in concert with the stator discs.
A plurality of axially spaced discs, referred to as rotors, 51, 52, 53, 54, 55, and 56 are interspaced with or, as variously termed, are interleaved between the stator discs 41 through 47. Those discs contain a plurality of circumferentially spaced openings along their outer periphery for engagement by the corresponding ribs 39 of the rotatable wheel as is old and well known in the art, thereby forming the rotor discs for the friction brake 10.
All of the nonrotatable discs, 41 through 47, and rotatable discs, 51 through 56, are fabricated from carbon, which is the present day preeminent wear-resistant material for withstanding high temperatures and is in accordance with the premise to this invention. Such carbon discs are marketed, as example, by the Aircraft Landing Systems of South Bend, Ind. The number of disc pairs in the stack may be varied as is necessary for the application involved. In one application, as example, there are six such disc pairs, as is illustrated. The respective stator discs and rotor discs that have the circumferentially spaced openings on the inner and outer periphery may accommodate reinforcing inserts, not illustrated, to provide reinforcement to the walls of such slotted openings and to enhance the life of such slots. Such reinforcing inserts are also referred to as drive clips.
The actuating mechanism for the brake includes the piston housing 27 which contains the circumferentially spaced cylinder housings 33, only one of which is illustrated, and which as shown in FIG. 1 is integral with the piston housing 27 and rim portion or hub 29. The cylinder housings 33 contain a piston cylinder and a piston head 47, the latter confronting front pressure plate 40. Since the piston cylinder is a known device, it is not necessary to further describe the details of its construction and assembly since those details are not material to the present invention.
The piston chamber is suitably connected to a hydraulic port, not illustrated, controlled by valve means, also not illustrated, in a manner old and well known in the art, whereby pressurization of chamber controls the movement of the piston or piston means. When actuated to produce braking, the piston head 47 moves axially, to the right in FIG. 1, to press against pressure plate 40 and axially move the pressure plate against the right side of the brake discs, forcing the discs into compressive frictional engagement between the piston head and the reaction plate 36 of the torque tube arm. Assuming the aircraft in which the disclosed brakes are installed has landed and is taxiing along the runway, the rotor discs are being turned by the aircraft wheels as the tires roll along the runway. The frictional engagement between the rotor and stator discs during braking helps transform the momentum that sustains the rolling movement into heat, thereby assisting to slow or bring the aircraft to a halt.
Reference is again made to the torque tube. Torque tube 35 contains a radially inwardly extending leg 48 and foot 49, referred to as the torque tube foot. Integrally formed with torque tube 35, the leg 48 and foot 49 circumferentially extend about the axis, as an annular member and cylindrical shaped member integrally joined to the annular member, respectively, with the foot's end surface or bottom supported by wheel axle 23, via intermediate heat insulators and/or bushings, as hereinafter described in greater detail. The torque tube foot provides mechanical support to the torque tube, allowing the torque tube to better support the weight and inertia of the stator discs, particularly under a dynamic vibration condition.
A ridge or flange 50, suitably integrally formed in axle sleeve 25, borders the left side of the torque tube foot 49. Wheel spacer 30 borders the right side of that foot. Spacer 30 also clamps in place on axle 23, between a radially inwardly directed annular member or rim 59 that is integrally formed on the right end of axle sleeve 25 and the inboard wheel bearing 21. The foregoing construction and the structure of the bottom of the torque tube foot, including the additional associated elements and their relationship are more clearly illustrated in the partial section view of FIG. 2 to which reference is made.
As better illustrated in this figure, torque tube leg 48, extending radially inwardly from torque tube 35, supports heat shield 32, which is fastened in position in part to the leg by rivets, and foot 49. The bottom end of torque tube foot 49 is hollowed out to create a cylindrical shaped annular cavity, leaving a narrow cylindrical rim or flange radially extending inwardly. A cylindrical heat insulator 57, suitably formed of stainless steel material, is fixed to the bottom of the foot structure, positioned within the cylindrical shaped recess formed in foot 49. Heat insulator 57 is sized in wall thickness so as to extend radially inwardly a distance slightly beyond the foot's end surface, and into abutment with a cylindrical "grommet" shaped bushing 58 that fits between the wheel axle sleeve 25 and torque tube foot 49. As illustrated, the principal cylindrical portion of bushing 58 fits under the torque tube foot and the short annular rim portion is located along a side of the torque tube foot, on the right side in the figure. The width of the bushing 58's cylindrical wall, from right to left in the figure, is slightly greater than the width of foot 49.
As shown in the figure, axle sleeve 25 contains the radially outwardly extending ridge or flange 50, integrally formed in the sleeve, and, axially spaced from that flange, the radially inwardly directed rim portion 59. A better view of the shape of the rim portion is presented in an enlarged section view in FIG. 3. The inner surface of the rim 59 is shaped and angled to abut against and generally conform to the surface of the radially inwardly tapered portion or step between portions labeled "e" and "f" in wheel axle 23. Flange 50 is shaped to define an annular cylindrical recess or rim along the outer edge on the flange's right hand side and a generally annular right side surface.
A grommet shaped bushing 61 of short height and relatively wide annular flange fits within the recess at the right side of the outer edge of flange 50 and essentially fills the space between the left side of foot 49 and sleeve flange 50, taking up any slack.
Wheel spacer 30, positioned to the right side of torque tube foot 49 contains a cylindrical central passage of sufficient diamenter to allow the spacer to fit over axle 23, including any sleeve member or spacer covering that axle. At a certain axial position along the height of that spacer's passage, the passage widens to a greater diameter, sufficient in diameter to allow the spacer to fit over the end of axle sleeve 25 and, further, defines an annular surface within the passage bordering the two different-sized cylindrical passage portions. The spacer 30 also contains a "washer shaped" or annular surface at its left end, sometimes referred to as the front end, and another annular surface at its right end, sometimes refered to as the rear end.
The washer shaped outer left hand edge of wheel spacer 30 is positioned on axle 23 contiguous to the bottom annular surface of bushing 58 and may abut that bushing or be spaced from same by a nominal manufacturing clearance. The washer shaped annular surface within wheel spacer 30's central passage abuts the outer surface of sleeve rim 59. Torque applied by the axle nut 20, illustrated in FIG. 1, creates an axial force on the various wheel members including, outboard wheel bearing 22 and therethrough to outboard wheel half 19, wheel hub 18 and therethrough to inboard wheel bearing 21, that, in turn applies a force to the rear annular surface of wheel spacer 30. Wheel spacer 30 in turn applies the force through sleeve rim 59, pressing the sleeve rim against the axle's step, clamping the sleeve rim in place. Such clamping prevents sleeve 25 from moving axially to the left in the figure and thereby also holds sleeve flange 50 in the prescribed axial position, preventing flange 50 from likewise moving or being moved further to the left. Notwithstanding that torquing force, the front edge of wheel spacer 30 is not required to exert any force upon the side of the torque tube foot 49 and/or bushing 58, and merely stands as a barrier to the foot preventing the foot from being moved axially to the right.
As is apparent from the foregoing description, the foregoing structure restricts any excursions of torque tube foot 49 to the right or to the left along the axis of axle 23, severely restraining or clamping the torque tube foot in place at the designated axial position. Should the shock of hard braking produce vibration within the torque tube 35 and in the torque tube leg 48, movement of the torque tube foot 49 is severely restrained. By so restraining the torque tube foot it was empirically found that the intermittently produced and unpredictable high frequency vibration, addressed in the preamble to this specification, and that caused so much damage in the past, was substantially reduced to minor significance or eliminated. In as much as the present computer modeling software was inadequate to explain or duplicate the prior vibration and consequent damage discovered, fortelling a lack of understanding of the cause and effect in theoretical evaluation, applicant is not ready to offer a rigorous specific theory beyond the fact that the invention functioned in practice and eliminated the vibration and the damage. It is appreciated that in operation the invention does not require adjustment, as do the prior turnbuckle techniques; it is simply assembled together.
In this embodiment, as shown in the partial section view of FIG. 4, to which brief reference may be made, the left end of sleeve 25 is spaced from the ridge in axle 23 by a very wide clearance to avoid the possibility of any physical contact therebetween, even should the sleeve lengthen due to thermal expansion. As also visible in this view, a bushing 62 is provided for the brake housing hub 29.
As illustrated in the partial section view of FIG. 4, the left edge of axle sleeve 25 is radially outwardly flared to define a peripheral rim. The left end of the sleeve and that rim is spaced from the step in axle 23, which is a characteristic of the present embodiment. Thus the left end of the sleeve is free and does not function to prevent the sleeve from axial movement to the left in this embodiment. Only the rim section 59 illustrated in FIG. 2 serves that function. As those skilled in the art appreciate, the foregoing construction contrasts with the prior art brake assembly, in which the left edge of the axle sleeve extended to and abutted the axle ridge, which served to prevent such leftward direction axial sleeve movement.
The present invention is employed with a landing gear wheel axle 23 that contains a somewhat complex geometry, which thereby governs the geometry of sleeve 25 employed in this embodiment, and serves to advantage in the construction of the vibration dampening elements to this embodiment. As illustrated in FIG. 1 to which reference is again made, the landing gear wheel axle contains various portions coaxially aligned, including a first portion "a" that is of a cylindrical geometry of a first diameter D1; a second portion "b", next to the first, defining a cylindrical flange of a second diameter D2, where D2>D1, which extends radially outwardly beyond the radial extent of the first portion by a predetermined amount; a third portion "c", located next to the second, having a cylindrical geometry of a third diameter D3, where D3<D2, providing a first annular tapered step between the second and third portions; followed by a fourth portion "d", that has the geometry of a right cone of predetermined height, that tapers from a diameter, D3, at one end, the same diameter as the preceding portion, to a lesser diameter D4 at the opposite end; a fifth portion "e" having a cylindrical geometry of an increased diameter D5, where D5>D4, defining a upwardly sloping step between the fourth and fifth axle portions; a sixth portion "f" having a cylindrical geometry of a reduced diameter D6, where D6<D5, providing a tapered annular step between the fifth and sixth portions; a seventh portion "g", having a right conical section geometry that tapers slightly from a diameter of D6 to a lesser diameter D7, where D7<D6; an eighth cylindrical portion "h", of a diameter D8=D6; and the final or ninth portion "i", having a cylindrical geometry of reduced diameter D9, where D9<D8. The ninth portion contains the threaded end for receiving the axle nut 20. Advantageously, thus, the embodiment allows a more simple retro-fit application of the invention to existing aircraft.
The foregoing structure is easily integrated and assembled. Axle sleeves 25 and 26 are shrink fit to the axle as part of the normal manufacture of a landing gear assembly. The brake is assembled by sliding the interleaved rotor and stator disks onto the torque tube, the slots in the stator disks fitting into the corresponding splines on the torque tube. The pressure plate is next slid onto the torque tube. Then the piston housing assembly is bolted to the torque tube to form a complete brake assembly.
Next the wheel spacer 30 is placed over the axle and adjacent the torque tube foot 49. Wheel assembly 11 is then slid onto the sleeved axle, the splines in the rotor disks lining up with the splines in the outer wheel web 12. Then the axle nut 20 is threaded onto the axle and tightened to the appropriate torque and safely locked into place.
The wheel nut applies an axial force to the outboard wheel bearing 22, the wheel members 18 and 19, and the inboard wheel bearing assembly 21. Through the left hand surface of inboard wheel bearing 21, the axial force is applied to wheel spacer 30 and that spacer in turn applies force to the portion of the axle sleeve 59 to clamp the sleeve to the axle at that location. Since flange 50 is integral with the sleeve member, that flange is clamped in place to the left side of the torque tube foot 49.
Thus on the right side of the torque tube foot, wheel spacer 30 serves to limit any excursion of the tube foot to the right, while on the left side of the tube foot, flange 50 limits any axial excursion of that foot end to the left in the figure to zero up to the amount of any manufacturing clearance, nominally 0.000 inches plus or minus 0.003 inches. Effectively, the tube foot end is clamped in axial position or as otherwise stated, is restrained. Any forces created by flexure in the torque tube leg, supporting the foot, cannot swing the foot end in an axial direction.
It is appreciated that because of the minimal clearances between the torque tube foot and adjacent restraints, the foregoing structure also serves to inhibit or restrain as well any rotational movement of the torque tube foot. Any temporary distortion of the torque tube as might be caused by a force as would induce high frequency vibration could produce a rotational force in addition to the axial force, creating a binding or frictional effect that inhibits rotational movement.
As those skilled in the art appreciate from the foregoing description, torque tube foot 49 and associated bushings are not required to be of the configuration illustrated, but may be changed to alternative forms without departing from the invention. As example, as illustrated in FIG. 5, two short height grommet shaped bushings, 58a and 58b, identical in structure, may be placed front to front, leaving a slight gap between, replacing the bushing 58 illustrated in FIG. 2.
Moreover, it is not necessary to employ the rims and flange 50 as integral with sleeve 25, in order to provide the restraints on the torque tube foot. In the alternative embodiment of FIG. 6 a generally cylindrical shaped member 65 contains a radially outwardly extending flange 66 to the left side of torque tube foot 49, abutting the annular base of bushing 58a', which in turn abuts the left side of the foot. At the right side a washer shaped spacer 67 fits over member 65 and an annular shaped nut 69, carrying a key washer 70 is threaded onto the threads 68 on the outer surface of member 65, and tightened, firmly positioning spacer 67 in fixed axial position against the right side of the torque tube foot. Key washer 70 has a key which slides onto a slot in the threads 68 preventing any rotation of the key washer. After nut 69 is tightened down, tabs on the key washer are bent down onto the nut, preventing the nut from backing off. Member 65 is fitted over a spacer 71 and locked axially by a groove in the spacer and the spacer in turn is clamped against the step or tapered portion of wheel axle 23.
Still another alternative is presented in FIG. 7 which contains all of the same elements for clamping the torque tube foot in fixed axial position as found in FIG. 6, excepting that no threads are required. In this embodiment member 65 of FIG. 6 is formed in two parts as 65a' and 65b' and the latter contains the flange like radially outwardly extending annular portion 69' that was served by lock nut 69, key washer 70 and spacer 58b' in the embodiment of FIG. 6. Still other variations of the torque tube foot clamping structure, become apparent to those skilled in the art.
As recognized by those skilled in the art, while the foregoing structure is particularly useful with carbon disc brakes in connection with which the invention has been described, the invention is not restricted thereto, and may be applied to like benefit in aircraft brake installations that employ steel brakes. It is believed that the foregoing description of the preferred embodiments of the invention is sufficient in detail to enable one skilled in the art to make and use the invention. However, it is expressly understood that the detail of the elements presented for the foregoing purposes is not intended to limit the scope of the invention, in as much as equivalents to those elements and other modifications thereof, all of which come within the scope of the invention, will become apparent to those skilled in the art upon reading this specification. Thus the invention is to be broadly construed within the full scope of the appended claims. | Axial and rotational movement of the torque tube foot of an aircraft's disc brake assembly is restrained to substantially dampen or eliminate the short interval high frequency vibration previously experienced on brake application. Restraining means is employed to restrain the torque tube foot and includes an annular flange member mounted to the axle by an axle sleeve and positioned adjacent a first side of the torque tube foot to stop lateral movement of the torque tube foot in the direction of the first side. Wheel spacer means is also provided containing a cylindrical passage for mounting the wheel spacer means to the axle opposite the annular flange member and on the opposite side of the torque tube foot. The wheel spacer means also contains an annular portion extending radially outwardly from the wheel axis and the annular portion is positioned adjacent the second side of the torque tube foot to stop lateral movement of the torque tube foot in the direction of the second side such that the torque tube foot is restrained from moving in both axial and rotational directions relative to the axle. Vibration damage experienced to brake and landing gear components with brake assemblies of the prior design is avoided. | 5 |
FIELD OF THE INVENTION
[0001] The present invention relates to an improved pierce nut manufacturing method and apparatus, more particularly to a method and apparatus delivering greater manufacturing flexibility.
BACKGROUND
[0002] Generally, pierce nuts have been used in industry for many decades and the improvements to the manufacturing processes of these nuts has been and continues to be, an area of great interest/effort. The present invention is the culmination of one such effort. It is believed that most, if not all, the focus in improving the manufacturing processes has been centered around the issue of increasing through-put and detection of quality defects. One such example may be found in U.S. Pat. No. 7,367,893, where a two-out die is used, incorporated herein by reference. It is believed that the area of manufacturing process flexibility has been largely ignored in the quest for higher production rates and lower rejection rates. It is also believed that manufacturing process flexibility can provide a manufacturer an advantage over those processes solely focused on speed and/or through-put. It is apparent that there is an unmet market need for a manufacturer to offer pierce nuts that can have differing characteristics and/or properties while still maintaining a high level of quality and a relatively low cost. The present invention seeks to address this unmet market need through its inventive process/method.
[0003] Among the other literature that may pertain to this technology include the following patent documents: U.S. Pat. No. 5,383,021; U.S. Pat. No. 5,348,429; U.S. Pat. No. 5,016,461; U.S. Pat. No. 4,971,499; U.S. Pat. No. 3,748,674; and U.S. Pat. No. 3,711,931, all incorporated herein by reference for all purposes.
SUMMARY OF THE INVENTION
[0004] The present invention is directed to one such solution, and particularly is directed to addressing the unmet market need discussed above. It is believed that the inventive process disclosed has the advantage of being able to produce pierce nuts with differing characteristics and/or properties form a single main production line.
[0005] Accordingly, pursuant to a first aspect of the present invention, there is contemplated a method of manufacturing rolled pierce nuts having a predetermined profile from a metal rod including the steps of: a. providing a articulating die including a punching station for punching a through-hole in the rod, a counter-sinking station for counter-sinking a least a portion of the through hole and a final trim station for cutting a blank nut to length; b. advancing the rod through the punching station and punching the through-hole; c. advancing the rod through the counter-sinking station and creating the counter-sunk portion of the through-hole; d. advancing the rod through the final trim station and cutting the blank nut to length; e. providing a hole sensor disposed after the final trim station for detecting the presence of the through-hole; f. providing a first hopper to collect blank nuts; g. advancing the blank nut past the hole sensor; h. removing the blank nut if a non-compliant hole is detected; i. advancing the blank nut into the first hopper if a compliant hole is detected; j. providing a tapper station for tapping the through-hole of the blank nut; k. advancing the blank nut from the first hopper to the tapper station; l. tapping a thread into the through-hole creating a tapped nut; m. providing a thread sensor after the tapper station for detecting the presence of the thread in the tapped nut; n. providing a second hopper to collect tapped nuts; o. advancing the tapped nut past the thread sensor; p. removing the tapped nut if a non-compliant thread is detected; q. advancing the tapped nut into the second hopper if a compliant thread is detected; r. providing at least one frangible wire; s. providing a cinching tool station to cinch the at least one frangible wire to the tapped nut creating a cinched pierce nut; t. providing a spooling station; u. advancing the tapped nut and the at least one frangible wire to the cinching tool station; v. cinching the tapped nut to the at least one frangible wire; w. advancing the cinched pierce nut to the spooling station; and x. spooling the cinched pierce nut, thus creating the rolled pierce nuts.
[0006] The first aspect of the present invention may be further characterized by one or any combination of the features described herein, such as including the step of removing the blank nuts from the first hopper to perform at least one first derivative operation on the blank nuts; including the step of performing at least one first derivative operation on the blank nut, thus creating a modified bank nut; including the step of returning the modified blank nut to the first hopper, the second hopper or both; the at least one first derivative operation is selected from the group consisting of plating, drilling, painting, inspecting, heat treating; annealing; and de-burring; including the step of removing the tapped nuts from the first hopper to perform at least one second derivative operation on the tapped nuts; including the step of performing at least one second derivative operation on the blank nut, thus creating a modified tapped nut; including the step of returning the modified tapped nut to the first hopper, the second hopper or both; the at least one second derivative operation is selected from the group consisting of plating, drilling, painting, inspecting, heat treating; annealing; and de-burring.
DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is an exemplary flow diagram according to teachings of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0008] The invention is an improved pierce nut manufacturing method and apparatus, more particularly to a method and apparatus delivering greater manufacturing flexibility. As further described below, the method and apparatus may utilize an number of “hoppers” along the processing line to function as places where the pierce nuts can be added and/or removed from the line, thus allowing derivative operation(s) to be conducted to the pierce nuts or to have “finished” nuts that do not require all the steps of the overall processing line (e.g. nuts without threads, nuts not placed on a frangible wire, etc.). It is contemplated that the processing line may be described as including a number of stations, where each station performs at least one operation in the manufacture of the pierce nut.
[0009] In a first station, a metal rod with a predetermined profile may be provided. For example, a rod that is supplied as a coiled roll. The first station may also include providing an articulating die set in a reciprocating press. The die set may include a punching station for punching a through-hole in the rod, a counter-sinking station for counter-sinking a least a portion of the through hole and a final trim station for cutting a blank nut to length. In a preferred embodiment, the articulating die set is a “one-out” die that produces single nuts, although it is contemplated that a “multiple-out die” may be possible. The process through the first station may include advancing the rod through the punching station and punching the through-hole; advancing the rod through the counter-sinking station and creating the counter-sunk portion of the through-hole; and advancing the rod through the final trim station thus cutting the blank nut to length.
[0010] In a preferred embodiment, the first station also includes providing a hole sensor disposed after the final trim station for detecting the presence of the through-hole, although this could also be located separately from the first station. The process may continue with advancing the blank nut past the hole sensor; removing the blank nut if a non-compliant hole is detected; advancing the blank nut into a first hopper (second station) if a compliant hole is detected. It is contemplated that the hole sensor may be a vision system that can detect the presence of the hole and provide feedback to a actuator that can remove a blank nut that does not have the required hole.
[0011] In a second station, the blank nuts that make it past the hole sensor, may be collected. This second station may serve as a loading and/or unloading point in the processing line for blank nuts. It is contemplated that the blank nuts may represent the finished product and unloaded at the second station as such. The blank nuts may be unloaded at this point to conduct derivative operations, such as, but not limited to: plating, drilling, painting, inspecting, heat treating; annealing; de-burring, and storing. After any derivative operation takes place, the second station may be used to introduce the “modified” blank nut back into the processing line. The second station may be referred to a first “hopper” wherein a hopper is commonly defined as a tapering container that discharges its contents at the bottom, but should not be limited as such so long as its function is to provide as a loading and/or unloading point in the processing line for the blank nuts.
[0012] A third station may be provided in the processing line, where the third station may include a tapper station for tapping the through-hole of the blank nut and a thread sensor after the tapper station for detecting the presence of the thread. The process may include advancing the blank nut from the first hopper to the tapper station; tapping a thread into the through-hole creating a tapped nut; advancing the tapped nut past the thread sensor; removing the tapped nut if a non-compliant thread is detected; and advancing the tapped nut into a second hopper (fourth station) if a compliant thread is detected. It is contemplated that the thread sensor may act in a fashion similarly to the hole sensor. The tapper station, in a preferred embodiment may be a simple machine that functions such as the machine taught in U.S. Pat. No. 3,582,225.
[0013] In a fourth station, the threaded nuts that make it past the hole sensor, may be collected. This fourth station may serve as a loading and/or unloading point in the processing line for threaded nuts. It also may serve as a loading point for other nuts (e.g. blank nuts, “modified” blank nuts, and/or “modified” threaded nuts) that may require the processing of the subsequent stations described below. It is contemplated that the threaded nuts may represent the finished product and unloaded at the fourth station as such. The threaded nuts may be unloaded at this point to conduct derivative operations, such as, but not limited to: plating, drilling, painting, inspecting, heat treating; annealing; de-burring, and storing. After any derivative operation takes place, the fourth station may be used to introduce the threaded nuts back into the processing line. The fourth station may be referred to a second “hopper” wherein a hopper is commonly defined as a tapering container that discharges its contents at the bottom, but should not be limited as such so long as its function is to provide as a loading and/or unloading point in the processing line for the nuts.
[0014] A fifth station, with nuts being fed from the fourth station, may include a cinching tool station. At least one frangible wire is also being fed into the fifth station (preferably from a coiled roll of wire). The cinching tool station may bring the nut and the frangible wire together creating a cinched pierce nut (the nut preferably being blank nuts, “modified” blank nuts, threaded nuts, and/or “modified” threaded nuts).
[0015] A sixth station (spooling station) may take the cinched nut from the fifth station and spool it onto a roll thus making the final product.
[0016] Of note, it is contemplated that any of the stations described above may include multiple components (e.g. two or more “hoppers, two or more “tapper stations”, two or more “articulating dies”) and feeds to and from the previous stations may be split between the multiple components.
[0017] Unless stated otherwise, dimensions and geometries of the various structures depicted herein are not intended to be restrictive of the invention, and other dimensions or geometries are possible. Plural structural components can be provided by a single integrated structure. Alternatively, a single integrated structure might be divided into separate plural components. In addition, while a feature of the present invention may have been described in the context of only one of the illustrated embodiments, such feature may be combined with one or more other features of other embodiments, for any given application. It will also be appreciated from the above that the fabrication of the unique structures herein and the operation thereof also constitute methods in accordance with the present invention.
[0018] The preferred embodiment of the present invention has been disclosed. A person of ordinary skill in the art would realize however, that certain modifications would come within the teachings of this invention. Therefore, the following claims should be studied to determine the true scope and content of the invention.
[0019] Any numerical values recited in the above application include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc. are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner.
[0020] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of “about” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to 30” is intended to cover “about 20 to about 30”, inclusive of at least the specified endpoints.
[0021] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes.
[0022] The term “consisting essentially of” to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination.
[0023] The use of the terms “comprising” or “including” to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist essentially of the elements, ingredients, components or steps.
[0024] Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of “a” or “one” to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps. All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1989. Any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. | The present invention is premised upon method of manufacturing rolled pierce nuts having a predetermined profile from a metal rod, more particularly to a method and apparatus delivering greater manufacturing flexibility through the use of multiple stations with flexible inputs and outputs. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to metal-to-metal seals and, more particularly, to a resilient metal-to-metal seal that in one embodiment may be mounted in a wellhead or BOP to control very high pressures, high temperature, and caustic fluids.
[0003] 2. Description of the Prior Art
[0004] Metal-to-metal seals have advantages over non-metallic seals in that they operate over a wider range of temperatures, fluids, and pressures. Non-metallic seals of various materials are best matched to a particular range of temperatures, fluids, and pressures. Neither the operator nor the manufacturer will always know the conditions under which wellhead devices may be utilized, which increases the risk of failure.
[0005] In the past, metal-to-metal seals have often been made of soft metals that deform to create a one-time-use seal. One of the problems of soft metal seals is that all seals must be replaced whenever the wellhead device is opened. The deformed material is unlikely to seal again when used more than once. Another problem is that these types of seals do not always make an initial seal, thereby necessitating opening up the wellhead device and replacing that seal as well as all other metal seals.
[0006] To the extent that hard metal-to-metal seals are utilized in the prior art, fine tolerances are often required that essentially limit the pressure that can be sealed. Moreover, small variations in the tolerances can render the seal ineffective.
[0007] To the extent resilient metal seals have been utilized, they are subject to problems in obtaining an initial seal and/or maintaining a seal with over wide pressure variations.
[0008] The following U.S. Patents describe various prior art efforts related to making metal-to-metal seals:
[0009] U.S. Pat. No. 4,911,245, issued Mar. 27, 1990, to Adamek et al, discloses a metal seal for sealing against casing in a well with a plurality of circumferentially axially spaced metal bands. An inlay material partially fills the cavities located between the metal bands. The metal bands are soft enough to deform when the seal is pressed into contact with the casing. The bands deform to a point flush with the inlay material. If the casing later moves axially relative to the seal because of temperature change or tension loading, then the inlay material will wipe across the band faces to maintain the seal.
[0010] U.S. Pat. No. 5,257,792, issued Nov. 2, 1993, to Putch et al, discloses a metal well head seal for sealing between inner and outer concentric well head components which includes a circular metal seal having a flat end and a tapered end and positioned between the inner and outer components. A forcing cone on one of the components engages the tapered end for sealing, a backup shoulder engages the flat end as the inner and outer components are longitudinally moved together for setting the metal seal. An adjusting nut adjusts the tolerances between the tapered end and the forcing cone.
[0011] U.S. Pat. No. 4,771,832, issued Sep. 20, 1988, to Bridges, discloses a wellhead assembly with a metal seal that accommodates misalignment between casing and the bore of the wellhead housing. The metal seal assembly includes a metal seal ring and a wedge ring. The seal ring has a cylindrical inner wall and a conical outer wall. The centerlines of the inner and outer walls are offset with respect to each other, making the ring eccentric. Similarly, the wedge ring has a conical inner wall and an outer wall. Its inner and outer walls are offset with respect to each other. The rings can be rotated relative to each other and to the casing to coincide the axis of the outer wall of the wedge ring with the axis of the wellhead housing bore. The inner wall of the seal ring has protruding bands which deform as a result of the softness of the metal to enhance sealing.
[0012] U.S. Pat. No. 3,166,345, issued Jan. 19, 1965, to Pinkard, discloses an improved sealing means including a seal ring, sealing between the cylindrical, upwardly extending neck of a tubing hanger element positioned in a tubing head, and a recess or socket of a bonnet flange, which is positioned over the upwardly extending cylindrical neck of the tubing hanger.
[0013] U.S. Pat. No. 4,455,040, issued Jun. 19, 1984, to Shinn, discloses a tubing head, tubing head adapter and tubing hanger sealed against annulus fluid or downhole pressure by an upper and a lower, pressure-energizing sealing assembly. The sealing assemblies are bidirectional, pressure-energizing and operate under working pressures of up to 30,000 psi. Each assembly consists of a metal seal ring made of highly elastic and ductile 316 stainless steel with a yield strength of approximately 30,000 psi, having a frustoconical shape, with the upper and lower tips of the cone enclosing an angle of approximately 28.degree. in the prestressed state. In the axial direction, the seal ring engages a support ring on one end and a tubing hanger shoulder at the other end, both of which form inclines of 30 degrees with the vertical (radial) plane. The support ring and the tubing hanger shoulders are made of materials having yield strengths of 50,000 psi and 75,000 psi, respectively. The preload applied to the seal assemblies is such that the seal ring plastically conforms to the harder surrounding surfaces and assumes a cone taper angle of 30 degree, in conformity with the mating support ring and tubing hanger shoulder. Thereafter, working pressure applied from either axial direction will be resolved along the incline of interacting surfaces into radial components which further enhance the sealing pressure along the inner and outer sealing surfaces. Because of this bidirectional pressure-enhancement, both seal assemblies may be tested through the application of test pressure from one common test port located between the two assemblies.
[0014] U.S. Pat. No. 4,056,272, issued Nov. 1, 1977, to Morrill, discloses an oil well pipe suspension apparatus including a wellhead having a pipe hanger supported therein and a Christmas tree supported thereon, a frusto-conical metal gasket providing a metal-to-metal seal between the hanger and the wellhead, and an “X” cross section resilient metal gasket providing a metal-to-metal seal between the hanger and the Christmas tree.
[0015] U.S. Patent Application No. 20050082829, published Apr. 21, 2005, to Dallas, discloses a metal ring gasket for a threaded union with a high-pressure, fluid-tight, metal-to-metal seal between subcomponents of a fluid conduit. The metal ring gasket is made of carbon steel or stainless steel depending on a composition of the fluid to be conveyed through the conduit. The metal ring gasket has beveled corners and is received in a beveled annular groove on mating surfaces of the subcomponents of the threaded union. When compressed in the annular groove between the subcomponents, the metal ring gasket creates an energized, high-pressure, fluid-tight seal that is highly resistant to pressure and is capable of maintaining a seal even at elevated temperatures resulting from direct exposure of the fluid conduit to fire.
[0016] U.S. Pat. No. 4,190,270, issued Feb. 26, 1980, to Vanderford, discloses a hanger for supporting tubing in a well head including a tubular body adapted for connection to a casing head and having a tapered and upwardly facing seat, a tubular hanger positioned within the body and supported on the seat, a downwardly converging annular space between facing portions on the exterior of the hanger and on the interior of the body, a metal seal ring positioned within the converging space, a seal actuator sleeve positioned between the hanger and the body and being movable axially to engage the seal ring, and a wedging screw extending through the body. The wedging screw engages the seal actuator sleeve and wedges the seal actuator sleeve onto the seal whereby the seal is forced into sealing engagement in the converging space between the hanger and the body.
[0017] U.S. Pat. No. 3,104,121, issued Sep. 17, 1963, to Nordin et al, discloses a seal assembly designed to withstand pressures such as those encountered at high pressure well heads which may be in the order of 20,000 p.s.i. A high pressure seal assembly for a flow control device, wherein the assembly includes co-acting surfaces between the flow control device and the main body for accommodating a seal structure to provide an improved seal equally effective against pressure applied from either direction.
[0018] U.S. Pat. No. 3,494,638, issued Feb. 10, 1970, to Todd et al, discloses a tubing hanger assembly including an adapter and seal assembly, mounted between the tubing head and the valve fitting at the top of a well, with the seal assembly being mounted in the bore of the adapter body, and held therein by a removable retaining nut and with the addition of a liquid seal injection valve communicating with the seal therein and a test port through the wall of the adapter for receiving a gauge for testing the seal prior to installing the adapter on the tubing head.
[0019] The solutions to the above described and/or related problems have been long sought without success. Consequently, those of skill in the art will appreciate the present invention, which addresses the above problems and other significant problems uncovered by the inventor that are discussed hereinafter.
SUMMARY OF THE INVENTION
[0020] It is a general purpose of the present invention to provide an improved metal seal assembly and method.
[0021] An object of the present invention is to provide an improved high pressure sealing assembly and method that may be utilized in pressure control equipment such as wellheads and BOPs.
[0022] Accordingly, the present invention provides a resilient and/or flexible metal seal that may be utilized without deformation. In one embodiment, a seal ring comprises seal members that are pliable, and which may be bent repeatedly within their range of operation without injury or damage. The metal seal comprises a metal seal ring that is capable of returning to an original shape or position after having been compressed. Unlike many metal seals, the metal seal assembly components of an embodiment of the present invention may be taken apart and when put back together will seal.
[0023] The apparatus in accord with one possible embodiment of the invention may comprise an energizing metal ring comprising metal energizing surface(s). The metal energizing surface(s) engage a groove in the metal sealing ring. When the metal energizing surfaces are urged into engagement with the metal groove of the metal sealing ring, one or both of an inner metal surface and an outer metal surface expand outwardly to increase the seal pressure applied by sealing surfaces. In this way, the present invention may be utilized to produce metal-to-metal seals, such as inner metal-to-metal seal and/or an outer metal-to-metal seal.
[0024] The apparatus may comprise forming an undercut portion which may be positioned at a mid-section of the metal sealing ring. The undercut portion decreases the thickness of at least one metal wall on which the sealing surfaces are formed to thereby increase flexibility of the inner metal member and/or the outer metal member.
[0025] The apparatus may comprise an initial seal mechanism positioned to engage the energizing metal ring and/or the metal sealing ring to form an initial metal-to-metal seal.
[0026] The apparatus may further comprise the initial seal mechanism comprising at least one threaded member and/or a third metal ring. The third metal ring may be a spacer ring sized to produce the initial metal-to-metal seal when engaging the energizing metal ring and/or the metal sealing ring. An inner and/or outer seal ring may be mounted on the third metal ring.
[0027] In one embodiment, the one or more metal energizing surfaces on the energizing metal ring or elsewhere can comprise one or more wedging surfaces such as a conical wedging surface and/or a flat wedging surface when viewed in a cross-section.
[0028] In another embodiment, the apparatus may comprise one or more protrusions mounted on the inner metal surface and/or the outer metal surface of the metal sealing ring wherein the line-of-contact metal-to-metal seals are produced by engagement with the protrusions. A protrusion may comprise rounded surfaces which engage surfaces such as inner and/or outer metal tubular surfaces. In one embodiment, the inner and/or outer metal tubular surfaces may comprise an annulus or pocket within pressure control equipment such as a BOP or wellhead.
BRIEF DESCRIPTION OF DRAWINGS
[0029] For a further understanding of the nature and objects of the present invention, reference should be had to the following detailed description, taken in conjunction with the accompanying drawings, in which like elements may be given the same or analogous reference numbers and wherein:
[0030] FIG. 1 is an elevational view of a wellhead device that shows metal-to-metal seals utilized within a wellhead device in accord with one possible embodiment of the present invention.
[0031] FIG. 2 is an elevational view, partially in cross-section, that shows a metal-to-metal seal assembly in accord with one possible embodiment of the present invention.
[0032] FIG. 3 is an elevational view, partially in cross-section, that shows a resilient expandable metal-to-metal sealing ring in accord with one possible embodiment of the present invention.
[0033] FIG. 4 is an elevational view, in cross-section, that shows an enlargement of region 4 of FIG. 1 wherein a metal-to-metal sealing ring is mounted in a wellhead device in accord with a possible embodiment of the present invention.
[0034] FIG. 5 is an elevational view, in cross-section, that shows an enlargement of region 5 of FIG. 1 wherein a metal-to-metal sealing ring is mounted in a wellhead device in accord with a possible embodiment of the present invention.
[0035] FIG. 6 is an elevational view, in cross-section, that shows an enlargement of region 6 of FIG. 1 wherein a metal-to-metal sealing ring is mounted in a wellhead device in accord with a possible embodiment of the present invention.
[0036] While the present invention will be described in connection with presently preferred embodiments, it will be understood that it is not intended to limit the invention to those embodiments. On the contrary, it is intended to cover all alternatives, modifications, and equivalents included within the spirit of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0037] Referring now to the drawings and more particularly to FIG. 1 , there is shown pressure control equipment 100 that is intended to be representative of various types of wellhead equipment, which may comprise wellheads, tubing assemblies, BOP's, spool assemblies, hanger assemblies, and the like. The present invention is not limited to use in pressure control equipment or to any particular pressure control equipment. Moreover, pressure control equipment 100 may comprise various additional components that are not shown.
[0038] Pressure control equipment 100 can be utilized to seal off a well to control fluids such as liquids and gasses. The fluids may be at high pressures or low pressures, may comprise a wide range of different fluids including acidic and caustic fluids, and may operate under a wide range of temperatures. In one embodiment of the present invention, a metal-to-metal sealing mechanism in accord with the present invention may be utilized to control pressures up to 30,000 psi for a wide range of fluids and temperatures.
[0039] Sealing assemblies in accord with embodiments of the present invention are shown at 10 A, 10 B, 10 C, and 10 D. In this embodiment, sealing assemblies 10 B and 10 D are actually the same assembly but are shown in different views that include different components. However, conceivably the components of 10 B and 10 D might be utilized in separate seal ring assemblies and are therefore referred to separately to show multiple possibilities. Various components applicable to sealing assemblies 10 A, 10 B, 10 C, and 10 D are also shown in greater detail in FIG. 2 and FIG. 3 . The embodiments of 10 A, 10 C and 10 D with surrounding features of pressure equipment 100 are shown enlarged in FIG. 4 , FIG. 5 , and FIG. 6 respectively. These components are discussed in greater detail hereinafter.
[0040] Pressure control equipment 100 may be utilized to control pressure in tubing 102 and casing 104 , which may be at different pressures, contain different fluids, and be at different temperatures. For example, tubing 102 may be under very high pressure, perhaps 30,000 psi while casing 104 might be under a relatively much lower pressure, such as 500 psi, atmospheric pressure, or even a vacuum. Different fluids and temperatures may also be present. The present invention is operable to control the fluids of different pressures, types of fluids, and temperatures.
[0041] As general background for pressure control equipment 100 , tubing head spool assembly 106 may be secured to tubing head adapter assembly 108 at flanges 110 and 112 by connectors such as stud/nut assemblies 114 . Tubing hanger 109 is secured within tubing head adapter assembly 108 . Tubing string 102 is supported by tubing hanger 109 . An end of tubing 102 may be threadably secured to tubing hanger 109 which is supported by internal shoulders within tubing head spool assembly 106 .
[0042] Casing hanger assembly 116 is secured to tubing head spool assembly 106 at flanges 118 and 120 by stud/nut assemblies 122 . Casing slip hanger assembly 124 secures casing 104 within casing hanger assembly 116 . Lockdown screw assembly 142 may be utilized for securing into position internal components of tubing head spool assembly 106 . Lockdown screw assembly 142 may also be utilized to provide energizing force for sealing assembly 10 D (and 10 C).
[0043] Various ports may be utilized for monitoring/testing seals in pressure control equipment 100 , for instance, to verify that the seals are not leaking. Seal monitor ports 126 and 132 may be utilized, for example, to monitor pressure at seal assembly 10 A and 10 C, respectively. Flange test ports 128 and 134 may be utilized for example, to monitor or perhaps inject test pressure at flange joints 130 and 136 , respectively. Pressures and other seals may be tested utilizing ports such as port 133 . Terminating sleeve assembly 140 may also be utilized for control lines and/or monitoring and/or testing pressures. Other pressure/control lines and/or test ports such as port 144 and control lines 146 and/or other related components may also be utilized, as desired. Outlet wing valves 168 and 170 may be utilized to control flow through outlets 172 and 174 , respectively.
[0044] Referring now to FIG. 2 , there is shown one embodiment of enlarged metal-to-metal sealing assembly 10 A. In this embodiment, metal-to-metal sealing assembly 10 A may comprise energizing ring 12 , seal ring 14 , and spacer ring 16 . In FIG. 3 , another embodiment of a seal ring, namely seal ring 14 A is shown, which is inverted as compared to seal ring 14 shown in FIG. 2 . In practice, seal ring assemblies 10 A, 10 B, 10 C, and 10 D may be mounted inverted or not, as is considered most suitable to the particular application. The seal ring assemblies seal in both directions.
[0045] In general operation, metal-to-metal sealing assembly 10 A produces an initial seal but is also responsive to a differential pressure applied across the assembly. If necessary and/or desired, the sealing force created may increase with increasing pressure and decreases with decreasing pressure. Due to the flexibility and relative movement of the sealing assembly components of the present invention, high tolerances are not required to provide a reliable hard metal-to-metal seal at high pressures. Pressure may be two-way and may be applied on either side of sealing ring 14 .
[0046] Spacer ring 16 is relatively movable with respect to sealing ring 14 . If pressure is applied to spacer ring 16 , then spacer ring 16 is urged against sealing ring 14 whereupon metal-to-metal sealing assembly 10 A responds to thereby increase the sealing force. If pressure against spacer ring 16 is relaxed, then spring pressure of inner and outer wings 20 and 22 may urge spacer ring 16 away from sealing ring 14 .
[0047] However, in the embodiment shown in FIG. 2 , spacer ring 16 may act as an initial seal mechanism by being mounted on a shoulder to provide an initial position for spacer ring 16 . Accordingly, spacer ring 16 may be sized to urge metal seal ring 14 against energizing ring 12 to provide an initial seal without pressure being present as discussed in more detail hereinafter. Thus, the present invention provides for a seal that is always effective low pressure as well as high pressures.
[0048] In one embodiment as best shown in FIG. 3 , seal ring 14 defines metal groove 18 which separates inner wing 20 and outer wing 22 , which are resiliently flexible. Many components of metal seal ring 14 and 14 A may be substantially the same, and therefore are numbered the same in either FIG. 2 or FIG. 3 . However, due to enlargement, some features metal seal ring 14 are more easily shown in FIG. 3 . Inner wing 20 and outer wing 22 may expand and contract with respect to each other. Unlike other metal seals which comprise deformable metal, inner wing 20 and outer win 22 are comprised of a hard metal alloy which does not deform during the operational range of movement, but instead may be arranged to allow inner wing 20 and outer wing 22 to elastically or resiliently flex with changing pressure requirements.
[0049] Energizing ring 12 may comprise inner and outer energizing surfaces 24 and 26 (See FIG. 2 ) which engage the interior surfaces 28 and 30 (See FIG. 3 ) of metal seal ring 14 and metal seal ring 14 A. In this embodiment, inner and outer energizing surfaces 24 and 26 comprise, at least in cross-section, a flat wedging surface that when urged against mating interior surfaces 28 and 30 act to expand inner wing 20 and/or outer wing 22 and/or allow contraction. While flat mating wedging surfaces are shown in cross-section, other surfaces may be utilized such as rounded or otherwise engagable surfaces that may allow expanding and/or contraction of inner wing 20 and outer wing 22 . In this embodiment, the angle of the wedging surfaces with respect to the horizontal are about 75 degrees. However, this amount may vary in one embodiment by five to ten degrees or in another embodiment by twenty or thirty degrees, and/or may be varied as desired. Energizing ring 12 engages sealing ring 14 to produce an initial seal. A force is applied by energizing surfaces 24 and/or 26 to expand inner wing 20 and outer wing 22 with respect to each other, which then engage corresponding metal surfaces to create a seal.
[0050] The force may vary due to differential pressure acting on surfaces 28 and 30 to provide a corresponding expansion of inner wing 20 and outer wing 22 . If the differential pressure decreases, the force will decrease and inner wing 20 and outer wing 22 may thereby reduce the force acting to expand inner wing 20 and outer wing 22 . Thus, depending on the desired configuration, it may not be necessary that a high sealing force be maintained at all times when a high force is not necessary to control the differential pressure. Instead, the sealing force may be adjusted to the differential pressures. This provides a long-lasting, reliable seal assembly that tightly seals even very high pressures, but which avoids the need for extremely tight tolerances for a high pressure metal-to-metal seal.
[0051] In one embodiment, the seal is made with line-of-contact metal-to-metal sealing. Thus, in metal seal ring 14 A, multiple round protrusions 32 and 34 are formed on outer surface 36 of metal seal ring 14 . In a cross-sectional view, the outermost tips of the protrusions will then engage an inner surface at what is effectively a point, because a circle makes contact with a line at a point. Because the point extends around metal seal ring 14 , this creates a circular line-of-contact. Metal seal ring 14 A comprises two inner seal contact points 44 and 46 , on inner surface 37 , and two outer seal contact points 32 and 34 . Contact points 34 and 46 may be configured to engage first and points 32 and 44 may subsequently engage. The contact pressure on the different sets of round protrusions may be different or may be approximately the same depending on the design.
[0052] The point of contact is shown in cross-section in FIG. 4 at line-of-contact point 38 for protrusion 40 . Thus, a line-of-contact seal is made at point 38 , as shown in cross-section, between metal seal ring 14 and inner tubular wall 148 . Likewise, a line-of-contact seal is made between metal seal ring 14 (or protrusion 42 ) and outer tubular wall 150 . Inner and outer tubular walls 148 and 150 are formed within pressure control equipment 100 , and essentially create a ring-shaped pocket which is utilized to hold seal assembly 10 A in position.
[0053] While the geometrical concepts of points and lines are an abstraction due to an assumption that the point and lines are infinitely small, the present invention provides a practical example of real world use of these concepts to provide a sealing mechanism. Therefore these contacts are described herein as points and lines even though they are not infinitely small.
[0054] As discussed above, it will be noted that metal seal ring 14 A has two outer protrusions 32 and 34 whereas metal seal ring 14 has only one outer protrusion 42 . Likewise metal seal ring 14 has only one inner protrusion 40 , whereas metal seal ring 14 A has two inner protrusions 44 and 46 . In one embodiment, for a radius of the protrusions might be in the approximate range of about 0.062 inches for a ring in the general range of 8 inches OD. However, this may vary.
[0055] The protrusions and/or other seal ring surfaces may comprise a contact surface that is overlaid with non-corrosive high strength hard alloy so that dents are not formed during operation. Thus, deformation of metal seal ring 14 and 14 A is avoided.
[0056] Another possible feature of metal seal ring 14 and 14 A is an undercut 48 which may be utilized to increase the flexibility of inner and outer wings 20 and 22 . In one possible embodiment, undercut 48 may comprise ends with radius of 0.06 inches. However, this may be adjusted as desired. Undercut 48 is positioned about midway at the bottom of the sloping portion of groove 18 . As well, inner and outer wings 20 and 22 may be made thinner or thicker depending on the desired flexibility.
[0057] Lower embodiment 50 may comprise a threaded socket to permit adjustment and/or mounting into an assembly and/or provide for easier removal. However, if desired, additional opening of groove 18 may be provided at lower portion 50 to provide even more flexibility of operation, if desired.
[0058] To provide back-up sealing, non-metallic seal rings may be utilized that may be likely to encounter lower pressures. For example, inner secondary seal ring 54 and outer secondary seal ring 52 may be utilized on spacer ring 16 as shown in FIG. 2 and FIG. 4 . As another possible example, as shown in FIG. 5 , inner secondary seal ring 74 and outer secondary seal ring 72 can also be utilized on an embodiment of a metal seal ring in accord with the invention, such as metal seal ring 14 A. Secondary seal rings may be comprised of non-metal materials and be of different types.
[0059] As discussed above, various means may be utilized for providing an initial seal for sealing mechanisms 10 A, 10 B, 10 C, and 10 D. In one embodiment, a spacer ring, such as spacer ring 16 may be sized so as to provide sufficient force to create an initial seal once the assembly is in position within pressure control equipment 100 . For example, as best shown in FIG. 4 , lower surface 58 of spacer ring 16 engages shoulder 152 formed within pressure control equipment 100 . Upper surface 56 of spacer ring 16 engages lower surface 62 of seal ring 14 . Moreover, upper surface 60 of energizing ring 12 has limited upper movement, which results in some spreading of protrusions 40 and 42 for making an initial metal-to-metal seal. Therefore, spacer ring 16 may comprise a sufficient vertical size, as shown in FIG. 4 , to urge metal seal ring 14 into sufficient engagement with energizing ring 12 to provide an initial metal-to-metal seal. Retaining ring 160 may be utilized to hold seal assembly 10 A in position during assembly. As discussed above, spacer ring 16 may also be slightly moveable and may act as a piston to increase pressure against sealing ring 14 .
[0060] A large differential pressure from above sealing assembly 10 A, as indicated by arrow 158 , will act on the interior surface of wings 20 and 22 , as discussed above, providing addition force for spreading protrusions 40 and 42 , and thereby increasing the sealing force applied at the line-of-contact seal. The large differential pressure may pass by energizing ring sidewalls 162 and 164 to engage surfaces 28 and 30 (see FIG. 3 ) of sealing ring 14 . Energizing ring sidewalls 162 and 164 may have a tolerance in the range of about five thousandths of an inch for sliding engagement with inner tubular wall 148 and outer tubular wall 150 . Likewise, as discussed above, pressure from below sealing ring assembly 10 A, as indicated by arrow 166 might be sufficient to urge spacer ring 16 upwardly and increase the sealing force.
[0061] In FIG. 5 , an enlarged view of sealing assembly 10 C is shown. In this embodiment, a different initial seal mechanism is utilized. In this embodiment, seal protector ring 64 , locking ring 66 , compression ring 68 , and/or screw 70 may be utilized to create an initial seal. In this embodiment, the assembly may be held in position during assembly by locking ring 66 and screw 70 . If the vertical height of compression ring 68 is not sufficient to produce an initial metal-to-metal seal, as discussed above in connection with spacer ring 16 operation, then screw 70 may be utilized to provide an additional initial metal-to-metal seal adjustment. Moreover, an additional lockdown screw assembly may be utilized, as discussed subsequently in conjunction with seal ring 10 D.
[0062] In operation, sealing assembly 10 C as shown in FIG. 5 , may function similarly to that of seal assembly 10 A. A high pressure above seal assembly 10 C, will create a differential pressure across seal assembly 10 C that will urge additional expansion or spreading force acting on an interior of inner and outer wings 20 and 22 and thereby increase the seal force produced by metal seal ring 14 C. Line-of-contact metal-to-metal seals are made at 78 and 76 . As noted above in this embodiment, inner secondary seal 74 and outer secondary seal 72 are provided on metal seal ring 14 C.
[0063] Sealing assembly 10 D may utilize wedging surfaces 82 and 84 to engage spacing ring 80 which urges sealing ring 14 D into engagement with energizing ring 12 . Wedging surfaces 82 and 84 may be activated by lockdown screw assembly 142 to force sealing ring 14 D into engagement with energizing ring 12 with a desired force for sealing. Thus, the sealing force can be adjusted if necessary. For instance, if pressure is detected across the seal, such at a test port, then addition sealing force may be applied.
[0064] In summary of general operation of a seal ring assembly, energizing ring 12 is urged against the sealing ring to spread the wings of the sealing ring whereby a metal-to-metal seal created. A spacer ring may be utilized to urge energizing ring into engagement with the sealing ring. The spacer ring may be sized to produce a desired force. The spacer ring may act as a piston that increases force with increasing differential pressure. Other means for urging energizing ring against seal ring may comprise bolts, locking mechanisms, and the like, some possible specific examples of which are illustrated herein.
[0065] In general, it will be understood that such terms as “up,” “down,” “vertical,” “upper,” “lower,” “above”, “below”, and the like, are made with reference to the drawings and/or the earth and that the devices may not be arranged in such positions at all times depending on variations in operation, transportation, mounting, and the like. As well, the drawings are intended to describe the concepts of the invention so that the presently preferred embodiments of the invention will be plainly disclosed to one of skill in the art but are not intended to be manufacturing level drawings or renditions of final products and may include simplified conceptual views as desired for easier and quicker understanding or explanation of the invention. One of skill in the art upon reviewing this specification will understand that the relative size and shape of the components may be greatly different from that shown and the invention can still operate in accord with the novel principals taught herein. While inner and outer seals are created as shown above, only an inner or outer seal might be created in accord with the present invention.
[0066] Accordingly, because many varying and different embodiments may be made within the scope of the inventive concept(s) herein taught, and because many modifications may be made in the embodiment herein detailed in accordance with the descriptive requirements of the law, it is to be understood that the details herein are to be interpreted as illustrative of a presently preferred embodiment and not in a limiting sense. | A high pressure metal-to-metal seal utilizes an expandable metal seal element able to withstand caustic fluids, high pressure, and high temperature. The metal-to-metal seal assembly is resilient for repeatable sealing and comprises an energizing metal ring and a metal sealing ring. Engagement of these two rings expands surfaces of the metal sealing ring to create inner and/or outer metal-to-metal seals. | 4 |
CROSS REFERENCE TO RELATED APPLICATION
[0001] This applications takes priority from and claims the benefit of U.S. Provisional Patent application Ser. No. 61/930,667 filed on Jan. 23, 2014, the contents of which are herein incorporated by reference.
COPYRIGHT STATEMENT
[0002] All of the material in this patent document is subject to copyright protection under the copyright laws of the United States and other countries. The copyright owner has no objection to the facsimile reproduction by anyone of the patent document or the patent disclosure, as it appears in official governmental records but, otherwise, all other copyright rights whatsoever are reserved.
BACKGROUND OF THE INVENTION
[0003] 1. Field of the Invention
[0004] Embodiments of the present invention relate to a vascular filter for protection during surgery. In certain embodiments, the present invention relates specifically to systems and methods involving angioplasty and/or stenting to protect against loose embolic material or other debris.
[0005] 2. Description of the Related Art
[0006] Angioplasty and stenting are performed to remove obstructions or blockages in arteries and thereby alleviate life-threatening conditions. The procedures may result in a fracturing or disintegration of the obstructing material and if the resulting particles, or debris, were permitted to flow downstream within the circulatory system, they can cause blockages in smaller arteries, or their microscopic branches termed the microcirculation, downstream of the treatment site. The result can be new life-threatening conditions, including stroke.
[0007] Various systems and techniques exist to remove debris from the circulatory system, including temporarily obstructing the artery by means such as a balloon and then suctioning debris and blood from the treatment site. While such techniques can effectively solve the problem stated above, they require that blood flow through the artery be obstructed, causing complete cessation or at least a substantial reduction in blood flow volume, during a time period which can be significant for organ or cell survival.
[0008] Filters have also been used to collect debris in the vascular system. The filters are generally inserted before the procedure to trap debris and then closed and removed with the trapped debris after the procedure. Multiple problems exist for filters in use today. One problem is that debris can escape a filter from the proximal end (opening) when the filter is closed for removal.
[0009] Another issue that arises focuses on debris that may be squeezed through the holes of the filter when the filter is closed. Another problem is that the size and/or inflexibility of the filter prevent the filters from being used in distal sections or peripheral arteries of the body. For example, a filter used in the carotid artery is unable to be used in a peripheral artery located in the foot. Another problem is that filters are fixed as to make it impossible for an additional device to enter the filter for additional treatment such as flushing or suction. Another problem is that the length and/or rigidity of the filters cause the filter poorly fit in strong bent arteries and thus be deformed or have gaps between the wall of the artery and the filter.
[0010] Another problem is that the length of filters cause the filters to be placed further away from the lesion. Another problem is that unwanted movement by the person holding the guideline for the filter may cause an unwanted influence in orientation or geometry of the filter. Another problem is that the membrane of the filter is thin and fragile and may tear during use, thus preventing from a sufficient number of holes being made in the membrane for filtering.
SUMMARY OF THE INVENTION
[0011] The instant apparatus and system, as illustrated herein, is clearly not anticipated, rendered obvious, or even present in any of the prior art mechanisms, either alone or in any combination thereof. A versatile system, method and series of apparatuses for creating and utilizing a vascular filter for protection during surgery. Thus the several embodiments of the instant apparatus are illustrated herein.
[0012] It is an object of the instant system to introduce a series of systems and methods involving angioplasty and/or stenting which protect against loose embolic material and other debris.
[0013] It is an object of the instant system to introduce a system including a filter with a membrane, a frame and a rod and the filter includes a self-expanding cylindrical nitinol stent.
[0014] It is an object of the instant system to introduce a system utilizing a distally disposed ring that slides on the rod at a distal end.
[0015] It is an object of the instant system to introduce a system utilizing a vascular filter for protection during surgery.
[0016] There has thus been outlined, rather broadly, the more important features of the versatile vascular filter for protection during surgery embodiments in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto.
[0017] In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
[0018] These together with other objects of the invention, along with the various features of novelty, which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be made to the accompanying drawings and descriptive matter in which there are illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Advantages of the present invention and better understanding will be apparent from the following detailed description of exemplary embodiments thereof, which description should be considered in conjunction with the accompanying drawings, in which:
[0020] FIG. 1 is an embodiment of a filter in various geometrical orientations;
[0021] FIG. 2 a is an example membrane of the filter in FIG. 1 ;
[0022] FIG. 2 b is an example membrane in FIG. 2 a from a different orientation;
[0023] FIG. 3 shows one embodiment of the frame of the filter in FIG. 1 ;
[0024] FIG. 4 a is an example strut connectors of the frame in FIG. 3 ;
[0025] FIG. 4 b shows a front view of the strut connector in FIG. 4 a;
[0026] FIG. 4 c shows a side view of the strut connector in FIG. 4 a;
[0027] FIG. 4 d shows a top view of the strut connector in FIG. 4 a;
[0028] FIG. 5 a is an example of the frame in FIG. 3 while the filter is in a collapsed position;
[0029] FIG. 5 b is an example of the frame in FIG. 5 a while the filter is in an open position;
[0030] FIG. 6 is a filter in FIG. 1 during removal of the filter;
[0031] FIG. 7 is a filter in FIG. 1 while a suction device is inserted into the filter;
[0032] FIG. 8 is a flowchart of an example method for inserting the filter in FIG. 1 ;
[0033] FIG. 9 is a flowchart of an example method for removing the filter in FIG. 1 ;
[0034] FIG. 10 illustrates a side perspective view of a pair of filter configurations with fiber reinforced membranes;
[0035] FIG. 11 illustrates an additional side perspective view of a filter configuration with fiber reinforced membranes;
[0036] FIG. 12 illustrates a side perspective view of a suction device entering the filter configuration with fiber reinforced membranes;
[0037] FIG. 13 illustrates a deployment and inflation diagram for one embodiment of the instant system and accompanying apparatuses; and,
[0038] FIG. 14 illustrates a mesh stent loaded inside a catheter for one embodiment of the instant system and accompanying apparatuses.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0039] Embodiments of the present series of apparatuses, systems and interrelated methods pertain to a vascular filter for protection during surgery. In certain embodiments, the present series of apparatuses, systems and interrelated methods relate specifically to systems and methods involving angioplasty and/or stenting to protect against loose embolic material or other debris. Throughout the description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention may be practiced without some of these specific details. In other instances, well-known structures and devices are shown in generic form to avoid obscuring the underlying principles of the present invention.
Filter
[0040] FIG. 1 is a photograph of an embodiment of a filter 100 various geometrical orientations. The filter 100 generally comprises: a membrane 101 ; a frame 102 ; and a rod 103 . In one embodiment, the filter 100 is based on a 7 mm long self-expanding cylindrical nitinol stent, acting as the frame 102 that keeps the filter 100 in position. In another embodiment, the length may range from 0.1 mm to 20 mm or any range within this range. Referring back to FIG. 1 , the frame 102 is connected to the membrane 101 . In one embodiment, the tip of the membrane 101 is connected to a distal ring ( 307 of FIG. 3 ) that slides on the rod 103 at a distal end. Distal is the end farthest away from the lesion where the device is to enter. On the proximal end, the rod is connected to the frame 102 . Proximal is the end opposite the distal end and closest to the lesion where the device enters.
[0041] The rod 103 may have a flexible, radio opaque distal tip to allow maneuverability within a blood vessel. In one embodiment, the rod is 0.35 mm in diameter and a guidewire for the person inserting the filter 100 . In another embodiment, the rod diameter ranges from 0.01 mm to 15 mm or any range within this range. The filter 100 may be housed by a sheath 104 (e.g., a tube) during insertion. In one embodiment, the tube 104 is used during the procedure as a suction or flushing device in order to remove debris from the filter 100 . Furthermore, in one embodiment the system may utilize a 0.018 mm guidewire.
Membrane
[0042] FIGS. 2 a and 2 b are photographs of an example membrane of the filter in FIG. 1 . In one embodiment, the membrane 101 is thin and pliable. The membrane 101 may be, but is not limited to, a mesh (e.g., wire mesh), paper filter, a perforated plastic, or any other opaque material with holes or porous material to allow the passage of fluid. The membrane may have a plurality of holes in order to filter blood or other fluids and trap debris. In one embodiment, the membrane includes approximately 1800 holes or apertures, wherein the diameter of each hole may be approximately 110 microns. In another embodiment, the number of holes may range from 1 to 10,000 or any range within this range. Also in another embodiment, the diameter of the holes may range from 30 microns to 500 microns or any range within this range. The holes may be cut into the membrane by a laser or other cutting devices.
Frame
[0043] FIG. 3 shows one embodiment of the frame 102 . In one embodiment, the frame 102 generally comprises: struts 301 ; free moving fibers 302 ; strut connectors 303 to connect struts 301 to free moving fibers 302 and/or reinforcement fibers 305 ; guide ring 304 to connect the free moving fibers 302 to the rod 103 ; and reinforcement fibers 305 connected to the struts 301 (by strut connector 303 ) and the membrane 101 .
[0044] In one embodiment, the free moving fibers 302 are fine ultra high molecular weight polyethylene fibers with high flexibility and extreme tensile strength and a thickness of approximately 50 microns. When expanded, the strut section 301 fits to the artery wall and leave the proximal entrance of the filter 100 open. In one embodiment, the struts are a shape memory alloy, such as nitinol, and the frame 102 is opaque to radio signals. Radio opacity of the frame 102 may be enhanced by a coating. For example, a gold-coating of 3 microns thickness may be applied to the frame 102 so that the status of deployment of the filter 100 is well visible on X-ray.
[0045] In one embodiment, the dimensions of the frame are a length of 7 mm and an external diameter of 0.7 mm collapsed and 7 mm expanded. In another embodiment, the external diameter may range from 0.1 mm collapsed to 20 mm expanded or any range within this range. The rod 103 may include a mechanical stop 306 to engage the guide ring 304 of the frame 102 or the distal ring ( 307 of FIG. 3 ) attached to the membrane 101 at the distal end when the rod 103 is moved far enough forward or backward. Therefore, the rod 103 may move in any direction without influencing, interfering, or changing the geometry and/or position of the filter 100 , as long as the stop 306 on the rod 103 stays within the range of free movement between the two rings 304 and 307 . The mechanical stop 306 does not require mechanical interaction and therefore allows the frame 102 to assume an ideal wall apposition, even if the filter 100 is placed in a strongly curved artery.
[0046] In one embodiment, the guide ring 304 allows inclusion of an additional device, such as a suction tube, into the filter 100 in order to suction it empty and thus prevent a pile-up of debris. In another embodiment, the free moving fibers 302 allow the insertion of such device. FIG. 7 illustrates a suction device being inserted into the filter 100 . In one embodiment, the sheath 104 acts as the suction tube. In another embodiment, the suction tube that fits in the guide ring 304 beside the rod 103 or between the free moving fibers 302 . Cleaning of the filter 100 allows the filter 100 to be left in place for a longer period without the problem of full occlusion, or to use it in cases where extreme amounts of debris are expected.
[0047] One embodiment of attaching the struts 301 to free moving fibers 302 is the strut connectors 303 . FIGS. 4 a - d illustrate an example strut connector 303 . In one embodiment, the strut connector is an anchor shaped end ( 401 of FIGS. 4 b - d ) of a strut 301 attached to a bend ( 402 of FIGS. 4 b - d ) of a free moving fiber 302 . Other embodiments of attaching the struts 301 to the free moving fibers 302 include, but are not limited to, tying the fiber 302 to the strut 301 and adhesives (e.g., glue).
[0048] As previously stated, in one embodiment, the frame 102 includes reinforcement fibers 305 connected to the membrane 101 . Since the membrane may be thin and pliable, reinforcement fibers 305 are connected to the membrane 101 in order to prevent cracking or separation of the membrane 101 from the frame 102 . In one embodiment, the fibers 305 are wrapped around the frame struts 301 and then embedded into the membrane 101 to prevent accidental detachment from the frame 102 . An example connection of the reinforcement fiber 305 to the strut 301 is illustrated in FIGS. 4 a - d . In one embodiment, the reinforcement fibers 305 run from a distal ring 307 connected to the membrane 101 (described above), loop around the end of the strut 301 , and connect back to the distal ring 307 . Alternatively or in addition, an adhesive may be used to attach the membrane 101 and/or the struts 301 to the reinforcement fibers 305 . One example adhesive includes polyurethane, which may be applied through a dipping process. In another embodiment, the reinforcement fiber 305 is woven through the holes of the membrane 101 .
[0049] The reinforcement fibers 305 may be from a multitude of materials, but one example reinforcement fiber is a fine multifilament fiber of high molecular weight polyethylene. In one embodiment, the tensile strength of the fiber exceeds 3000 mega Pascal (MPa) and flexible. In one embodiment, the flexibility of the fiber is limited in the length direction such that the maximum increase in length is approximately 3%. The fibers retain the properties of flexibility and tensile strength after thousands of cycles of use. The reinforcement fibers 305 also allow the membrane 101 to wrap around debris without squeezing during closure of the filter 100 . The reinforcement fibers 305 also receive the tensile stress from the rod 103 when removing the filter 100 from a sheath 104 and pull the membrane 101 into place.
[0050] The size, flexibility, and expandability of the filter 100 allow for the filter 100 to be used in multiple size blood vessels, including large arteries, such as the carotid artery or aorta, to peripheral arteries, such as those found in distal limbs of the body (e.g., the foot or hand).
Insertion of Filter
[0051] FIG. 8 is a flowchart of an example method of inserting the filter 100 into a blood vessel of the body. Beginning at 801 , a lesion is created in the blood vessel. In one embodiment, the blood vessel is punctured by a hollow wire. Proceeding to 802 , the sheathed filter 100 (e.g., in a tube) is inserted into the blood vessel far enough so as to set the filter 100 in the desired place within the blood vessel. Once the sheath 104 is inserted the desired distance into the blood vessel, the filter 100 is extracted from the sheath 104 in 803 . In one embodiment, the filter 100 is extracted by pushing the rod 103 so that the mechanical stop 306 ( FIG. 3 ) engages the distal ring 307 and pushes the ring 307 out of the sheath 104 . The distal ring 307 pulls the reinforcement fibers 305 out of the sheath 104 , which pulls the membrane 101 and struts 301 out of the sheath 104 . Once the struts 301 are pulled out of the sheath 104 , the struts 301 of the frame 102 expand to fit to the walls of the blood vessel in 804 .
[0052] FIG. 5 a illustrates the struts 301 of the frame while in the sheath 104 . The frame 104 is compressed into a small diameter for easy insertion into the blood vessel. FIG. 5 b illustrates the struts 301 when removed from the sheath 104 . The frame 104 expands and spreads the membrane 101 in order to filter the blood vessel for debris.
Removal of Filter
[0053] In one embodiment, the strut section of frame 102 of the filter 100 may be collapsed without changing the shape of the membrane 101 . FIG. 9 is a flowchart of an example method for removing a filter 100 . Beginning in 901 , the rod is pulled towards the user and the mechanical stop 306 of the rod 103 engages the guide ring 304 of the frame 102 . The guide ring 304 is then pulled into the sheath 104 . Pulling the guide ring 304 into the sheath 104 pulls the free moving fibers 302 connected to the guide ring 304 into the sheath 104 ( 902 ). Once the free moving fibers 302 are in the sheath 104 , the free moving fibers pull the struts 301 at the strut connectors 303 so as to radially compress the proximal edge of the strut section and pull the section into the sheath 104 ( 903 ). The proximal fibers pulling at the strut connectors 303 of the struts 301 creates a conical section in the frame. FIG. 6 illustrates the canonical form of the frame during removal of the filter.
[0054] FIG. 6 also illustrates that, while the struts 301 are pulled further inside the sheath 104 , the membrane 101 is still in its fully deployed state and gives full distal protection. When the strut section is compressed, the gaps between the struts 301 of the frame 102 close. In one embodiment, the closing frame acts as a cap that closes the proximal entrance of the filter, thus preventing any loss of captured debris, and acts as an additional filter. Referring back to FIG. 9 , the filter is extracted with the membrane 101 expanded and the proximal edge of the struts 301 sheathed. Since the membrane is expanded during extraction, no debris is able to escape from the filter during removal.
[0055] Embodiments of the invention may include various processes or components as set forth above. It will be apparent to one skilled in the art that not all components or processes are required, and the processes described for insertion and extraction of the filter may be in different order. In addition, while the filter has been described in terms of being used in the vascular system, other uses of the filter exist.
[0056] For example, the filter may be used in various piping not associated with the human body, the gastrointestinal system, the respiratory system, and/or other fluid conduits. In another example, while the reinforcement fibers are shown as lying longitudinally and approximately parallel to the rod, the reinforcement fibers may be any network or pattern, including a randomly oriented network. In another example, while the membrane is described as being stretched like an umbrella, reinforcement fibers may be fused with or be a shape memory alloy (e.g., nitinol) so as to control the shape the membrane. In another example, expandable or deformable frames are used.
[0057] In another example, while the filter is described as being attached, other devices may be attached to the sheath or rod. In an embodiment, additional proximal fibers are attached to such devices. Examples include removable temporary stents, occlusion devices, grafts, valves, clips, retrieval bags, inflatable members, devices for body tissue replacement and delivery platforms for drugs, radiation or gene therapy.
[0058] In another example, while a sheath is described as a tube, a sheath may include, but is not limited to, a ring to compress the frame, a latch attached to the struts to lock the frame in a compressed state, an at least one Micro Electrical Mechanical (MEM) motor or other motor to open and close the frame, or the frame being a piezoelectric material in order to compress when an electric current is introduced. In another example, while the frame is described as including a stent structure, the frame may alternatively include a plurality of crossbeams attached to the rod in order to open the membrane for filtering. In another example, while the strut connector is described as including an anchor shape structure, many shapes may be utilized, including a loop or a hook.
[0059] In another example, while a mechanical means is described for inserting, opening and removing the filter, the filter may be opened by other means including, but not limited to, fluid pressure to open the membrane for filtering or pressure from the artery wall to trigger opening of the filter. In a further example, while a radio opaque material is described for coating the frame for tracking the location of the filter, other materials may coat or be embedded in the material of the frame or filter including, but not limited to, a slight radioactive material that emits energy (e.g., through doping of the metal or coating) or a photo luminescent material to reflect light shined on the filter. In another example, while fibers are described as being polyethylene, other materials including metal, textiles, glass, or plastics may be used. In addition, while fibers are described, other means including threads or rope may be used. In another embodiment, while debris is described as embolic material, debris may be any material unwanted (e.g., foreign object) and thus to be removed.
[0060] In another example, removing the filter while the membrane is open is described, other removal means may occur including the membrane being closed and/or compressed to wrap around trapped debris during removal. In another example, while rings are described for engaging a stop, other engagement means may exist including, but not limited to, a hook, nub, protrusion, or friction surface.
[0061] In additional embodiments, much like FIG. 1 , FIG. 10 illustrates a side perspective view of a pair of filter configurations with fiber reinforced membranes. Additionally, FIG. 11 illustrates an additional side perspective view of a filter configuration with fiber reinforced membrane. And, FIG. 12 illustrates a side perspective view of a suction device entering the filter configuration with fiber reinforced membranes.
[0062] FIG. 13 illustrates a deployment and inflation diagram for one embodiment of the instant system and accompanying apparatuses. Moreover, FIG. 14 illustrates a mesh stent loaded inside a catheter for one embodiment of the instant system and accompanying apparatuses.
[0063] For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein above. Of course, it is to be understood that not necessarily all such objects or advantages may be achieved in accordance with any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein. All of the herein described embodiments are intended to be within the scope of the invention herein disclosed. | A filtration system to collect debris in the vascular system and/or other systems and a method for using such filter. An internally disposed apparatus for inside a fluid conduit during a medical procedure which includes a filtering membrane and a frame connected to the membrane. In one embodiment of the filtration system, a filter may generally include a membrane, a frame, and a rod. | 0 |
BACKGROUND OF THE DISCLOSURE
[0001] 1. Field of the Invention
[0002] The invention relates generally to data communication systems, and, more particularly, to methods and apparatus for synchronizing transmissions of serial data signals transmitted via such systems.
[0003] 2. Description of the Prior Art
[0004] Currently, high speed serial line communications is experiencing increasing use across many application areas, not the least of which being telecommunications. Generally, serial line communication systems transmit digital data, whether digitized voice in a telephone system or data from a computer, as a serial bit stream over various transmission media, such as wire cables, radio waves, fiber optic cables and the like. Typically, to efficiently transfer large quantities of data, individual bit streams from multiple data sources are multiplexed to form a single, serial bit stream. After transmission along a single transmission medium, the multiplexed bit stream is demultiplexed to reproduce the individual bit streams.
[0005] To facilitate proper routing of the individual bit streams to their respective destinations, the multiplexed serial bit stream must be organized so that a demultiplexer can identify and separate the bits, within the multiplexed bit stream, that are associated with each individual bit stream. Proper routing is accomplished by organizing the multiplexed bit stream into sequential frames each containing a sequence of time-slots. In practice, at a transmitter end of a serial line communication system, a multiplexer inserts bits from each individual bit stream into a corresponding time-slot within each frame. The locations of the bits within a frame comprising any one individual bit stream are known by counting bit positions, or time-slots, relative to the beginning, or end, of each frame. For example, in a 30 time-slot frame carrying bits from three data sources, bits from the first, second and third sources may be separately carried in the first, second and third successive ten time-slots relative to the beginning of the frame. Thus, specific time-slots, illustratively ten such slots, in each frame correspond to each data source. In this manner, each individual bit stream can be extracted from the frames and reassembled into individual bit streams associated with each particular data source.
[0006] Consequently, through proliferation of such serial line communications systems utilizing frame formatted data, a need has existed in the art to accurately determine a beginning, or an end, of each frame. Typically, a specific sequence of bits known as a “framing sequence” marks the beginning (or end) of each frame. To maintain frame synchronization, a data receiver, which may be a component of a demultiplexer, monitors a received bit stream for the framing sequence. Subsequently, the data receiver produces a frame synchronization signal upon each occurrence of the framing sequence. For example, in a 30-channel pulse code modulation (PCM) system commonly used for telephone transmissions in Europe and Asia, a frame comprises 32 time-slots with each slot containing 8 bits of data. Of these, 31 time-slots contain information bits from individual bit streams with the remaining time-slot, specifically the first in the frame, containing an 8-bit framing sequence. The eight bits in the framing sequence are typically:
[0007] X0011011, for even frames, and
[0008] X1AYYYYYY, for odd frames,
[0009] where the bits labeled X and Y are usually set to 1. The bit labeled A can be used as an alarm bit that is set to 1 whenever frame synchronization is lost.
[0010] Detrimentally, due to errors which typically arise from noise in the transmission medium, the information bits within a frame can be corrupted such that these bits identically resemble the framing sequence. In this instance, the data receiver would erroneously synchronize to the information bits rather than the framing sequence thereby causing a frame synchronization error and a resulting loss of data. To avoid such errors, oftentimes a second signal, a frame synchronization signal, is transmitted via a separate and independent transmission medium to the data receiver. The frame synchronization signal, in combination with the framing sequence, indicates the beginning (or end) of the frame. This arrangement avoids any ambiguities that may arise between information bits and the framing sequence. However, due to the additional transmission medium and associated receiver circuitry, such a dual transmission arrangement is costly and complex.
[0011] Thus, a need currently exists in the art for a technique, specifically apparatus and an accompanying method, for providing accurate frame synchronization in a serial line communication system. Advantageously, this technique should be immune to frame synchronization errors caused by certain data sequences in a transmitted frame. Furthermore, this technique should carry both a frame synchronization signal and a data bit stream, i.e., the information and framing sequence bits over a single serial transmission medium.
SUMMARY OF THE INVENTION
[0012] Accordingly, an object of the present invention is to provide a technique that can receive frame synchronization signals and data over a single serial transmission medium.
[0013] A specific object is to provide such a technique that is substantially immune to frame synchronization errors caused by information bit sequences which are identical to the framing sequences.
[0014] These and other objects are advantageously achieved through my inventive serial line synchronization technique. Specifically, in accordance with my inventive teachings, a frame synchronization signal, a clock signal and a data signal are encoded to form a single bi-phase mark signal wherein the frame synchronization signal is incorporated into the bi-phase mark signal as a phase-shift. The bi-phase mark signal is then transmitted through a transmission medium. A receiver, connected to the transmission medium, receives and amplifies the bi-phase mark signal. Subsequently, the receiver decodes the amplified bi-phase mark signal and reproduces the clock, frame synchronization and data signals.
[0015] By advantageously incorporating a frame synchronization signal into the bi-phase mark signal, my inventive serial line synchronization technique does not require a second transmission medium and associated receiver circuitry to transmit a frame synchronization signal separate from the data signal.
BRIEF DESCRIPTION OF THE DRAWINGS
[0016] The teachings of the present invention can be readily understood in conjunction with the accompanying drawings, in which:
[0017] [0017]FIG. 1 is an amplified high level block diagram of data transmission system 100 which incorporates my inventive serial line synchronization technique;
[0018] [0018]FIG. 2 is a schematic diagram of my inventive encoder 150 ;
[0019] [0019]FIG. 3 is a timing diagram for the encoder depicted in FIG. 2;
[0020] [0020]FIG. 4 shows the proper alignment of FIGS. 4A and 4B; and
[0021] [0021]FIGS. 4A and 4B collectively show a schematic diagram of my inventive decoder 225 .
[0022] To facilitate understanding, identical reference numerals have been used, where possible, to designate elements that are common to the figures.
DETAILED DESCRIPTION
[0023] Though the ensuing disclosure of my inventive technique illustratively discusses my invention in the context of a telecommunications system, those skilled in the art will recognize that the invention is useful in any serial line communication system that uses frame formatted data. Such systems include integrated services digital networks (ISDN), local area networks (LAN), packet radio systems and the like.
[0024] [0024]FIG. 1 depicts a simplified, high level block diagram of data transmission system 100 incorporating my inventive serial line synchronization technique. System 100 comprises serial line transmitter 105 connected, via optical fiber 170 , to serial line receiver 175 . Line 110 carries previously multiplexed and framed data (DATA) to an input of transmitter 105 . Additionally, line 115 carries a frame synchronization signal (SYNC) and line 120 carries a clock signal (CLOCK), both to respective inputs of transmitter 105 . Transmitter 105 merges the DATA, SYNC and CLOCK signals into a single serial bit stream using my inventive bi-phase mark modulation protocol. Subsequently, the serial bit stream is transmitted, via optical fiber 170 , to receiver 175 . A fiber optic transmission medium is, of course, illustrative. In practice, the transmission medium can also be, e.g., a twisted wire pair, a coaxial cable, a microwave transmission channel and the like. Upon reception of the signal propagating on the transmission medium, receiver 175 separates the CLOCK, SYNC and DATA signals and produces each of these signals on lines 230 , 235 and 240 , respectively. Ultimately, a demultiplexer (not shown) utilizes the individual signals to demultiplex the various individual bit streams contained in the DATA signal appearing on lead 235 .
[0025] Generally speaking, the CLOCK, SYNC and DATA signals are related to one another. In this regard, the CLOCK signal is phase synchronous with bits comprising the DATA signal; the SYNC signal indicates a reference point within a frame of data bits. Illustratively, the reference point is an end of a last time-slot in the frame. My invention uses a modulation technique known as a bi-phase mark protocol to combine the CLOCK and DATA signals into a serial bit stream. Simultaneously, the invention encodes the SYNC signal into this serial bit stream as a violation of the bi-phase mark protocol.
[0026] More specifically, transmitter 105 comprises delay line 125 , encoder 150 and light emitting diode (LED) driver 165 . Delay line 125 receives, on line 120 , the CLOCK signal and produces four delayed clock signals (CLK 1 , CLK 2 , CLK 3 , and CLK 4 ) each having a different delay relative to the CLOCK signal. For instance, the delayed clock signal on line 130 is delayed by approximately ¼ of a data bit relative to the input CLOCK signal. Similarly, the delayed clock signals on lines 135 , 140 and 145 are delayed ½ bit, ¾ bit and 1 bit, respectively. Typically, a data bit has a duration (or interval) equivalent to one clock cycle. For example, in a system having a bit duration of approximately 40 nS, i.e., a bit rate of 24.576 Mb/s, the delay line provides delays in 10 nS increments.
[0027] Encoder 150 has DATA, SYNC and the four delayed clock signals appearing on lines 130 , 135 , 140 , and 145 as inputs. Generally, the encoder merges the CLOCK, DATA and SYNC signals into a single serial bit stream. This is accomplished by phase synchronizing the CLOCK and DATA signals and then merging these two signals into a bit stream using a bi-phase mark protocol (as described in detail below). Suffice it to say, the bi-phase mark protocol permits the frame synchronization signal to be inserted into the bit stream as a phase-shift.
[0028] Encoder 150 produces, on line 160 , a bi-phase mark signal which serves as an input to LED driver 165 . The LED driver converts an electrical signal representing the bi-phase mark signal into an optical signal. LED drivers are well-known in the art, and therefore, a detailed description of such a driver is unnecessary to understand my invention. The optical signal produced by LED driver 165 is then propagated over optical fiber 170 to receiver 175 .
[0029] Receiver 175 , in general, reverses the encoding process of the transmitter and produces, on lines 230 , 235 , and 240 , the CLOCK, DATA, and SYNC signals, respectively. Specifically, receiver 175 comprises electro-optic (E-O) device 180 , amplifier 190 , delay line 200 and decoder 225 . E-O devices are well-known in the art, and therefore, a detailed description of such a device is also unnecessary to understand my invention. E-O device 180 accepts, as an input, the optical signal emanating from optical fiber 170 . As is well-known in the art, an E-O device converts the optical signal into a representative electrical signal. Typically, the representative electrical signal, on line 185 , has relatively low signal strength and thus must be amplified. Amplifier 190 amplifies and “squares up” the electrical signal and produces a bi-phase mark signal that is substantially identical to the bi-phase mark signal that was produced, on line 160 , by encoder 150 . Circuitry for accomplishing the amplification and squaring functions is well-known in the art and thus need not be described in any further detail.
[0030] Delay line 200 receives the bi-phase mark signal, appearing on line 195 , as an input and, as with the CLOCK signal above, generates four delayed output signals (D 1 , D 2 , D 3 , and D 4 ). Each delayed signal on lines 205 , 210 , 215 , and 220 is respectively delayed by a ¼, ½, ¾, and 1 bit interval, with respect to the bi-phase mark signal on line 195 . Using the four delayed bi-phase mark signals, decoder 225 separates the CLOCK, SYNC and DATA signals and produces each signal on lines 230 , 235 and 240 , respectively.
[0031] Next, a detailed discussion of the bi-phase mark protocol is presented. This discussion is followed by a detailed description of encoder 150 and decoder 175 that are used to implement my inventive synchronization technique.
[0032] Generally, encoder 150 combines the DATA, SYNC and CLOCK signals into a serial bit stream. My inventive technique merges the data and clock signals into a serial bit stream using a bi-phase mark protocol. The frame synchronization signal is introduced into the bit stream as a violation of that protocol. Generally, the bi-phase mark protocol encodes a digital stream of ones and zeros as a series of transitions during each bit interval, i.e., a clock cycle. Specifically, each zero is encoded as a transition at the beginning of a bit interval and each one is encoded as a transition at the beginning and at the middle of each bit interval. In this manner, the clock signal is inherently encoded into the bi-phase mark bit stream, i.e., as a transition at the beginning of each bit interval.
[0033] The frame synchronization signal is inserted by violating the requirement for a transition at the beginning of each bit interval. As discussed above, the data signal, after being formatted into frames, arrives at the transmitter. Thus, the framing sequence is already present in a time-slot within each frame when the frame arrives at the transmitter. The frame synchronization signal occurs, i.e., is high, during the occurrence of the framing bits in the data stream. For example, an individual frame may contain 32 time-slots each containing 8 bits of data. Illustratively, time-slots 0 through 30 carry information bits from a number of individual data sources and time-slot 31 carries the framing sequence to indicate the end of a frame. Hence, during all or a portion of time-slot 31 , the SYNC signal is high. Specifically, the frame synchronization signal should be high for at least one clock cycle in a bit position just prior to the position in the framing sequence where the protocol violation is to be inserted. Thus, continuing with the example, if the framing sequence in time-slot 31 is “00001011” and the protocol violation is to be positioned between the two consecutive ones, the frame synchronization signal should occur simultaneous with the second one, i.e., the second least significant bit. Accordingly, encoder 150 inserts a protocol violation between the last two bits, i.e., the framing sequence becomes “0000101v1”, wherein the violation (v) is a 180° phase-shift which removes a transition from the beginning of the last bit interval in time-slot 31 .
[0034] Encoder 150 will now be discussed with simultaneous reference to FIGS. 2 and 3. Therefore, the reader should refer to both of these figures throughout the ensuing discussion. FIG. 2 depicts the circuit details of encoder 150 , while FIG. 3 depicts a timing diagram showing the interrelation of important signals used and produced by encoder 150 .
[0035] As shown in FIG. 2, encoder 150 comprises timing generator 250 and bi-phase mark modulator 251 . Using the four delayed clock signals (CLK 1 , CLK 2 , CLK 3 , and CLK 4 ) on lines 130 , 135 , 140 and 145 , respectively, encoder 150 combines the CLOCK, DATA and SYNC signals and produces, on line 295 , a bi-phase mark signal (BIMDAT). Specifically, timing generator 250 processes the four delayed clock signals to generate a clock signal (CLK) on line 255 and a signal (2XCLK), on line 260 , the latter signal having double the frequency of the CLK signal and delayed by ⅛ of a bit interval relative to the CLK signal. The DATA signal, on line 110 , and the SYNC signal, on line 115 , in addition to the CLK and 2XCLK signals, form input signals to bi-phase mark modulator 251 .
[0036] [0036]FIG. 3 shows a timing diagram indicating the relative temporal positions of DATA 305 , SYNC 310 , CLK 315 , 2XCLK 320 , and BIMDAT 325 signals that form the input and output signals of the bi-phase mark modulator. CLOCK signal 300 is shown for reference purposes. CLOCK signal 300 , DATA signal 305 and SYNC signal 310 are phase coherent, while CLK signal 315 is delayed by ¾ of a bit interval with respect to CLOCK signal 300 . The signals shown correspond to the illustrative example, wherein time-slot 31 contains the framing sequence “00001011”. For the sake of simplification, the timing diagram depicts only a portion of the framing sequence near where the protocol violation is inserted. Specifically, the sequence “01011” is shown.
[0037] Bi-phase mark modulator 251 , shown in FIG. 2, contains logical AND gates 275 and 280 , NOR gate 285 , inverters 265 and 270 , and J-K flip-flop 290 . In effect, the modulator enables the CLK and inverted CLK signals to sample, through AND gates 275 and 280 , both an inverted DATA signal and the SYNC signal. To facilitate this sampling, inverters 265 and 270 invert DATA and CLK signals 305 and 315 , respectively. Subsequently, the resulting inverted signals are applied to one input of each AND gate 275 and 280 . Line 255 which carries CLK signal 315 connects to the second input of AND gate 275 . Line 115 which carries SYNC signal 310 connects to the second input of AND gate 280 . The outputs of AND gates 275 and 280 , i.e., a sampled inverted DATA signal and a sampled SYNC signal, serve as inputs to NOR gate 285 . The sampled inverted DATA signal and SYNC signal are combined in NOR gate 285 to produce a single bit stream. The output of NOR gate 285 connects to both J and K inputs of J-K flip-flop 290 . Additionally, line 260 connects the 2XCLK signal to the clock (CK) input of flip-flop 290 .
[0038] As is well-known in the art, a J-K flip-flop toggles at each rising edge of a signal applied to its CK input as long as high level signals are applied to both J and K inputs. Thus, in effect, the output of OR gate 285 controls when flip-flop 290 toggles. As shown, flip-flop 290 toggles upon each rising edge of 2XCLK signal 320 as long as the output of NOR gate 285 is high. Since a rising edge of 2XCLK signal 320 occurs at the beginning and a middle of a bit interval, the NOR gate output must blank, i.e., become low, during each zero data bit and during the protocol violation. As a result, the Q output of flip-flop 295 is a bi-phase mark signal, i.e., BIMDAT signal 325 .
[0039] In operation, bi-phase mark modulator 251 transforms DATA signal 305 into a bi-phase mark signal wherein each zero in DATA signal 305 appears as a transition at the beginning of a bit interval and each one in DATA signal 305 appears as a transition at the beginning and at the middle of a bit interval. In addition, SYNC signal 310 is encoded into the bi-phase mark signal as a violation of the protocol mandating that a transition occur at the beginning of each bit interval. In essence, SYNC signal 310 is used to block or mask a transition within the framing sequence. Alternatively, SYNC signal 310 can be viewed as causing a 180° phase-shift at the bit interval transition. Illustratively, the protocol violation occurs between the last two bits of the framing sequence in BIMDAT signal 320 . A driver circuit coupled to a transmission medium transmits BIMDAT signal 320 to a receiver and ultimately, to a decoder to recover the individual DATA, CLOCK and SYNC signals.
[0040] The encoder depicted in FIG. 2 is shown only as an illustration of one possible implementation using discrete components. Alternatively, for example, a circuit having a similar function can be implemented using programmable logic devices (PLD) such as the EP330-12 PLD manufactured by Altera Corporation of Irvine, Calif., or using an application specific integrated circuit (ASIC). Additionally, the position of the protocol violation discussed above is merely illustrative. The actual position of the violation will depend upon each individual application of the inventive technique. Also, the frame synchronization signal was illustratively described as occurring simultaneously with the position in the data where the protocol violation is to be placed in the framing sequence. However, those skilled in the art will realize that, broadly speaking, the protocol violation could be positioned anywhere within the entire frame.
[0041] [0041]FIGS. 4A and 4B, in combination, collectively show a schematic diagram of decoder 225 . Decoder 225 comprises 2X clock recovery circuit 400 , transition detector 405 , bit clock generator 410 , mask generator 420 , dejitter filter 425 , data recovery circuit 430 , frame sync recovery circuit 435 , and bit resynchronizer 440 .
[0042] In particular, from the four delayed BIMDAT signals, inputs (D 1 , D 2 , D 3 and D 4 ) on lines 205 , 210 , 215 , and 220 , respectively, decoder 225 recovers the CLOCK, DATA and SYNC signals. Generally, using the delayed BIMDAT signals, 2X clock recovery circuit 400 generates a 2XCLK signal which is two times the bit interval frequency. Simultaneously, transition detector 405 generates a pulse that represents each transition in the BIMDAT signal. Subsequently, an output of transition detector 405 , shown as the transition indicator signal (TRS), is used by bit clock generator 410 to generate a bit clock signal (BCLK). However, the missing transition at the protocol violation must be replaced to generate an accurate bit clock signal. Mask generator 415 produces a signal that inserts a transition into the BCLK signal at the protocol violation. Subsequently, the bit clock signal is filtered by dejitter filter 425 to produce, on line 230 , the CLOCK signal.
[0043] Data recovery circuit 430 and frame sync recovery circuit 435 use BCLK, and its inversion, in combination with transition indicator signal TRS, and its inversion, to recover data and sync signals, RDATA and RSYNC, respectively. Subsequently, the recovered CLOCK signal is used by bit resynchronizer 440 to reclock the RDATA and RSYNC signals and produce, on lines 235 and 240 , the DATA and SYNC signals, respectively. The DATA, SYNC and CLOCK signals are then passed along to a demultiplexer (not shown) to recreate the individual bit streams that comprise the information carried by the frames.
[0044] I will now discuss each individual circuit mentioned above in FIGS. 4A and 4B in detail. 2X clock recovery circuit 400 comprises exclusive OR (XOR) gate 445 , AND gates 450 and 455 , OR gate 460 and buffer 465 . The AND gates, the XOR gate, and the OR gate logically combine the four delayed BIMDAT signals to produce a clock signal (2XCLK) having a cycle duration that is half the duration of a bit interval in the BIMDAT signal. Specifically, XOR gate 445 combines, using an exclusive OR function, the ½ bit delayed (D 2 ) and the ¾ bit delayed (D 3 ) BIMDAT signals, on lines 210 and 215 , respectively, to produce a pulsatile signal having a ¼ bit long pulse corresponding to each transition in the BIMDAT signal. Simultaneously, AND gate 450 inverts and then combines, using an AND function, all of the delayed BIMDAT signals on lines 205 , 210 , 215 , and 220 . Simultaneously, AND gate 455 combines, using an AND function, all of the delayed BIMDAT signals. OR gate 460 combines, using an OR function, the output signals from XOR gate 445 and AND gate 450 and 455 . Buffer 465 buffers a resultant output from OR gate 460 . The OR gate output exits 2X clock recovery circuit 400 as output 2XCLK. The 2XCLK has a frequency which is twice the bit interval.
[0045] Transition detector 405 comprises XOR gate 470 , buffer 475 and D flip-flop 480 . Generally, XOR gate 470 produces pulses representing each transition in the BIMDAT signal; and flip-flop 480 lengthens the pulses representing each transition. Specifically, XOR gate 470 combines, using an exclusive OR function, the ¼ bit delayed (D 1 ) and the ½ bit delayed (D 2 ) BIMDAT signals, on lines 205 and 210 , respectively, to produce a pulse having a ¼ bit duration for each transition in the BIMDAT signal. Buffer 475 buffers each such pulse as it exits XOR gate 470 . D flip-flop 480 operates as a pulse stretcher to elongate each ¼ bit duration pulse to a ½ bit duration, i.e., equivalent to 1 cycle of the 2XCLK signal. The Q and {overscore (Q)} outputs from flip-flop 480 are respectively labeled TRS and {overscore (TRS)}. Importantly, the TRS signal is high for the first half of each zero bit and high for the entire bit interval for each one bit except at the protocol violation.
[0046] Bit clock generator 410 comprising J-K flip-flip 490 produces the bit clock signal (BCLK) in response to the TRS signal and the 2XCLK signal. Flip-flop 490 produces BCLK by toggling its Q output at each rising edge of the 2XCLK signal. In this manner, the BCLK signal has a frequency that is double the 2XCLK signal frequency. In other words, the BCLK signal has a cycle duration equivalent to one-bit interval. However, the protocol violation will cause flip-flop 490 to produce an improper transition in the BCLK signal. Therefore, mask generator 420 produces a masking signal at the protocol violation. OR gate 485 inserts the masking signal into the TRS signal. The insertion of the masking signal causes flip-flop 490 to ignore the protocol violation while producing BCLK.
[0047] Mask generator 420 comprises counter 415 and J-K flip-flop 510 . Counter 415 , itself containing AND gate 505 and flip-flops 495 and 500 , is a two-bit counter which is enabled by the {overscore (Q)} output of flip-flop 510 . In this manner, when a bit pattern occurs in the BIMDAT signal having the binary form “10” this counter is enabled and flip-flop 510 generates, at its Q and {overscore (Q)} outputs, a masking pulse having a two-bit duration. The masking pulse masks the occurrence of a protocol violation, if any, that follows the “10” bit sequence. During the occurrence of data bits with a binary “10” pattern that are not within the framing sequence, the flip-flop 510 generates a masking pulse, but the masking pulse has no effect upon the bit clock generator. However, when a “10” pattern appears in the framing sequence “0000101v1”, the “10” pattern initiates the masking pulse which replaces the improper TRS signal at the input of flip-flop 490 within bit clock generator 410 . As a result, the bit clock generator produces an accurate bit clock signal (BCLK). As those skilled in the art will readily recognize, the bit pattern that initiates the masking pulse could be any pattern. Also, circuitry could be implemented requiring recognition of a longer bit pattern than 2 bits prior to producing the masking pulse.
[0048] Dejitter filter 425 comprises buffer 515 , filter 520 and schmitt trigger 525 . Dejitter filter 425 reduces variation, which can result during the transmission and receiving processes, in the positions of the rising edges of the BCLK signal. Specifically, buffer 515 buffers the BCLK signal. The buffered BCLK signal is then sent to filter 520 . Filter 520 has a low pass frequency response and a phase response such that the input signal, BCLK, and an output signal, CLK, maintain a phase relationship having a difference of less than 90°, with transitions of CLK always occurring later than corresponding transitions of BCLK. Subsequently, schmitt trigger 525 sharpens the edges of a filtered signal at the output of the filter and produces the CLK signal.
[0049] As previously noted, the TRS signal is high for the first half of each zero bit and is high for the entire bit interval for each one bit. From the TRS signal, data recovery circuit 430 converts the TRS signal into a data signal having a one represented by a high level and zero represented by a low level. Data recovery circuit 430 comprises AND gates 530 and 535 , and flip-flops 540 and 545 . The data recovery circuit decodes the TRS signal using the BCLK and 2XCLK signals. The output of the data recovery circuit (RDATA) represents the data which was encoded by the transmitter. Importantly, the BCLK signal is high during the second half of each bit interval. The BCLK signal samples the TRS signal, and its inversion, through AND gates 530 and 535 . When the TRS signal indicates a logical one data bit, the TRS signal is high during the second half of each bit interval. When signals TRS and BCLK are both high, the output of AND gate 530 is high, as is the J input of flip-flop 540 . Consequently, output Q of J-K flip-flop 540 is high during an entire bit interval. Conversely, when TRS is low ({overscore (TRS)} is high), during the second half of the bit interval, the K input controls the output of flip-flop 540 and the Q output of this flip-flop is low for an entire bit duration. D flip-flop 545 reclocks the output of flip-flop 540 and generates, at its Q output, signal RDATA having a zero represented as a low signal for a full bit interval and one represented as a high signal for a full bit interval.
[0050] Similarly, frame sync recovery circuit 435 recovers the frame synchronization signal in response to the BCLK and TRS signals. As with data recovery circuit 430 , the frame sync recovery circuit decodes the TRS signal using the BCLK and 2XCLK signals. The output of the frame sync recovery circuit represents the SYNC signal that was encoded by the transmitter. Importantly, the {overscore (BLCK)} signal is high during the first half of each bit interval. Signal BCLK samples the TRS signal, and its inversion, using AND gates 550 and 555 . To effectuate decoding the SYNC signal, the output of AND gate 550 , and consequently the J input of flip-flop 560 , both become high only when a protocol violation occurs, i.e., when {overscore (TRS)}, during the first half of a bit interval, is high. Usually, AND gate 555 maintains a high signal at the K input of flip-flop 560 , thus maintaining a low output at the Q output of flip-flop 560 . However, upon the occurrence of a protocol violation, the Q output of flip-flop 560 becomes high and produces RSYNC.
[0051] Both the RDATA and RSYNC signals are reclocked by bit resynchronizer 440 using the CLK signal. The bit resynchronizer comprises two D flip-flops 570 and 575 . Specifically, flip-flop 570 reclocks RDATA with the CLK signal; similarly, flip-flop 575 reclocks RSYNC with the CLK signal. The outputs of decoder 225 are buffered by buffers 580 , 585 and 590 to produce the CLOCK, DATA and SYNC signals, respectively.
[0052] As with the encoder, the decoder depicted in FIGS. 4A and 4B is shown only as an illustration of one possible implementation. For example, a circuit having a similar function can be produced using a programmable logic device (PLD) or an application specific integrated circuit (ASIC).
[0053] Additionally, the foregoing discussion only described a transmission in a single direction. Duplex transmission is easily implemented by installing a transmitter with a receiver at each end of the transmission medium. Those skilled in the art will recognize that some minor modification to the receiver and transmitter would be necessary to propagate full duplex signals on a single transmission medium.
[0054] Although I have shown and described, in detail, a single embodiment of my invention, those skilled in the art can readily devise many other varied embodiments that still incorporate my inventive teachings. | Apparatus, and an accompanying method, for transmitting a frame synchronization signal and a data signal simultaneously through a serial transmission medium ( 170 ). Specifically within a data transmitter ( 105 ), a frame synchronization signal, a clock signal and a data signal, are encoded to form a single bi-phase mark signal having the frame synchronization signal incorporated into the bi-phase mark signal as a phase-shift. The bi-phase mark signal is then transmitted through a suitable serial transmission medium. A receiver ( 175 ), connected to the transmission medium, receives and amplifies an incoming bi-phase mark signal appearing on the medium, and, in turn, synthesizes the clock, frame synchronization, and data signals from this bi-phase mark signal. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a damper assembly which can attenuate the vibration occurring during washing, and more particularly, to a snubber base which moves up and down in a damper cap of a damper assembly in a washing machine, during which the snubber base makes contact with the damper cap.
2. Discussion of the Related Art
A washing machine, strips off contaminants such as dirt that is stuck on laundry, in general, by means of water circulation formed from the rotational force of a pulsator, and conducts either a washing or rinsing mode by means of pulsatile and rotational circulation of the water in an outside tub. The rotational force is formed by a regular or reverse direction rotating force of a motor. A driving force, is transmitted to the pulsator through a clutch-controlled speed reduction mechanism of clutch to rotate the pulsator. A washing machine also conducts a spin drying mode by means of the centrifugal force produced as the inside tub rotates. In a washing machine that uses water circulation strength or form to wash the laundry, the washing is carried out by stripping contaminants off the laundry with a combination of the mechanical actions of water shearing force, the bending and, stretching of the laundry, the friction exerted by and on the laundry, and chemical action of detergent.
FIG. 1 illustrates a cross sectional view of a conventional washing machine, including an outside tub 2 in a body 1 of the washing machine supported by a plurality of damper assembly 3, an inside tub 4 rotatably mounted in the outside tub for accommodating laundry (not shown), and a pulsator 5 rotatably mounted on a bottom of the inside tub 4 at a center thereof for generating a pulsatile circulation. The pulsator 5 is fixed to a shaft 7 rotated by a motor 6. A and there is a clutch under the shaft can be engaged to selectively rotate either the inside tub 4 or the pulsator 5. The rotational force generated by the motor is transmitted thereto through a timing belt 8. A water supplying device at the top of the body 1 selectively supplies, depending on selection of a water supplying mode of a user, either cold water and hot water simultaneously or cold water or hot water selectively, into the outside tub A detergent box 11 is located at an outlet in the water supplying device for automatic introduction of detergent into the outside tub 2 with the initial water supply when a washing mode is set A drain valve 12 is located at a lower portion of the outside tub for draining waste water after completion of washing.
Accordingly, after opening a door 13 on top of the body 1, and introducing the laundry into the inside tub 4, opened door 13 is closed and a washing mode is set on the control panel. When operating, the washing, rinsing, and dehydrating cycles are conducted in succession in response to control signals from a controller. Upon setting the washing mode in the controller, after the pulsator 5 is rotated to determine a weight of the laundry to determine a quantity of water to be supplied, the determined quantity of water is supplied into the inside tub 4. The detergent in the detergent box 11 is automatically introduced into the inside tub 4 together with the water supply. Upon completion of supply of the water and detergent into the inside tub 4, power is applied to the motor 6, generating a rotating force, to rotate a motor shaft in regular and reverse directions, intermittently. When the rotating force of the motor is transmitted to the clutch 9 through the timing belt 8 wound between the pulleys 14a and 14b, as the motor is driven, the clutch 9 rotates the pulsator 5 fixed to the shaft 7 at a reduced speed, to form a pulsatile circulation in the water in the inside tub 4 to circulate the laundry. Thus, washing of the laundry is made by a pulsatile circulation, friction between the inside tub 4 and the laundry and dissolving effect of the detergent. After proceeding through the aforementioned washing cycle for the laundry for a preset time period, drain valve 12 opens in response to a control signal from the controller drain waste water in the inside tub 4 to outside of the body 1. Upon completion of draining the waste water from the inside tub 4, water is supplied to inside tub 4 by an operation identical to the above operation, and pulsator 5 is operated for a preset number of pulses, to conduct the rinse cycle. While the water is supplied for the rinse cycle, no detergent is present in the detergent box 11. After completion of the rinse cycle, the clutch 9 is changed over from the pulsator 5 to the inside tub 4, to rotate a inside tub 4 without reduction in speed while leaving the pulsator 5 stationary in this manner, the washing machine conducts its spin cycle to remove water from the laundry. When the spin cycle is finished, an alarm indicates that the washing is complete and operation of the washing machine is finished.
In the washing machine, described above while in the washing, rinsing and spinning cycles where is a vibration resulting from the to driving of the motor in each of the modes and also from the circulation of the water and the laundry during washing and rinsing. This vibration causes noises during operation of the washing machine. In order to attenuate the vibration produced during operation of the washing machine, the outside tub 2, which has parts such as motor 6 and clutch 9 mounted thereon as shown in FIG. 1, is suspended from body 1 by means of a plurality of damper assemblies 3. The damper assembly 3 gradually attenuates vibration with spring damping, frictional damping from sliding between solid state bodies and air compression damping.
FIG. 2 schematically illustrates a perspective view showing conventional damper assemblies mounted in a washing machine. FIG. 3 illustrates a cross sectional view of the damper assembly shown in FIG. 2.
The damper assembly 3, mounted between the body 1 and the outside tub 2 for absorbing and attenuating the vibration generated during operation of the washing machine, will be explained with reference to FIGS. 2 and 3.
The damper assembly 3 includes an upper corner 15 at every corner inside of the body 1, an upper pivot 16 coupled to each of the upper corners, a snubber bar 17 having one end supported by the upper pivot and the other end hung from the one end, a plurality of supporting members 18 each formed on an outside circumference of the outside tub 2 at a lower side thereof, a damper which receives the other end of the snubber bar and supported by the supporting member 18 for damping the vibration. The damper 19 includes a guide bar 20a formed at top of a damper cap 20 as a single unit therewith for guiding up and down movements of the damper cap 20 along the snubber bar 17, a snubber base 21 coupled with the snubber bar at a bottom thereof for making up and down movements while making a close contact with an inside circumference of the damper cap, a damping spring 22 accommodated in the damper cap, inserted in the snubber bar and held in place by the snubber base, and a washer 23 inserted to the snubber bar under a bottom of the snubber base for preventing deformation of rubber of the snubber base during operation.
The aforementioned damper assembly 3 gradually attenuates the vibration generated either from the pulsatile circulation caused by centrifugal force of the pulsator 5 rotation and the laundry gathered to one side as the laundry circulate during washing or rinsing mode, or by inclination of the inside tub 4 and the laundry gathered as the inside tub 4 rotates during a dehydrating mode.
For example, if the laundry is gathered to one side at completion of drainage in the dehydrating mode, the inside tub 4, rotated with an inclination at an initial rotation, generates vibration, which is attenuated by the damper 19 between the body 1 and the outside tub 2. That is, the damper cap 20, supported by the supporting member 18 surrounding an outside circumference of the snubber bar 17 passed through and hung from the upper pivot 16 and having a top thereof connected to the outside tub 2, dampens the vibration as it is compressed and expanded in directions as shown by arrows in FIG. 3.
If the body 1 is away from the outside tub 2 due to the inclination of the inside tub 4, the outside tub 2, guided by the guide bar 20a at top of the damper cap 20, moves down along the outside circumference of the snubber bar 17. As the damper cap 20 moves down, the damper cap 20 rubs against an outside circumference of the snubber base 21 which is in close contact with the inside circumference of the damper cap 20 and the air inside of the damper cap 20 is compressed, to attenuate most of the vibration occurring during rotation of the inside tub 4. Moreover, the spring in the damper cap 20 is compressed when the damper cap 20 moves down to dampen the vibration.
If, on the other hand, the body 1 and the outside tub 2 come closer due to the inclination of the inside tub 4, the damper cap 20, guided by the guide bar 20a at top of the damper cap 20, moves up along the outside circumference of the snubber bar 17. As the damper cap 20 moves up, the damper cap 20 makes friction with an outside circumference of the snubber base 21 which is in close contact with the inside circumference of the damper cap 20 and the air inside of the damper cap 20 is expanded, to attenuate most of the vibration occurring during rotation of the inside tub 4. Moreover, the spring in the damper cap 20 is extended when the damper cap 20 moves up to dampen the vibration.
Of these vibration absorbing mechanisms of solid state friction damping (i.e., produced from sliding of the inside circumference of the damper cap 20 in contact with the outside circumference of the snubber base 21, air compression damping produced from compression of the air in the damper cap 20, and spring damping produced from compression and extension of the damping spring 221, the most important component to the damping is the snubber base 21 that moves up and down inside of the damper cap 20 to compress and extend the damping spring 22. This component to damping is important because the damping coming from friction as well as the damping coming from air compression results only if the outside circumference of the snubber base 21 makes close contact with the inside circumference of the damper cap 20. The part that continuously maintains the damping of the damper 19 effective by causing the outside circumference of the snubber base 21, i.e., the sliding surface to make a close contact with the inside circumference of the damper cap 20 is the snubber base spring 24 inserted in the inside circumference of the snubber base 21. The snubber base spring 24 should be adapted to keep a state in which the snubber base spring 24 is fitted in the snubber base 21 and to apply a force to the snubber base 21 continuously to expand the snubber base 21. To do this, as shown in FIG. 4, there is a recess 21 a formed in the inside circumference of the snubber base 21 which is held at the other end of the snubber bar 17 for making up and down movements in the damper cap 20, for the purpose of inserting the snubber base spring 24 therein. Although in most cases, the snubber base 21 is formed of a rubber, it may be formed of a plastic. When the damper 19 has a rubber snubber base, since it is not self lubricative with a great friction, a coat of fluororesin is applied to the outside circumference of the snubber base 21 to reduce the friction, for smoother sliding movements at a contact surface between the damper cap 20 and the snubber base 21. And, there is a steel washer 23 fixed under the bottom of the snubber base 21 which is held at a lower end of the snubber bar 17 for preventing distortion of the snubber base 21 of a comparatively soft material during operation. However, when the damper 19 has a plastic application snubber base 21, though the application of fluororesin coating to the sliding surface(the outside circumference) is not required because the plastic is self lubricative and no washer is required because rigidity of the plastic is greater than the rubber, an appropriate friction between the inside circumference of the damper cap 20 and the outside circumference of the snubber base 21 will not be provided unless a separate elastic body is not inserted in the inside circumference of the snubber base 21. Because injection molding of the recess 21a in the inside circumference of the snubber base 21 for inserting the elastic body, under-cutting the snubber base 21, is not easy to process, the elastic body is not actually provided to the snubber base 21.
Instead either a coil spring 24a as shown in FIG. 5A or a tension spring 24b as shown in FIG. 5B is used as a substitute for the snubber base spring 24 and expand the snubber base 21 so that the snubber base 21 can make close contact with the inside circumference of the damper cap 20. However, as the coil spring 24a has a smaller elastic force that is not enough to cause the outside circumference of the snubber base 21 to make a close contact with the inside circumference of the damper cap 20, the tension spring 24b is used in most of the cases. Both ends of the tension spring are bent inwardly for easy of assembly and preventing tearing of the snubber base 21 of rubber.
However, the aforementioned conventional damper assembly has the following problems.
First, if tension spring 24b is use as the snubber base spring 24, because there is no means for preventing the tension spring 24b from moving in a direction of the arrow shown in FIG. 4 along the recess 21a formed in the inside circumference of the snubber base 21 during the up and down movements of the snubber base 21 inside of the damper cap 20, it is frequently observed that the tension spring 24b comes off out of its position, resulting in degradation of the solid state friction damping coming from the sliding friction because the outside circumference of the snubber base can not make a close contact with the inside circumference of the damper cap 20 during the up and down movements of the snubber base 21. If coil spring 24a is applied as the snubber base spring 24, and the spring does not have enough force to expand the snubber base 21, the space inside of the damper cap 20 will be insufficiently can be hardly sealed and there may insufficient friction at the contact surface between the damper cap 20 and the snubber base 21.
Second, there can be a distortion of the snubber base 21 caused by the temperature rise resulting from the friction between the damper cay 20 and the snubber base 21 during vibrations. The distortion causes the seal to break between the inside circumference of the damper cap 20 and the snubber base 21 of vibration by the friction and sealing is minimal. Furthermore, as the fluroresin applied to the sliding surface 21b wears down the friction caused by the direct contact of the rubber outside circumference of snubber base 21 with the inside surface of the damper cap 20, causes the lower lip of the snubber base 21 to turn inside out. In other words, the strong friction at the direct contact of the rubber, which has a greater friction than the fluororesin, with the inside circumference of the damper cap when the damper cap 20 moves down causes the lip of the snubber base 21 to turn inside out. This inversion of the lip results in the snubber base spring coming out of the recess 21a and causes the aforementioned problem namely, breaking the seal between damper cap 20 and snubber hase 21.
Third, if due to a severe vibration the snubber base 21 comes out of the damper cap 20, through the bottom opening of the damper cap 20 snubber base spring 24 may fall out of the snubber base. The soft rubber of snubber base 21 is expanded by the elastic force of the snubber base spring 24 to a diameter greater than the inside diameter of the damper cap 20. Thus, if snubber base spring 24 hits the bottom of the damper cap 20 at rise of the snubber base 21, the spring may fall out of the snubber base and cause the aforementioned problem.
Fourth, under certain circumstances can extend the lower end of the snubber bar 17, beyond the bottom of the snubber base and hit the steel washer 23 which generates noise or, if the snubber base 21 is plastic, in which case no steel washer is inserted in the snubber base 21 due to the rigidity of plastic, the plastic snubber base may break when the snubber bar hits the snubber base 21 due to the incapability of pushing down of the snubber base 21 during the upward movement of the damper cap 20 coming from degradation of the elastic force of the damping spring 22 after repeated vibration absorption action. This leads to an impact on the bottom of the snubber base 21 when the damper cap 20 moves down again, which causes the lower end of the snubber bar 17 to hit the steel washer or plastic snubber base.
SUMMARY OF THE INVENTION
Accordingly, the present invention is directed to a damper assembly in a washing machine that substantially obviates one or more of the problems resulting from the limitations and disadvantages of the related art.
An object of the present invention is to provide a damper assembly in a washing machine which can prevent the snubber base spring therein from falling out of the snubber base and the snubber base from being distorted to maintain effective damping by the damper.
Another object of the present invention is to provide a damper assembly in a washing machine that can reduce vibration and noise of a washing machine and prevent breakage of a snubber base.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be apparent from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
To achieve these and other advantages and in accordance with the purpose of the present invention, as embodied and broadly described, the damper assembly in a damping system comprises a plurality of snubber bars each having an upper portion supported at a corner of a washing machine body, a damper cap coupled to an outside surface of an outside tub for supporting a lower portion of each of the snubber bars, a snubber base held at a lower end of each of the snubber bars and elastically inserted inside of each of the damper caps by a damping spring for making up and down movements while making a close contact with an inside circumference of the damper cap, and a snubber base spring inserted in an inside circumference of the snubber base for expanding the snubber base so that an outside circumference of the snubber base makes a close contact with the inside circumference of the damper cap, the damper assembly includes spring holding means having upper projections and lower projections formed on the inside circumference of the snubber base for keeping the snubber base spring in position, and at least a cut-away portion formed in a circumferential surface of the snubber base for uniform distribution of an elastic force of the snubber base spring so that the close contact of the snubber base with the inside circumference of the damper cap can be improved.
Further, there is stopper means formed inside of the snubber base for preventing rotation of the snubber base spring during the up and down movements of the snubber base. The stopper means may preferably be formed at a position located away from the cut-away portion.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are intended to provide further explanation of the invention as claimed.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention:
In the drawings:
FIG. 1 illustrates a cross sectional view of a conventional washing machine;
FIG. 2 schematically illustrates a perspective view showing conventional damper assemblies mounted in a washing machine;
FIG. 3 illustrates a cross sectional view of the damper assembly shown in FIG. 2 as mounted;
FIG. 4 illustrates a front view of a conventional snubber base with a partial cut-away view;
FIG. 5A illustrates a plane view of a coil type snubber base spring;
FIG. 5B illustrates a plane view of a steel wire type snubber base spring;
FIG. 6 illustrates a cross sectional view of a snubber base in accordance with a preferred embodiment of the present invention;
FIG. 7 illustrates a bottom view of a snubber base in accordance with a first embodiment of the present invention;
FIG. 8 illustrates a section across line I--I in FIG. 7;
FIG. 9 illustrates a bottom view of a snubber base in accordance with a second embodiment of the present invention;
FIG. 10 illustrates a section across line II--II in FIG. 9;
FIG. 11 illustrates a cross sectional view of a snubber base in accordance with a third embodiment of the present invention; and,
FIG. 12 illustrates a cross sectional view of a snubber base in accordance with a fourth embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Reference will now be made in detail to the preferred embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The present invention is applicable to a damper assembly 3 using a snubber base 21 formed of a plastic and a tension spring 24b as a snubber base spring 24.
A preferred embodiment of the present invention will be explained with reference to FIGS. 6˜8.
There is snubber base spring coupling means provided on the inside surface of the snubber base 21 applicable to the preferred embodiment of the present invention, having upper and lower projections 25 and 26 for preventing a snubber base spring 24 from falling out of the snubber base. A detailed configuration of the snubber base spring coupling means having upper and lower projections 25 and 26 is as follows.
There are a plurality of lower projections 26 formed on an inside surface of the snubber base 21 at fixed intervals to support lower portions of the snubber base spring 24 for preventing the snubber base spring from falling out of the snubber base 21, and a plurality of upper projections 25 formed at an upper portion of the snubber base 21 to support an upper portion of the snubber base spring 24 for preventing the snubber base spring from being moved to an upper portion of the snubber base. The upper, and lower projections 25 and 26 may be formed to be aligned vertically on the inside surface of the snubber base 21 as shown in FIG. 7 for inserting the snubber base spring 24 therebetween, or to straddle on the other for inserting the snubber base spring 24. However, the upper, and lower projections 25 and 26 are not restricted to the aforementioned individual configuration because objects of the present invention can be achieved even if the upper, and lower projections 25 and 26 are not formed individually. Namely, each of the upper, and lower projections 25 and 26 may be formed as a single unit. However, this configuration of the upper, and lower projections 25 and 26 may cause problems in that it may not be favorable in view of mass production because processing of an undercut portion with injection molding is difficult. Furthermore, fitting or taking out the snubber base spring 24 in or from the upper, and lower projections 25 and 26 is cumbersome. Of the plurality of upper and lower projections 25 and 26 formed on inside surface of the snubber base 21, the upper projections 25 may be formed vertical and the lower projections 26 may be formed vertically below the upper projections 25 to reinforce the strength of the outside circumference of the snubber base, i.e., the sliding surface.
A thickness t of the sliding surface 21b at a portion between the upper and lower projections 25 and 26 is set to be in a range of 0.1˜0.7 mm because if the thickness t of the sliding surface 21b is set less than 0.1 mm, the thickness is too thin to have a good injection moldability and will result in many defects. If the thickness t of the sliding surface 21b is set greater than 0.7 mm, the thickness may be too thick to permit the outside surface of the snubber base 21 to make the appropriately close contact with the inside surface of the damper cap 20 because even if the snubber base spring 24 is inserted between the upper and lower projections 25 and 26 to expand the snubber base 21, sliding surface 21b may not be expanded by the elastic force of the snubber base spring 24 as intended because of thicknes of the sliding surface. The thickness t of the sliding surface 21b may most preferably be in a range of 0.3˜0.5 mm to have the best injection moldability of the snubber base 21 and also permit the snubber base 21 to be expand by the elastic force of the snubber base spring 24 and thereby make a close contact with the inside circumference of the damper cap 20.
And, a plurality of cut-away portions 21c are formed on the outside circumference of the snubber base 21 to be in communication with a inside space thereof for a satisfactory expansion of the sliding surface 21b by the elastic force of the snubber base spring 24 inserted between the upper and lower projections 25 and 26. Though it is not necessary to restrict the cutting direction of the cut-away portions 21c, considering formability, it is preferable to cut them in an axis direction (vertical direction on the drawing) as shown in FIG. 6. And, a size of the cut-away portion 21c, i.e., a length L from bottom of the snubber base 21 to an upper end of the cut-away portion 21c, is set such that the upper end of the cut-away portion 21c is positioned above a center of a section of the snubber base spring 24 inserted between the upper and lower projections 25 and 26. This positioning provides a satisfactory expansion of the sliding surface 21b by the elastic force of the snubber base spring 24 inserted between the upper and lower projections 25 and 26 so that the sliding surface can make a close contact with the inside circumference of damper cap 20. If the length L from bottom of the snubber base 21 to the upper end of the cut-away portion 21c is formed short so that the center of the snubber base spring 24 inserted between the upper and lower projections 25 and 26 is positioned above the upper end of the cut-away portion 21c, there will not be any satisfactory expansion of the snubber base 21 even if the elastic force of the snubber base spring 24 acts thereon. This will result in less than desirable contact between the inside circumference of the damper cap 20 and the outside circumference of the snubber base 21. Consequently, the solid state friction damping produced by the sliding friction between the inside surface of the damper cap 20 and the outside surface of the snubber base 21 as well as the air compression damping by the air inside damper cap 20, may be insufficient.
Other embodiment of the present invention will be explained with reference to FIGS. 9 and 10.
Another embodiment of the damper assembly of the present invention further includes a stopper means 27 for preventing rotation of the snubber base spring 24 that may occur during the up and down movements of the snubber base. The stopper means 27 is in addition to the first embodiment of snubber base 21 of the present invention explained above. As shown in FIGS. 9 and 10, although the stopper means 27 is illustrated as a rib formed on the inside surface of the snubber base 21 in an axis direction (a vertical direction on the drawings) as a single unit with the snubber base 21, the configuration of the stopper means 17 is not restricted to this particular configuration only because a separate stopper means may be attached on the inside surface of the snubber base 21 to obtain the desired effect of preventing rotation of the snubber base spring 24 during the up and down movements of the snubber base 21 within the damper cap 20. The rib, illustrated as stopper means 27, is preferably formed a certain distance from the cut-away portion 21c in the outside surface of the snubber base 21 to prevent distortions. If stopper means 27 is placed such that both ends of the snubber base spring 24 are positioned close to any one of the cut-away portions 21c in the elastic force of the snubber base spring may distort snubber base 21, there is a possibility that the snubber base 21 is distorted into an ellipse as shown in dotted line in FIG. 9. That is, since the snubber base spring 24 inserted between the upper and lower projections 25 and 26 with a compression force has the greatest expansion force at both ends thereof having inwardly bents, if one of the cut-away portions 21c exists close to both ends, the snubber base 21 may be distorted into an ellipse. Therefore, if there are a plurality of cut-away portions 21c as shown in FIG. 9, the stopper means 27 should be formed substantially in the middle of the adjacent cut-away portions 21c for preventing the sliding surface 21b from being deformed excessively. The stopper means 27, formed in the axis direction in a form of a rib as a unit therewith, also serves to reinforce the snubber base 21.
Another embodiment of the damper assembly of the present invention will be explained with reference to FIGS. 11 and 12.
This other embodiment of the damper assembly is devised such that the lower end of the snubber bar 17 does not impact at the bottom of the snubber base 21 even if the restoring force of the damping spring 22, which acts as a spring damper, is reduced do to the prolonged use of the washing machine. That is, even if the restoring force of the damping spring 22 is reduced until it is incapable of pushing the snubber base 21 down at rise of the damper cap 20, leading the lower end of the snubber bar 17 to extend beyond the bottom of the snubber base 21 as shown in FIGS. 11 and 12, this embodiment of the damper assembly is devised to prevent the lower end that extends beyond the bottom of the snubber base 21 from impacting the bottom of the snubber base 21 before damper cap 20 moves down. In order to achieve this result, a washer 28 is provided at a bottom of the snubber base 21 occurs. The washer 28 is formed of a sound absorbing material that can absorb the impact that when the lower end of the snubber bar 17 hits the bottom of the snubber base 21 because of the degradation of the restoring force of the damper spring 22. The washer can be made of any material if it can absorb the impact the and noise caused of impact by the snubber bar. However, it is preferable to use a rubber, sponge or textile because of production cost and commercial availability. Washer 28 fitted on bottom of snubber base 21 may be fixed directly, and after to the bottom of the snubber base 21 as shown in FIG. 11, or it may be fixed in a recess 21d formed in the bottom of the snubber base 21 as shown in FIG. 12. However, in the case when the washer 28 is accommodated in the recess 21d, to obtain satisfactory impact absorption the washer 28 should be fitted such that the washer 28 is extended beyond the bottom of the snubber base 21 or occupies an area wider than an area of the lower end of the snubber bar 17. Various joining means, such as press fit, bonding, thread joining, and hooking are applicable in fitting washer 28 to the bottom of the snubber base 21.
The damper assembly of the present invention as has been explained has the following advantages.
First, even if a tension spring 24b is used as the snubber base spring 24, the solid state firction damping produced form the sliding friction can be maintained because of the close contact between the outside circumference of the snubber base and the inside circumference of the damper cap. The close contact results from stopper means 27 preventing the snubber base spring from rotating along the recess 21a and falling out during the up and down movement of snubber base 21 within damper dap 20. since the
Second, even if there is a temperature rise in damper cap 20 and snubber base 21 due to the repeated friction between them, because the upper and lower projections 25 and 26 formed on the inside surface of the sliding surface 21b prevent the distortion of the snubber base 21, there will be close contact between the outside circumference of the snubber base 21 and the inside circumference of the damper cap 20 resulting in continued absorption of vibration by means of friction and air compression/expansion furthermore, even if the rubber outside circumference of snubber base 21 and the inside circumference of damper cap 20 rub together creating friction because fluororesin coating applied on the sliding surface 21b is worn down from repeated friction, snubber base 21 will not be turned inside out because the upper and lower projections 25 and 26 formed on the inside surface of the sliding surface 21b can sustain their strength.
Third, even if snubber base 21 comes out of damper cap 20 through the bottom opening of damper cap 20 due to a severe vibration, the snubber base spring can be kept in postion by the strong support of the upper and lower projections 25 and 26.
Fourth, even if the lower end of the snubber bar 17, is extended beyond bottom of the snubber base 21 due to the inability to push snubber base 21 down of during an upward movement of the damper cap 20 and impact the bottom of the snubber base 21 when the damper cap 20 moves down again, no impact will be given to the snubber base because washer 28 is formed of a sound absorbing material fitted at an underside of the snubber base 21. This prevents breakage of the snubber base as well as generation of noise.
Fifth, the close contact between sliding surface 21b and the inside circumference of damper cap 20, permitted by the satisfactory expansion of the sliding surface 21b due to the formation of the cut-away portions 21c in the snubber base 21, improves a damping effect.
It will be apparent to those skilled in the art that various modifications and variations can be made in the damper assembly in a washing machine of the present invention without departing from the spirit or scope of the invention. Thus, it is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents. | A damper assembly for a washing machine includes a snubber bar, a damper cap, a snubber base, and a snubber base spring. The snubber bar has an upper portion supported at a corner of a washing machine body. The damper cap supports a lower portion of the snubber bar. The snubber base is held at a lower end of the snubber bar and is elastically inserted inside the damper cap by a damping spring. The snubber base spring is inserted in an inside circumference of the snubber base to expand the snubber base such that an outside circumference of the snubber base makes close contact with the inside circumference of the damper cap. Furthermore, at least a cut-away portion is formed in a circumferential surface of the snubber base for uniform distribution of an elastic force of the snubber base spring, thus improving contact between the snubber base and the inside circumference of the damper cap. | 3 |
FIELD OF THE INVENTION
The present invention relates to an improved microwave plasma chemical vapor deposition apparatus which enables one to form a large-area deposited film usable in semiconductor devices or the like at a high deposition rate.
BACKGROUND OF THE INVENTION
Forming a film of a large-area semiconductor or the like at a high deposition rate at a reduced cost is essential to the improvement of productivity of the production line and the reduction of cost in manufacturing semiconductor devices including photovoltaic devices, optical sensors, electrophotographic photoconductors and liquid crystal driving circuits.
Plasma CVD processes are the most general and preferable processes of forming a large-area semiconductor film by deposition. The plasma CVD process is to decompose a raw material gas to produce plasma causing the formation of a deposited film on a substrate.
Among various plasma CVD processes, glow discharge decomposition process (hereinafter referred to as "GD process") has most widely been used because of its satisfactory plasma control performance and capability of comparatively easily forming a large-area film In the GD process, high RF waves are applied to a raw material gas to decompose the raw material gas in plasma state and the deposition of a film is caused on a substrate. However, the deposition rate of the GD process is not sufficiently high; for example, the deposition rate of the GD process is on the order of 20 Angstrom/sec at the maximum in depositing a hydrogenated amorphous silicon film (hereinafter referred to as "a-Si:H film"). And the GD process is accompanied with a problem that when the supply power is increased to enhance the deposition rate beyond the foregoing limit, in most cases, the quality of the film deteriorates sharply with the increase of the supply power Furthermore, increase in the supply power accelerates the vapor phase reaction excessive, entailing the deposition of a large amount of powdery substances on surfaces, such as the walls of the film forming chamber, other than the surface of the substrate. Such powdery substances leaking from the film forming chamber has the danger of burning and the possibility of falling on the substrate to form a defective film. Although dependent on the type of the raw material gas, and the shape and distance between the electrodes for applying a high RF voltage to the raw material gas, it is one of causes of such a problem that the reduction of the pressure of the gas below 0.1 torr in the GD process is difficult and hence the supply of large power is liable to accelerate the vapor phase reaction excessively. Furthermore, plasma density in the GD process is on the order of 10 10 /cm 3 at the highest because the plasma is intercepted.
Recently, the microwave plasma CVD process, which decomposes the raw material gas by microwave energy to produce a plasma of the raw material gas, causing the formation of a deposited film on a substrate, has been used increasingly. Since the microwave plasma CVD process uses microwaves of frequencies higher than those of the high-frequency waves employed in the GD process, discharge occurs at a comparatively low voltage and the density of the plasma is as high as 10 12 /cm 3 .
In the microwave plasma CVD process, discharge can occur easily even if the pressure of the material gas is, for example, on the order of 10 millitorr, so that the vapor phase reaction is not accelerated excessively, and hence powdery substance is not deposited even if a large power is supplied. Consequently, a semiconductor film of a satisfactory quality can be formed at a high deposition rate. For example, the deposition rate of the microwave plasma CVD process in forming an a-Si:H film is 100 Angstrom/sec or higher.
In the microwave plasma CVD process, transmitting high-energy microwaves through a waveguide and a dielectric window into a film forming chamber is the most prevalent and practical. However, when high-energy microwaves are transmitted through the dielectric window, problems arises in this microwave transmitting method; that is, the decomposed material gas forms a film over the dielectric window, the film falls off the dielectric window onto a substrate on which a film is to be formed, forming defects in a film deposited over the substrate; the film adhering to the dielectric window is heated by the microwaves, cracking the dielectric window or the film formed over the dielectric window reduces the microwave transmittivity of the dielectric window, entailing variation in the deposition rate. These problems become intensified particularly when the energy of the microwaves is increased and the duration of film forming operation is extended.
In some cases, the interior of the film forming chamber is etched after completing the film forming operation to avoid the breakage of the dielectric window and to prevent the reduction of deposition rate, which, however, requires additional time increasing film-formation cycle time and there is the possibility of the components of the etching gas being mixed in a film deposited in the next film-formation cycle to deteriorate the quality of the deposited film.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide an improved microwave plasma CVD apparatus capable of solving the foregoing problems found in conventional plasma CVD apparatus and capable of operating for a long time using high electric power.
The inventor of the present invention has found, through zealous studies to achieve the object of the invention, that, when a microwave plasma CVD apparatus is provided with a plurality of microwave introducing windows including a movable microwave introducing window exposed to a film forming space, the formation of film over the microwave introducing windows can be prevented by moving the movable microwave introducing window to an etching chamber isolated from the film forming chamber and removing the film formed over the movable microwave introducing window by etching during the film forming operation, so that the microwave plasma CVD apparatus is able to operate continuously for film forming operation for an extended period of time.
The present invention has been completed through further studies on the basis of the foregoing finding
In one aspect of the present invention, there is provided a microwave plasma CVD apparatus (hereinafter referred to as "MW-PCVD apparatus") for forming a functional deposited film on a substrate, said apparatus comprises a film-forming vacuum chamber having a film forming space and having a substrate holder in said space, said chamber being provided with a microwave introducing window unit for introducing microwave into said film forming space to excite a raw material gas as supplied with the energy of microwave so that a film is deposited on a substrate placed on said substrate holder, and an etching chamber having an etching space isolated from the film forming space. The microwave introducing window unit comprises a plurality of concentric microwave introducing windows, one of which microwave introducing windows being exposed to the film forming space is made movable between the film forming chamber and the etching chamber, and a film deposited on the movable microwave introducing window is removed by etching while the film forming operation is being performed in the film forming chamber.
The MW-PCVD apparatus of the present invention reduces the deposition of a film on the microwave introducing window remarkably and it enables one to continuously carry out the film forming process using a large electric power for a desired long period of time without entailing damages for the microwave introducing window.
The MW-PCVD apparatus of the present invention is not accompanied with such occasion that a film is deposited on the microwave introducing window and the film deposited on the microwave introducing window is removed to contaminate into a film to be deposited on the substrate
Further, according to the MW-PCVD apparatus of the present invention, the microwave transmittivity of the microwave introducing window always remains constant and because of this, the deposition rate of a film is stabilized. Further in addition, according to the MW-PCVD apparatus of the present invention, since it is provided with the etching chamber situated separately from the film forming chamber and etching of the microwave introducing window is conducted not in the film forming chamber but in the etching chamber, there is not any occasion for the components of an etching gas to be incorporated into a film to be deposited on the substrate.
The microwave introducing windows employed in the present invention are formed preferably of a dielectric material having a high microwave transmittivity, such as quartz or Al 2 O 3 . The shape of the microwave introducing windows may be cylindrical or circular depending on the mode of microwave transmission In any case, the microwave introducing window unit in the present invention comprises at least a first window having a vacuum-sealed portion, and a second window capable of moving in a vacuum. Desirably, the thickness of the gap between the window capable of moving in a vacuum and the adjacent window is preferably 5 mm or less, more preferably, 2.5 mm or less, most preferably, 1 mm or less in order to prevent the raw material gas from leaking into the gap. In the case where there is a fear that the raw material gas is entered into the gap, it is possible to flow hydrogen gas (H 2 ) or an inert gas such as He gas, Ne gas or Ar gas through the gap. A film formed over the window which moves in a vacuum (hereinafter, referred to as "movable window") is removed by dry etching in the etching space while the movable window moves alternately through the film forming chamber and the etching chamber isolated from the former. Accordingly, film is scarcely formed over the microwave introducing window including the movable window, so that the MW-PCVD apparatus is able to operate continuously for a long period of time using a large electric power at a stable deposition rate without entailing the cracking of the microwave introducing windows.
The film forming chamber and the etching chamber may be isolated from each other so that the raw material gas and the etching gas is not mixed by isolating ducts as shown in FIG. 3 or an isolating gate as shown in FIG. 7. The isolating ducts may be scavenged as shown in FIG. 3 by hydrogen gas or an inert gas, such as He gas, Ne gas or Ar gas. The movable window may be moved continuously or intermittently across the boundary between the film forming chamber and the etching chamber.
In order to remove the film deposited on the microwave introducing window (removable window) by etching using an etching gas in the etching chamber, it is possible to produce the etching gas using the microwave to be introduced into the film forming chamber Other than said activation energy, an activation energy of microwave, RF wave or light may be selectively used. Further, heat energy or an energy of a current of charged particles such as ions may be also selectively used.
As for the manner of introducing microwave into the film forming chamber in the present invention, there can be mentioned, for example, a manner of introducing microwave through a microwave introducing window from a waveguide into the film forming chamber, a manner of introducing microwave through a cylindrical microwave introducing window from an antenna rod extending from a waveguide into the film forming chamber as shown in FIG. 1, etc. The manners may be selectively employed as desired in the present invention. A desired material gas and a desired etching gas may selectively be used in the present invention.
When the isolating ducts as shown in FIG. 3 are employed, the depth of the isolating ducts, namely, the distance between a partition plate and the movable window, is preferably 10 mm or less, more preferably, 5 mm or less, most preferably, 3 mm or less.
The partition plates of the isolating ducts may be formed of a metal, such as a stainless steel, or a dielectric material.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic sectional view of a typical MW-PCVD apparatus in an embodiment according to the present invention.
FIG. 2 is a schematic perspective view of a mechanism for rotating a movable window embodying the present invention.
FIG. 3 is a fragmentary view of assistance in explaining a isolating duct embodying the present invention.
FIG. 4 is a graph showing the variation of deposition rate with the number of film formation cycles obtained through the operation of a MW-PCVD apparatus embodying the present invention.
FIG. 5 is a schematic sectional view of a MW-PCVD apparatus in another embodiment according to the present invention.
FIG. 6 is a schematic sectional view showing the configuration of a device fabricated by using the MW-PCVD apparatus of FIG. 5.
FIG. 7 is a fragmentary perspective view of a MW-PCVD apparatus in a further embodiment according to the present invention.
FIG. 8 is a schematic sectional view of the MW-PCVD apparatus of FIG. 7.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described hereinafter with reference to MW-PCVD apparatus embodying the present invention and the results of film forming operation of those apparatus, which, however, are intended to illustrate the invention and are not to be construed to limit the scope of the present invention
First Embodiment (FIGS. 1, 2, 3, 4)
Referring to FIG. 1, a MW-PCVD apparatus in a first embodiment according to the present invention includes a microwave transmitting antenna rod 101 made of a stainless steel, a fixed, cylindrical quartz window (hereinafter, referred to as "fixed window") 102, and a movable, cylindrical quartz window (hereinafter, referred to as "movable window") 103. The MW-PCVD apparatus comprises a film forming chamber having a film forming space 104 and an etching chamber having an etching space 105. Numeral reference 109 stands for a exhaust pipe open into the film forming space 104 at one end and which is connected through an exhaust valve to an exhaust device (not shown).
In film forming operation, microwave generated by a microwave oscillator (not shown) is guided by a waveguide (not shown) for propagation and is transmitted through the fixed window 102 and the movable window 103 into the film forming space 104 and the etching space 105 by the microwave antenna rod 101 to create a discharge region A raw material gas is introduced into the film forming space 104 through gas supply manifolds 111 extending from a gas reservoir (not shown) and the raw material gas as introduced is decomposed to cause the formation of a film on substrates 106 heated by electric heaters 107. The movable window 103 exposed to the film forming space 104 is rotated by a mechanism as shown in FIG. 2. Referring to FIG. 2, the movable window 203 is rotated through gears 205 disposed outside the film forming space 104 and gears 206 disposed within the film forming space 104 by motors 204. Gaps between shafts 208 and the wall of a vacuum vessel defining the film forming space 104 are sealed hermetically. The movable window 203 is disposed within the vacuum vessel. The space between the fixed window 202 and the movable window 203 is sealed by an O ring put on the fixed window 202 at a position 207.
Now, referring to FIG. 1, the etching space 105 is isolated from the film forming space 104 by partition plates 108 and isolating ducts as shown in an enlarged view in FIG. 3. Referring to FIG. 3, hydrogen gas is supplied through a supply manifold 301 into the isolating duct 302 to prevent the flow of the film-forming raw material gas into the etching space 105 and the flow of the etching gas into the film forming space 104. The etching gas is supplied through etching gas supply manifolds 306 into the etching space 305. The etching gas is excited in the etching space 305, for example, by microwave to remove a film deposited on the circumference of the movable window 303 by the etching action of the excited etching gas.
Returning to FIG. 1, the movable window 103 is rotated continuously to remove the film deposited thereon in the film forming space 104 by the etching gas in the etching space 105 to prevent cumulative film deposition over the circumference of the movable window 103; consequently, the MW-PCVD apparatus is able to operate stably for a long period of time using high-energy microwave.
Experiment I
The MW-PCVD apparatus as above described was operated in the following manner, to thereby form an a-Si:H film on four aluminum substrates 106 respectively of 75 mm×300 mm in size.
SiH 4 gas and H 2 gas were introduced through the gas supply manifolds 111 into the film forming space at respective flow rates of 300 sccm and 100 sccm. The gaseous pressure of the film forming space was adjusted to 15 mTorr. And all the substrates 106 were maintained at 250° C. Then, microwave of 2KW was introduced from the antenna rod 101 through the fixed window 102 and the movable window 103 into the film forming space 104 to thereby cause glow discharge in a gaseous mixture composed of said two gases in the space between said plurality of substrates 106 and the movable window 103 in the film forming space 104, whereby a 30 μm thick a-Si:H film on each of the substrates 106.
During the above film forming process, the movable window 103 was rotated continuously at a rotating speed of two turns per minute And, CF 4 gas and O 2 gas were introduced though the gas supply manifolds 306 (see FIG. 3) into the etching space 105 at respective flow rates of 200 sccm and 20 sccm.
Then, the gaseous pressure of the etching space 105 was maintained at 15 mTorr by exhaust means comprising an exhaust pipe connected through an exhaust valve to an exhaust device which is provided on the side indicated by a numeral reference 110 of the etching space 105 (this part is not shown in FIG. 1). A gaseous mixture composed of said two gases gas excited with the action of the microwave introduced into the etching space 105 from the foregoing antenna rod through the fixed window 102 and the movable window 103 and the film deposited on the movable window 103 was etched off by the excited etching gas
In addition, the film forming space 104 and the etching space were isolated from each other by supplying H 2 gas into the isolating ducts 302 (see, FIG. 3) at a flow rate of 50 sccm.
In this case, the cylindrical movable window 103 was made 70 mm in radius, 4 mm in thickness and 400 mm in length, the width of the gap between the fixed window 102 and the movable window 103 was made 1 mm, and the size of the gaps between the circumference of the movable window 103 and the isolating ducts 301 was made 2 mm.
FIG. 4 illustrates the resultant situations with respect to the variation in the film deposition rates in the cases of having carried out the above process of forming said 30 μm thick a-Si:H film twenty five times.
In FIG. 4, the plots represented by circles indicate the results obtained when the MW PCVD apparatus of the present invention was used, and those represented by crosses indicate the results obtained by carrying out the foregoing film forming process with the use of a MW-PCVD apparatus having substantially the same in constitution except that it is provided with neither the movable window 103 nor the etching space 105 as a comparison.
As shown in FIG. 4, in the case of the comparison, which is not provided with neither the movable window nor the etching space, the film deposition rate decreased as the number of film-formation cycles increased, and the fixed window (a quartz tube) was broken in the fourteenth film-formation cycle due to the adverse influence of the film deposited on the circumference of the fixed window. On the other hand, in the case of the MW-PCVD apparatus of the present invention, the film deposition rate remained substantially constant and neither the movable window nor the fixed window was broken.
Second Embodiment (FIGS. 5, 6, 7)
In FIG. 5, there is shown a second embodiment of the MW-PCVD apparatus according to the present invention for continuously forming a functional deposited film on a substrate web which comprises a plurality of film forming chambers, at least one of which comprising the MW-PCVD apparatus of the present invention having substantially the same constitution as that shown in FIG. 1 to 3.
The MW-PCVD apparatus shown in FIG. 5 comprises a substrate feed chamber 501, a first MW-PCVD chamber 503, a second MW-PCVD chamber 504, a third MW-PCVD chamber 505 and an unload chamber 507 being arranged in this order.
The substrate feed chamber 501 contains a payout reel 508 having a web substrate 510 wound thereon and a feed roller 508'.
The unload chamber contains a takeup reel and a feed roller 509'. The web substrate 510 is continuously unwound from the payout roll 508, fed into the first, second and third MW-PCVD chambers where a first, second and third constituent layers are respectively formed thereon, finally fed into the unload chamber 507 where it is wound up on the takeup reel through the feed roller 509'.
The adjacent chambers are separated one from the other by a gas separating duct 517 having a gas gate 518 through which an inert gas is passed in order to prevent each of the gases of the adjacent chambers from reversly flowing from one into the other.
There is provided a preheating chamber 502 for heating the substrate web 510 in advance prior to entrance into the first MW-PCVD chamber to a desired temperature. The preheating chamber 502 contains means for heating the substrate web 510. The preheating chamber 502 is provided with an exhaust pipe being connected to a vacuum pump in order to maintain the inner pressure thereof at a desired value (not shown in the figure). The inside of the preheating chamber 502 is filled with the foregoing inert gas. Likewise, each of the substrate feed chamber 501 and the unload chamber 507 is provided with an exhaust pipe (not shown) and it is filled with the foregoing inert gas. There is provided a cooling chamber 506 between the third MW-PCVD chamber 505 and the unload chamber 507 which is provided with means for cooling the substrate web 510 having a plurality of layers being formed thereon to a room temperature or below. The cooling chamber 506 is provided with an exhaust pipe being connected to a vacuum pump in order to maintain the inner pressure thereof at a desired value (not shown in the figure). The cooling chamber 506 is filled with the foregoing inert gas.
Each of the first and third MW-PCVD chambers has a cylindrical film-forming space encircled by the substrate web supported by a pair of external feed rollers (503', 504' or 505') and a plurality of internal feed rollers (503", 504" or 505").
And in each case of the first and third MW-PCVD chambers, at the center position of the cylindrical film-forming space, there is provided microwave introducing means comprising a microwave transmitting antenna (511 or 513) and a fixed cylindrical quartz window (514 or 516) as well as in the case of the foregoing first embodiment. Each of the first and third MW-PCVD chambers is provided with means for externally heating the substrate web and an exhaust pipe being connected through an exhaust valve to an exhaust device (not shown). Each of the first and third MW-PCVD chambers is provided with means for supplying a raw material gas into the film-forming space (not shown).
The second MW-PCVD chamber is provided with microwave introducing means comprising a microwave transmitting antenna 512, a fixed cylindrical quartz window 515 and a movable cylindrical quartz window 520 at the center position of the film-forming space, to which microwave introducing means an etching chamber having an etching space 521 for etching the movable window 520 with an etching gas which is defined by partition plates 522.
This situation is the same as in the foregoing first embodiment. The second MW-PCVD chamber is provided with means for externally heating the substrate web 510 and an exhaust pipe being connected through an exhaust valve to an exhaust device (not shown). The MW-PCVD chamber is provided with means for supplying a raw material gas into the film-forming space (not shown).
Experiment II
Using the above apparatus, there was prepared a pin type solar cell having the configuration shown in FIG. 6. In FIG. 6, there are shown a substrate 101 (which functions also as a lower electrode), an n type layer 602, an i-type layer 603, a p-type layer 604, an upper electrode 605 and a collecting electrode 606.
In this experiment, as the substrate web, there was used an aluminum web.
Firstly, a roll of an aluminum web wound on the payout reel 508 was provided It was set to the substrate feed chamber 501. The aluminum web was unwound, passed through the preheating chamber 502, the first MW-PCVD chamber 503, the second MW-PCVD chamber 504, the third MW-PCVD chamber 505 and the cooling chamber 506, then fixed to the takeup reel 509 in the unload chamber 507.
Then, air of all the inside spaces of the apparatus were replaced by an inert gas and the aluminum web 510 which had been exposed to the air was wound up by the takeup reel 509. During this process, an inert gas was supplied at a desired gaseous pressure into each of the gas gates 518 in the perpendicular direction and the portion of the aluminum web 510 to be placed in the first MW-PCVD chamber 503 was heated to a temperature of 280° C. by actuating the heating means 519 comprising infrared lamp of the preheating chamber 502. SiH 4 gas, H 2 gas and PH 3 gas (diluted with H 2 gas to 3000 ppm) were fed into the first MW-PCVD chamber 503 at respective flow rates of 100 sccm, 100 sccm and 50 sccm while maintaining the aluminum web positioned in the first MW-PCVD chamber at 280° C. After the flow rates of all the gases became stable, the gaseous inner pressure was adjusted to 10 mTorr by regulating the exhaust valve of the exhaust pipe. Then, microwave of 300 W was applied through the microwave introducing means into the film-forming space to thereby cause glow discharge, whereby an about 300 Å thick n-type a-Si:H film as the n-type layer 602 is formed on the aluminum web.
Thereafter, the aluminum web 510 was moved again so that its portion having the above n-type a-Si:H film formed thereon was positioned in the second MW-PCVD chamber 504. The aluminum web was maintained at a temperature of 280° C. Then, SiH 4 gas and H 2 gas were fed into the second MW-PCVD chamber at respective flow rates of 400 sccm and 100 sccm. After the flow rates of the two gases became stable, the gaseous inner pressure of the film-forming space was adjusted to 15 mTorr and microwave of 2KW was applied through the microwave introducing means into the film-forming space to thereby cause glow discharge. During this process, the movable window 521 was rotated at a rotating speed of 1.5 times per minute, and NF 3 gas was fed into the etching space 521 at a flow rate of 150 sccm and the gaseous inner pressure of the etching space was maintained at 15 mTorr to thereby etch off a film deposited on the movable window.
Thus, there was formed an about 4500 Å thick non-doped i-type a-Si:H film as the i-type layer 603 on the previously formed p type layer.
Then, the aluminum web 510 was moved so that its portion having the above two layers laminated thereon was positioned in the third MW-PCVD chamber 505 The aluminum web was maintained at a temperature of 250° C. Then, SiH 4 gas, H 2 gas and B 2 H 6 gas (diluted with H gas to 1%) were fed into the film-forming space at respective flow rates of 50 sccm, 200 sccm and 50 sccm. After the flow rates of all the gases became stable, the gaseous inner pressure of the film-forming space was adjusted to 7 mTorr and microwave of 700 W was applied into the film forming space to thereby cause glow discharge. Thus, there was formed an about 100 Å thick p-type microcrystalline Si:H film as the p-type layer 604 on the previously formed i-type a-Si:H layer. Thereafter, the portion of the aluminum web 510 having the above three layers laminated thereon was moved into the cooling chamber 506 to cool sad portion to room temperature and the thus cooled portion was moved into the unload chamber 507. Then, said portion was cut off and transferred into a conventional CVD chamber where a about 700 Å thick ITO film as the collecting electrode 605 was formed on the p type layer 604. And a about 1 μm thick Cr film as the upper electrode 606 was disposed on the collecting electrode 605.
Thus, there was obtained a solar cell having the configuration shown in FIG. 6.
The above procedures were continuously repeated to thereby obtain a plurality of solar cells respectively having the configuration shown in FIG. 6.
The resultant solar cells were evaluated and as a result, it has been found that the solar cells obtained until 24 hours lapsed when the above procedures were continuously repeated exhibit about 10% or at least 9% of photoelectric conversion efficiency and they are practically acceptable. But the solar cells obtained thereafter are not practically acceptable because they do not exhibit a satisfactory photoelectric conversion efficiency, and their n-type and p-type layers are contaminated with foreign matters and inferior in the film quality.
Separately, the foregoing film-forming procedures were continuously repeated to prepare a plurality of solar cells respectively having the configuration shown in FIG. 4 where the microwave introducing window 514 of the first MW-PCVD chamber 503 and the microwave introducing window 516 of the third MW-PCVD chamber 505 were replaced by new ones by suspending the film-forming procedures when 24 hours lapsed. Thus, there were obtained practically acceptable solar cells continuously.
Third Embodiment (FIGS. 7, 8)
A MW-PCVD apparatus in a third embodiment according to the present invention shown in FIGS. 7 and 8 is characterized by a pair of flat movable windows 701 and 702 having identical shapes and attached respectively to the opposite ends of a swing arm supported for swing motion at the middle point thereof by a rotary shaft 703. One of the pair of movable windows 701 and 702 is disposed within a film forming space while the other is disposed within an etching space.
Referring to FIG. 8 while also referring to FIG. 7, microwave generated by a microwave oscillator, not shown, are propagated into a cavity 808 (708) by a waveguide 801 (701). The microwaves are transmitted through a fixed alumina window 804 (704) and a movable alumina window 801 (701) into a film forming space 809 (709) to excite and decompose a raw material gas to form a deposited film on a substrate 810 (710) heated by a heater 814. After the completion of one film-formation cycle, a movable gate 806 (706) is lowered, the rotary shaft 803 (703) is turned through an angle of 180° to replace the alumina window 801 (701) with the alumina window 802 (702) to place the alumina window 801 (701) outside the film forming space 809 (709), namely, in the etching space 811, and to place the alumina window in the film forming space 809 (709), and then the movable gate 806 (706) is raised to its initial position. During the subsequent film formation cycle, the alumina window 801 (701) is subjected to the etching action of an etching gas excited by RF wave applied across parallel flat electrodes 812 and 813 in the etching space 811 separated from the film forming space 809 (709) by the movable gate 806 (706) and a fixed gate 805 (705) to remove a film formed over the surface of the alumina window 801 (701). Thus, this MW-PCVD apparatus does not require an additional time for etching, so that the MW-PCVD apparatus is able to operate at a high rate of operation.
Since the film forming space 809 (709) and the etching space 811 are isolated perfectly from each other, the contamination of the components of the etching gas into the film formed on the substrate 810 (710) is prevented.
Experiment III
Using the above MW-PCVD apparatus, there was formed an a-Si:H film in the way as follows.
SiH 4 gas and H 2 gas were fed through a gas supply pipe 817 into the film forming space 809 at respective flow rates of 300 sccm and 100 sccm and the gaseous pressure of the film forming space 809 was maintained at 10 mTorr. Then, microwave of 1.5 KW was applied through the fixed alumina window and the movable alumina window into the film forming space 809 to thereby cause plasma discharge, whereby an a-Si:H film of 20 μm in thickness was formed on an aluminum substrate maintained at 250° C. During this process, ClF 3 gas was fed into the etching space 811 at a flow rate of 300 sccm and the gaseous pressure of the etching space 811 was maintained at 0.6 Torr. Then, RF wave of 150 W was applied across the parallel flat electrodes 812 and 813 to cause plasma discharge and excite the ClF 3 gas, whereby the film deposited on the previously used movable alumina window was etched off with the action of the excited ClF 3 gas. In this way, there were repeatedly formed a plurality of 20 μm thick a-Si:H films. In each case, the deposition rate of the a-Si:H film was 70 Å/sec±3%.
The same MW-PCVD apparatus was operated without using the movable alumina windows 802 and 805 as a comparison. In this case, the fixed alumina window had to be cleaned by etching using an etching gas ClF 3 after every film-formation cycle in order to maintain the deposition rate at 70 Å/sec±3%. In this way, there were repeatedly formed a plurality of 20 μm thick a-Si:H films.
The films formed by the MW-PCVD apparatus provided with the movable alumina windows and the film formed by MW-PCVD apparatus not provided with the movable alumina windows were analyzed by a SIMS. Cl was detected in the films formed by the MW-PCVD apparatus not provided with the movable alumina windows, while no Cl was detected in the films formed by the MW-PCVD apparatus of the present invention. There were repeatedly formed a plurality of 20 μm thick a-Si:H films by repeating the above procedures except for using a gaseous mixture of CF 4 and O 2 for etching. Each of the resultant films was examined in the same manner as in the above. As a result, it was found that each of the a-Si:H films formed in the case of the comparison contained both C and O respectively with a concentration of about 5×10 17 cm -3 and its electron spin density measured by ESR was about 5×10 16 /cm -3 , while each of the a-Si:H films formed by the MW-PCVD apparatus of the present invention contained C or/and O with a negligible concentration, and its electron spin density was not more than 5×10 15 /cm -3 . Further, the a-Si:H films formed by the MW-PCVD apparatus of the present invention had only a few dangling bonds.
As is apparent from the foregoing description, the MW-PCVD apparatus according to the present invention is provided with the fixed window and the movable window exposed to the film forming space, and the movable window is cleaned in the etching space isolated from the film forming space during the film forming operation. Accordingly, the initial microwave transmittivity of the movable window is maintained in a desirable state so that the MW-PCVD apparatus enables one to continuously operate the film forming operation for a desired period of time. Furthermore, since the initial microwave transmittivity of the movable window is maintained, the deposition rate is stabilized at a desired deposition rate. There is not such an occasion for the MW-PCVD apparatus of the present invention that the film formed on the microwave transmitting window falls onto the substrate to cause defects for the film formed on the substrate.
Further, since the movable window is etched in the etching space isolated from the film forming space during the film forming operation, the MW-PCVD apparatus does not require an additional time for cleaning the movable window and is able to operate at a high rate of operation. | A microwave plasma chemical vapor deposition apparatus for continuously forming a functional deposited film on a substrate, comprising a substantially enclosed film forming chamber containing means for holding said substrate, said film forming chamber being provided with means for feeding a film-forming raw material gas into said film forming space, said film forming chamber being provided with a microwave introducing window connected to a microwave power source and means for evacuating the film forming space, said film forming chamber being provided with an etching chamber for cleaning said microwave introducing window with an etching gas, said etching chamber having an etching space and being provided with means for feeding an etching raw material gas into said etching space, said etching chamber being provided with means for applying an activation energy into said etching space to excite said etching raw material gas to be said etching gas, characterized in that said microwave introducing window comprises a plurality of concentric cylindrical microwave transmitting windows; one of said plurality of microwave transmitting windows to be exposed in the film forming space is made movable between the film forming chamber and the etching chamber such that the microwave transmitting window previously used in the film forming chamber is cleaned by etching off the film deposited on said microwave transmitting window with the etching gas in the etching chamber while film forming operation being performed in the film forming chamber. | 2 |
FIELD OF THE INVENTION
This invention relates to polymers, and methods for producing polymers of novel structure. More particularly, it relates to a process for cross-linking polymers to produce cross-linked polymers stabilized into particularly useful, dense structures. It also relates to novel polymeric materials having unusual properties.
BACKGROUND OF THE INVENTION
It is known that cross-linking of polymers substantially alters the physical properties of the polymers. Cross-linking can change a thermoplastic polymer to a thermoset polymer, can alter its solubility, density and other physical characteristics. Normally, cross-linking of a polymer is an irreversible process, so that the shape, configuration and density of a cross-linked polymer remain substantially permanent once the cross-linking process is complete.
A variety of different methods of polymer cross-linking are known. One method is reaction with chemical cross-linking reagents. This is particularly applicable where the starting polymer is unsaturated (polybutadiene, polyisoprene, styrene-butadiene copolymers, EPDM etc.), so that the groups of unsaturation take part in the cross-linking. Other methods involve creation of reactive sites such as free radicals on the polymer chains, e.g. by hydrogen abstraction using a free radical-generating initiator, by irradiation with V-rays, X-rays, etc. Cross-linking can take place with the polymer in solution in a suitable solvent, in suspension or in bulk. Cross-linking is normally a random process, which may involve links between different polymer chains and links between points on the same polymer chain, and permits only limited control over its course and extent. In solution and suspension, non-cross-linked polymers tend to adopt an extended, coiled conformation, which is altered in a generally uncontrollable manner during cross-linking. There is a need for stable, solid particulate polymers of predetermined shape, size and density, for use for example in ink-jet printers, photocopiers and other imaging applications, where the achievement of fine definition and resolution of images depends upon the particle size and uniformity of the particles comprising the imaging medium, and on the viscosity of the imaging medium.
SUMMARY OF THE INVENTION
The present invention provides a process whereby polymers in solution are diluted so as effectively to disentangle and isolate the individual macromolecules from one another in the solution, and then caused to contract from the normal, random coil conformation to adopt an approximately spheroidal configuration. Then the macromolecules are stabilized in this conformation, e.g. by applying cross-linking conditions to the solution, so that the dissolved polymer is internally stabilized in its newly assumed, spheroidal configuration, to form independent particles stabilized in that conformation. In essence, the particles are single macromolecules, independent of other, surrounding macromolecules.
By means of the present invention, dense, spherical particles of polymers can be made, having a high degree of uniformity as to particle size, shape and density. The particle size is largely a function of molecular weight of the polymer, a parameter which is controllable by known methods, during polymerization. Polymers of very narrow molecular weight distribution can be made by known methods of polymerization, and these will lead to stabilized polymer particles of substantially uniform particle size, following the method of the present invention. A solution of the polymer is first prepared using a solvent or mixture of solvents in which the polymer fully dissolves, and at a concentration below the critical concentration, and caused to contract into a spheroidal conformation. Then the polymer is stabilized, e.g. by cross-linking. Polymer particles of very small size, average diameter in the range 0.1–10 nanometers (nanoparticles), can be made in this way.
The resulting polymeric materials are internally cross-linked macromolecules, i.e. substantially all of the cross-links are between groups on the same polymer chain as opposed to cross-links between groups on different polymer chains to bond the polymer chains together in a network. These internally cross-linked polymers according to the invention have solution properties which are quite different from those of the same polymeric material either before cross-linking or after cross-linking in bulk. Conventional high molecular weight polymers (100,000 and higher) have high viscosity in solution, resulting at least in part from entanglement of and interaction between individual macromolecules. If such a polymer is cross-linked in the bulk phase, the resulting polymer will not dissolve in any solvent, but may swell when contacted with solvents. Internally cross-linked materials of the invention, in contrast, even with molecular weights in excess of 1,000,000 can be dispersed in a wide variety of solvents and non-solvents, but scarcely affect the viscosity of the solution or dispersion at all. This remarkable property makes these new compositions of the invention of potential utility not only in imaging compositions as described above, but also in drug delivery applications.
Thus according to one aspect of the present invention, there is provided a process for preparing polymeric material in the form of stable nanoparticles having substantially spherical particulate form, which comprises:
dissolving a polymeric material in a solvent system to form a solution of the polymeric material at a concentration therein of less than the critical concentration for the polymeric material; causing the macromolecules of said polymeric material to contract into an approximately spheroidal conformation in solution; and stabilizing the polymeric material in solution in said spheroidal conformation so assumed by creating intra-molecular bonds.
Stable, intra-molecularly bonded, approximately spheroidal polymeric nanoparticles can be recovered from the solution, if desired, by standard methods.
The term “intra-molecularly bonded” as used herein indicates the presence of internal cross-links or other bonds linking parts of the same macromolecule to itself, to the substantial exclusion of bonds linking different macromolecules together (“inter-molecular bonds”).
According to another aspect, the invention provides internally crosslinked particulate independent macromolecules having substantially spheroidal particle shapes, said particles having the ability to be dispersed in a liquid medium without significantly changing the viscosity of the medium.
BRIEF REFERENCE TO THE DRAWINGS
FIG. 1 of the accompanying drawings is a digrammatic illustration of a preferred process according to the invention;
FIG. 2 is an atomic force microscopy picture of one product of Example 1 below;
FIG. 3 is an atomic force microscopy picture of another product of Example 1 below;
FIG. 4 is an atomic force microscopy picture of the product of Example 3 below;
FIG. 5 is the UV-visible spectrum of the product of Example 9 below;
FIG. 6 is an electron microscope image, with an enlargement of the circled portion, of the product of Example 9 below;
FIG. 7 is a curve showing the size distribution of the metal particles of Example 9 below; and
FIG. 8 is Raman spectra of the polyacrylic acid particles and the polacrylic acid silver salt particles of Example 9 below.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The process of the present invention is applicable to a wide variety of polymeric materials, natural and synthetic. The polymeric materials can be homopolymers or copolymers of two or more monomers, including block copolymers and graft copolymers. It is necessary that the chosen polymeric material be soluble to a substantial extent in at least one solvent system, so as to enable it to adopt a contracted spheroidal conformation in solution, as described below.
The chosen polymeric material is first dissolved in an appropriate solvent system. This may be water, an organic solvent or a mixture of two or more such solvents. The polymeric material is dissolved such that, in solution individual macromolecules thereof remain distinct, separated and non-entangled with one another. This can be achieved by arranging that the concentration of polymer in solution is below the “critical concentration,” which is the concentration at which the individual polymer chains in the solution interpenetrate. The separated, non-interpenetrating macromolecules in solution can be condensed e.g. by changing the solution characteristics, and stabilized by internal cross-linking, to a particle size which, assuming spherical shape, can be calculated from the molecular weight of the polymer. The ability of the macromolecules to achieve a condensed particle size largely in accordance with theoretical calculations, assuming spheroidal shape, acts as a check or test that the polymer in solution, prior to condensation and cross-linking, was indeed in the form of independent, separated, non-interpenetrated macromolecules for the initial stages of the process of the present invention. A person skilled in the art can readily conduct such calculations from a knowledge of the chemistry and molecular weight of the polymer under consideration, and simple experiments to determine particle size after stabilization as described. Comparison of this with theoretical calculation and prediction can determine the critical concentration for the specific polymer solution.
Either as it dissolves (for example in the case of sodium styrene sulfonate-vinyl naphthalene copolymers and similar copolymers), or by reduction of the solvent power of the solution, for example by adding to it a precipitating non-solvent, or a salt which changes the ionization conditions of the solution, the polymer is caused to condense and to contract to dense spheroidal structures. Then it is internally stabilized preferably by cross-linking, using a system which is compatible with the chosen polymer and the chosen solvent system, for example by exposure to γ-radiation. When each polymer molecule contains three or more internal cross-links, it can no longer expand to form its normal random coil configuration in solution. Instead, it retains its spheroidal confirmation, the density of which increases with the degree of cross-linking. In the case of some polymers, e.g. those having mutually reactive chemical groups such as polypeptides, stabilization may occur by reaction of these groups with one another as the polymer is caused to condense and contract, e.g. by formation of disulphide bridges, without application of a specific cross-linking step.
A wide variety of polymers and copolymers can be used in the present invention, provided only that a suitable solvent system is available for them, and that the random coils can be condensed to denser spheroidal particles prior to cross-linking. Preferred polymers have ionic charges (polyelectrolytes) so that, in the preferred aqueous solvent systems, the macromolecules are mutually repellant and less likely to agglomerate prior to cross-linking.
Examples of useful polymers in the present invention include polymers and copolymers derived from such monomers as styrene, vinyl naphthalene, styrene sulphonate, vinylnaphthalene sulphonate, acrylic acid, methacrylic acid, methylacrylate, acrylamide, methacrylamide, acrylates, methacrylates, acrylonitrile, N-lower alkyl acrylamides and the like.
One preferred embodiment of the invention involves the use of polymers having a critical solution temperature, i.e. a temperature below which they are soluble in water, and above which they are insoluble in water. Using the process of the present invention, such polymers can be dissolved in water, caused to assume a condensed, spheroidal conformation and internally cross-linked as described. They can then be used for delivery and controlled release of other organic compounds such as drugs. The drug can be dispersed in a suspension of the cross-linked polymer at a temperature above the critical solution temperature, at which the drug will be absorbed by the polymer in its collapsed-particulate form. When the temperature is reduced below the critical solution temperature, the polymer particle swells and slowly releases the drug. Polymers having critical solution temperatures include polymers of N-isopropylacrylamide (NIPAM), the critical solution temperature of which can be adjusted by copolymerization with other monomers.
FIG. 1 of the accompanying drawings diagrammatically illustrates a process according to an embodiment of the invention. At stage 1 , the polymer exists in a concentrated solution, in which the macromolecule chains 10 are intertwined and interpenetrated, so that any attempt to cross-link them at this stage would cause inter-reaction between the polymer chains.
Upon dilution of the solution, stage 2 , below the critical concentration, the polymer macromolecules 10 are spaced apart from one another, but still in their random coil configuration. Upon reducing the solvent power of the solvent system, e.g. by introducing a non-solvent or a salt, the macromolecules condense, stage 3 , into generally spherical conformation 12 , and can now be cross-linked, eg. by application of ionizing radiation, at stage 4 , whereupon internal cross-linking, as opposed to inter-macromolecular cross-linking occurs, effectively locking the macromolecules into the configurations assumed in stage 3 . Then the cross-linked, approximately spherical macromolecule particles can be recovered e.g. by freeze drying, for use in applications referred to above.
When the macromolecule particles are re-dissolved e.g. in water, they have very little, if any, effect on the viscosity of the solvent (in any event less than a 10% resulting increase in the viscosity). This is due to the fact that the macromolecules do not agglomerate to any significant extent, nor do they expand or mutually interact to any significant extent. This unusual property renders the nanoparticles useful in a number of specialty applications. The nanoparticle macromolecules having critical solution temperature as described above are, fro example, especially useful as drug carriers, where drugs are associated with the polymers in solution and delivered to very small veins and capillaries of the body, e.g. certain areas of the brain, which are so small that they cannot be penetrated by drug solutions of other than very low viscosity.
Whilst water is the preferred solvent for use in the present invention, other polar solvents can also be used if desired, alone or in mixtures with each other and in admixture with water. The best choice of solvent depends to a large extent on the choice of polymer. Polar solvents such as lower alkanols, ketones, amines, dimethylsulfoxide and the like are suitable alternatives to water, when working with a polymer of limited solubility in water.
Another aspect of the present invention comprises the use of internally cross-linked macromolecules as described above in the preparation of nanoparticles of metals, i.e. metal particles which are substantially spherical in shape, and which have an average diameter in the range 0.1–10 nanometers, preferably from 0.1–8 nanometers and more preferably from 0.1–5 nanometers. Such nanoparticles of metals comprise another aspect of the invention. This process aspect uses internally cross-linked polymers as described above, in which the polymer is a polyelectrolye such as polyacrylic acid or a salt thereof e.g. sodium polyacrylate. For example, by dissolving them in water containing a large excess of ferrous ions, the sodium ions can be replaced by ferrous ions. After removal of the sodium ions, the particles can be heated in air or oxygen to above 200–300° C. The polymer content is largely removed by pyrolysis, leaving extremely small particles of iron oxide with very large surface area and important electrical and catalytic properties. If the process is carried out in a reducing atmosphere, high surface metal particles can be obtained. Other metal salts such as silver salts (silver nitrate for example), copper salts and gold salts can be used to produce finely divided metal particles useful in imaging and, because of their very high surface area, in catalysis. Palladium, platinum, titanium and molybdenum are examples of metals which can be prepared in nanoparticle form according to the present invention, for use in catalysis. Substantially any metal which is stable in its metallic form and which has a water soluble salt can be used in this way. The metal salt can be dialyzed against the sodium polyacrylate (or similar polymeric salt) particles of the invention, to remove the alkali metal and replace it with the other metal. Then the product is reduced, e.g. by application of laser radiation, and solid metal nanoparticles e.g. silver particles, in some cases surrounded by a fine layer of residual polymer which has a stabilizing effect, are obtained.
In another modification, ionic groups on internally cross-linked polymers of the present invention, for example the sodium acrylate groups in the particles made in examples 1, 2 and 8 below, can easily be converted to other useful functional groups. Sodium acrylate groups for example can be converted converted to the corresponding acid chloride by treatment with thionyl chloride. Dye molecules containing reactive hydroxyl or amino groups can then be permanently bound to both the surface and the interior of the particles giving rise to products useful in imaging applications such as in inkjet printing.
The invention is further described with reference to the following specific illustrative examples.
EXAMPLE 1
Internally Cross-Linked Polyacrylic Acid
The sodium salt of poly(acrylic) acid (Polysciences Inc. Cat #18755), of molecular weight of 1,300,000, was used in a cross-linking process according to the invention. 97 mg of polymer was dissolved in 100 ml of distilled water. After solution was complete the pH was 8.2, and 98 mg of sodium chloride was slowly added to cause the polymer particles to contract. 5 cc. of the solution was flushed with nitrogen, sealed in a glass vial, and irradiated with 10 megarad of Co 60 γ radiation. After radiation the vial was opened and the solution dialysed against water for 5 days to remove the salt, and the polymer particles recovered by freeze drying under vacuum. The particles were studied by atomic force microscopy (A.F.M) (film cast onto mica, to produce tapping mode AFM height image) and shown to be perfectly spherical, with diameters of 6 to 10 nanometers (see FIG. 2 ). No such particles were observed in the uncross-linked control sample. The particles observed are close to the size calculated for a completely collapsed macromolecular chain of molecular weight one million. When dispersed in water at a concentration of 1%, the solution had a viscosity virtually the same as pure water. At the same concentration a water solution of uncross-linked starting material was much more viscous.
The procedure was repeated with a polyacrylic acid (sodium salt) of molecular weight about 700,000, and the A.F.M. picture of this product is presented as FIG. 3 hereto. The spherical shape of the particles is clearly apparent from this picture. The scale on the Figure is in millimicrons. The particles have a diameter of approximately 4 nanometers (0.4 millimicrons).
EXAMPLE 2
The procedure of Example 1 was repeated except that before addition of the sodium chloride the pH of the solution was reduced to 3.2 by addition of small amounts of 0.1 N hydrochloric acid. After addition of sodium chloride and cross-linking with 10 megarad of γ-rays, nanoparticles of the same size (6–10 nanometers) were observed as in Example 1 by A.F.M.
EXAMPLE 3
Copolymers of sodium styrene sulfonate and vinyl naphthalene containing about equal quantities of each comonomer are known to form hypercoiled pseudomicellar conformations in water, i.e. they do not form expanded random coils, but are collapsed into much smaller spherical structures with much higher coil density due to the hydrophobic interactions between the naphthalene groups and water. These particles are negatively charged due to the ionization of the styrene sulfonate groups in water. The polymers can also be internally cross-linked by the following procedure. A polymer containing 50% by weight sodium styrene sulfonate and 50% of vinyl naphthalene was prepared in benzene solution AIBN as catalyst. After isolation and purification by dialysis against pure water it had a molecular weight M w of 200,000.
100 mg of this polymer was dissolved in 100 ml distilled water and after purging with oxygen-free nitrogen was irradiated with a dose of 0.40 megarad of Cobalt 60 γ-rays. A.F.M. analysis of the resulting particles showed spherical particles with an average diameter of 7.5 nanometers. The A.F.M. picture of the particles is presented as FIG. 4 hereof. A 1% solution of these particles in water showed very little increase over that of water itself.
EXAMPLE 4
Internal cross-linking can be carried out by other means besides y radiation. In some cases, irradiation of the aqueous dispersion with high intensity U.V. laser light will cause internal cross-linking. A simpler procedure is to prepare a copolymer with a small number of double bonds which can be connected by vinyl polymerization. In this example a copolymer of 50% styrene sulfonate and 48% vinyl naphthalene and 2% divinyl benzene was prepared as in Example 3. 100 mg of this polymer was dissolved in 100 ml of water to which was slowly added with stirring 1.0 cc of benzene containing 4 mg styrene and 1 mg of AIBN (azobis-iso-butyryl nitrile). After purging with nitrogen 2 cc of this mixture was heated to 70° C. for 5 hours with stirring. After isolation and purification by dialysis spherical nanoparticles were observed by A.F.M.
EXAMPLE 5
An additional 2 cc of the solution prepared in Example 4 was shaken with a small amount of styrene monomer and allowed to separate. Excess styrene was removed and the polymer was internally cross-linked by exposure of the solution to near ultraviolet light (λ=313 nm from the American Ultraviolet Irradiation System for 1 hour. After isolation and purification cross-linked nanoparticles with the viscosity properties of the γ irradiated materials from Example 1 and 2 were produced.
EXAMPLE 6
Poly N-isopropyl acrylamide (NIPAM) is an important polymer which is often used in drug delivery systems. It has a lower critical solution temperature (LCST) of 31° C. It is soluble in water below this temperature but precipitates sharply above this. This temperature can be lowered by copolymerization with hydrophobic monomers such as acrylonitrile and raised by hydrophilic monomers such as acrylamide. These co-polymers can be internally cross-linked by any of the procedures described above. In a specific example 100 mg of polyNIPAM with a molecular weight of 200,000 g/mole was dissolved in 100 ml water at 20° C. and was cross-linked with 10 megarads of γ radiation. After isolation and purification, the internally cross-linked 5–10 nm nanoparticles can be used for the controlled delivery of other organic compounds. For example the drug can be absorbed by the collapsed particle in a water dispersion above LCST. After removal of the unabsorbed drug, the dispersion will remain stable until the temperature of the water is reduced below LCST, at which point the particle swells and slowly releases the drug. Since the size of the internally cross-linked nanoparticle is extremely small (˜10 nm) it can access almost any part of the human body including the smallest blood capillaries which makes it of interest in a variety of medical therapies. The delivery polymers can also be made sensitive to pH instead of temperature.
EXAMPLE 7
Polymers such as NIPAM, polyacrylamide and polyethylene oxide, which do not contain ionized groups, are difficult to keep separate in water solution while the cross-linking process is taking place. This reduces the yield and purify of the desired internally cross-linked nanoparticles. Cleaner products and higher conversions can be achieved by including an ionizable comonomer. A copolymer of 2% acrylic acid and 98% NIPAM was prepared. At a pH of about 8–9 in water most of the acrylic acid units will be ionized, thus giving a strong negative charge to each polymer molecule. At high dilution, this prevents the agglomeration of individual chains to form larger particles. 100 mg of this polymer was internally cross-linked by the procedure of Example 6. A.F.M. studies of the internally crosslinked particles showed a much lower concentration of larger agglomerated particles than those prepared in Example 6.
EXAMPLE 8
A solution of sodium polyacrylate was prepared as in Example 1, and after the addition of sodium chloride, 4 mg of 4,4′-diazidostilbene-2,2′ sodium sulfite dissolved in 1 cc benzene was added slowly with continuous stirring. After flushing with nitrogen, the ampoule was sealed and irradiated for 1 hour with 313 nm U.V. light in the American Ultraviolet Irradiation system. After irradiation the product was isolated by freeze drying and purified by dialysis as in Example 1. A.F.M. measurements showed particles similar to those found in Example 1.
EXAMPLE 9
Nanoparticles of Metal
Nanoparticles of polyacrylic acid sodium salt prepared according to Example 1 were dialysed against dilute hydrochloric acid to remove the sodium ions, and then treated with excess silver nitrate in aqueous solution to form the silver salt of the acrylic acid groups in the polymer particles. Irradiation of these particles in aqueous dispersion with γ-radiation (10 Mrad) gave a dark orange solution. The UV-visible spectrum shown in FIG. 5 shows peaks corresponding to the well-known surface plasmon of silver colloids of size smaller than the wavelength of light, indicating that the silver ions have been reduced to metallic silver. The silver colloids are much more stable than those reported in the literature, as indicated by the fact that the plasmon band intensity did not change for many weeks after preparation.
After isolation of the particles and drying of them, spherical particles of diameter about 5 nm were observed by AFM. An electron microscope examination (TEM), FIG. 6 , shows that the spherical silver particles are surrounded by a hazy region believed to be unreacted polymer, a possible factor in the enhanced stability of the silver nanoparticles.
The average diameter of the reduced silver particles was 3.5±0.53 nm. The diameter of the exterior, including the hazy region, was 5.2±0.8 nm. The particle size distribution is shown on FIG. 7 .
Similar results were obtained by irradiation of the original salt particles with an intense laser pulse from a picosecond quadrupled Nd:YAG laser or XeF excimer laser, and by a chemical reducing agent such as sodium in liquid ammonia.
Similar experiments with iron and copper salts gave similar results, with aqueous solutions giving rise to various colours, depending upon the size of the particles.
Further evidence of encapsulated particles is shown on FIG. 8 , Raman spectra, showing the surface enhanced Raman effect of silver nanoparticles on poly acrylic acid, PAA. In the absence of the reduced metal, the Raman peaks for pure polyacrylic acid are hardly discernible, but after the silver salt is reduced to metallic silver, strong enhanced Raman peaks are observable. This is strong evidence for the encapsulation of the silver particles by the remaining polymer from the original particle. This coating can be easily removed by washing with a suitable solvent, or by heating to 300° C. or higher in a reducing atmosphere.
EXAMPLE 10
Larger Particles
Larger particles of polyacrylic acid salts and other polymers for the preparation of metal particles by the process of the invention can be made by emulsion polymerization in the absence of surfactant, by the method of O'Callaghan et. al, Journal of Applied Plymer Science, Vol 58, 2047–2055 (1995). This paper describes a method of making monodisperse polymer latices with sizes of 40 nm and higher.
By following the procedure of this paper, there was prepared a copolymer of butyl acrylate (30%) with acrylic acid (70%), cross-linked with 3% divinylbenzene. The average size of these particles was 230±20 nm. Treatment with silver nitrate as in Example 9 followed by laser irradiation with the Nd:YAG laser while stirring the aqueous dispersion gave silver containing nanoparticles about 200 nm in diameter. | There are provided internally cross-linked, stable polymeric materials, in the form of substantially spherical particles, each particle consisting essentially of a single macromolecule. They have the unusual property of being soluble or dispersible in a liquid medium without significantly increasing the viscosity of the medium, rendering them potentially useful in imaging applications such as ink jet printers. They can be prepared by dissolving polymeric material in a solvent system to form a solution of the polymeric material at a concentration therein of less than the critical concentration for the polymer, causing the polymeric material to contract into an approximately spheroidal conformation in solution, cross-linking the polymeric material in solution in said spheroidal conformation so assumed, and recovering stable, cross-linked approximately spheroidal polymeric particles from the solution. | 8 |
BACKGROUND OF THE INVENTION
The invention relates to reins for use with a bit for controlling the direction of a domestic riding animal, such as a horse, mule or donkey, when the animal is being ridden. In particular, the invention relates to a braided romal rein having an integral connector at the bit end for directly attaching the rein to a bit, thus providing direct contact between the bit in the animal's mouth and the rider's hands.
During a long period of history of horsemanship, various devices have been invented to assist the rider in controlling the animal and causing it to move in the desired direction. Refinement of the control devices has resulted in the now familiar tack arrangement illustrated in FIG. 1 of a bridle 1 comprised of straps which adjustably fit around the animal's head 2, a metal bit 3 including a mouthpiece 4 adapted to fit in the animal's mouth and extend over and atop its tongue, and a set of reins 5 which are conventionally attached to end rings 6 of the bit 3 at either side of the animal's mouth.
There are two basic styles of Western reins: split reins which are two separate reins, and the romal rein, schematically illustrated (not to scale) in FIG. 2, which is one continuous rein 7 forming a loop 8, and a third part (the romal) 9 which hangs from the loop 8 and is attached to it by a connector 10. Most conventional braided romal reins are made by hand braiding leather around a heavy nylon rope core that extends through the entire length of the continuous rein, including oval loops 11. The oval loops 11 extend from the bit end 12 of the rein and are formed by turning the ends of the covered (braided) core to the inside and securing them by tightly braiding a terminal "barrel" 18 around them. Various ornamentations may be added to the reins, such as the illustrated braided leather buttons 16, knots 17, and barrels 18, or, in many cases, more ornate silver ornamentations.
For over two hundred years, conventional braided romal reins have been made with the oval braided loops 11 at the bit end 12 and a pair of removable braided connectors 13 (FIG. 3) for connecting each of the braided loops 11 to an end ring 6 of the bit 3. This conventional rein/connector design has been problematic because the loose joints created between the braided connector and the end ring of the bit, and again between the braided connector and the oval loop of the rein, cause a loss of direct contact between the rider's hands and the bit in the animal's mouth.
For many years, riding and saddlery professionals have attempted to overcome this problem. For example, one reported solution has been to run a stiff wire from the rein, along the connector, to the bit, and to tape or wire the whole unit together. However, this type of connection has now been declared illegal by the International Arabian Horse Association and the American Horse Show Association. Recently, a leather connector 14 (FIG. 4) has been developed that attempts to more rigidly connect the bit ring 6 with the braided loop 11 at the bit end 12 of the rein by means of a chicago screw 15. However, this design still requires a separate "connector" piece between the bit ring and the loop at the end of the reins and does not provide tight connections at either the rein end or the bit end. This connector also is not very stiff because a lightweight piece of leather must be employed to be thin enough to fit through the end ring of the bit.
In view of the foregoing, there is still a need for a rein design, especially for braided romal reins, that effectively provides direct contact between the bit in the animal's mouth and the rider's hands. In particular, there is a need for eliminating the problem of loose connections between the rein and the bit that presently exist when using conventional braided romal reins.
SUMMARY OF THE INVENTION
The invention provides a braided romal rein having a bit end that is directly attachable to the bit, without the need for a separate connecting piece between the rein and the bit. In particular, the bit end of the rein comprises a rigid member that is integral with the rein and which has a connector portion that can be tightly connected to the end ring of the bit. As used in the context of the invention, the term "rigid" refers to a member that has a strength and stiffness that is approximately equivalent to the strength and stiffness of an 8 ounce (oz.) piece of leather normally used in strap goods, such as reins and bridles. As used herein, the term "ounce" when referring to the weight of various leather pieces means ounces per square foot.
Because the entire length of the rein of the invention, including the portion that connects to the bit, is a continuous construction, the former problem of a loose joint at the rein end is eliminated. The stiff connector portion of the rigid member also assures a tight connection between the rein and the bit, and eliminates the former problem of a loose joint at the bit end. Thus, the braided romal rein of the invention provides direct contact between the bit in the animal's mouth and the riders hands.
In a preferred embodiment, the rigid member at the bit end of the rein comprises at least three layers, i.e., two thin, lightweight outer layers, preferably of leather, and one or more inner reinforcing layers of material, such as plastic coated cotton webbing, vinyl coated nylon material, and the like. The reinforcing layer(s) is the major source of the strength and stiffness of the rigid member. The outer and inner layers are secured to each other for part or all of their length by sewing, glueing, binding, or other means of attachment known to those skilled in the art. For aesthetic purposes, the outer layers of the rigid member can be type- and/or color-matched to the leather used in the braided portion of the rein.
An important feature of the preferred embodiment of the rigid member is that the required strength and stiffness can be achieved by employing a reinforcing layer that is thin (e.g., 1/16 inch thickness or less), together with thin outer layers of leather, such as 4 oz. leather pieces that each have a thickness of 1/16 inch or less. Thus, the total thickness of the rigid member can be about 1/8 inch to about 3/16 inches. As will become apparent in the embodiments of the invention described below, the thinness of the rigid member is advantageous, not only because it allows the member to fit through the end ring of the bit, but also because the rigid member can be integrally secured with or to the braided portion of the rein within a flexible rein member (described below) in a manner that is not bulky. Thus, in the preferred embodiments of the invention, the flexible member typically has a diameter similar to that of the terminal braided barrel of a conventional braided romal rein.
In each of the embodiments of the braided romal rein of the invention, the length of the braided core of the rein is shortened compared with that of a conventional braided core, such that it does not form a conventional oval loop at the bit end of the rein. Rather, the bit end of the core of the invention rein is tightly secured within the flexible tubular interior of a flexible member of the rein. As used in the context of the invention, the terms "end of the core" and "core end" of the braided rein, are intended to encompass both a naked rope core end and a braided core end.
One end of the rigid member of the rein is also secured within the flexible tubular interior. As used in the context of the invention, the terms "flexible tubular interior" and "flexible member" refer to a construction in which a tubular interior containing both the core end and the rigid member end is formed by tightly enclosing and securing both ends with a flexible binding material. For example, such a construction could be formed by tightly binding a flexible cord (e.g., cotton, plastic or leather) around the core and rigid member ends or, more preferably, by tightly braiding a flexible cord (e.g., cotton, plastic, or thin, 1-2 oz. leather strands) around the ends. The flexible member thus comprises the construction including the flexible tubular interior and the outer flexible binding material ("outer wall") and the construction is considered "flexible" by virtue of the fact that it conforms to the shape of the enclosed ends. An example of a flexible member is a terminal braided barrel in a conventional braided romal rein.
In a preferred embodiment of the invention, the rigid member comprises at least two layers that enclose the end of the core of the rein in a sandwich configuration. The rigid member layers are stitched and/or glued or otherwise attached to the core, thus securing the rigid member directly to the core of the rein. Other embodiments of the positioning and securing of the core and rigid member within the flexible member are described herein below.
Regardless of the manner in which the core and rigid member ends are secured, the rigid member becomes integral with the length of braided rein, and the rein, including the rigid member, comprises a continuous construction.
The bit end of the rigid member extends externally from the flexible member and comprises a connector portion for connecting the rein to the end ring of the bit. In embodiments of the invention, the connector portion may have several configurations, described below, each of which is designed to ensure a tight connection between the rein and the bit and to prevent a loose "joint". In a preferred embodiment of the connector portion, the rigid member comprises at least two layers that are separated from each other at the connector end. For connecting to the end ring of the bit, the separated layers form a sandwich around the ring. The whole sandwich assembly is then secured by a bolt arrangement, such as a chicago screw, that passes through the layers and the end ring of the bit. More preferably, at least one of the separated layers further comprises the reinforcing layer that imparts strength and stiffness to the rigid member.
In other embodiments, the connector portion of the rigid member may be in the form of a strap that has a strap end for passing through the end ring of the bit to form a loop and which may then be fastened to the rigid member by a fastener, such as a snap fastener, a buckle, a chicago screw, or the like, or tied with a cord. In another embodiment, the connector portion of the rigid member may comprise a rigid snap end fastener that is integrally attached to and extends from the rigid member, for snapping onto the ring of the bit.
The invention provides other romal reins and split reins, described further below, that have bit ends that provide a tight connection between rein and bit.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of a conventional tack arrangement for use when riding a horse.
FIG. 2 is a schematic illustration (not to scale) of a conventional braided romal rein.
FIG. 3 is a schematic illustration of prior art connectors for attachment of conventional braided romal reins to a bit.
FIG. 4 is a schematic illustration of a prior art connector for connecting a conventional braided romal rein to a bit.
FIG. 5 is a schematic illustration of a romal rein of the invention having an integral connector portion of a rigid member for direct attachment of the rein to the bit.
FIGS. 6A, 6B and 6C are schematic cross-sectional illustrations of preferred embodiments for securing the rigid member (comprising two thin leather layers and at least one reinforcing layer) and the end of the core of the rein within a flexible member.
FIG. 7 is a schematic illustration of an embodiment for securing the end of the core of the rein within a sandwich formed by layers of the rigid member.
FIGS. 8A, 8B and 8C are schematic cross-sectional illustrations of another embodiment of the rigid member (comprising two leather layers) and for securing the rigid member and core of the rein to each other within the flexible member.
FIGS. 9A, 9B and 9C are schematic illustrations of a preferred embodiment having a sandwich configuration for connecting the preferred rigid member of the rein to the bit. This embodiment may also be used when the rigid member comprises two leather layers.
FIGS. 10A, 10B and 10C are schematic illustrations of another embodiment for connecting the preferred rigid member of the rein to the bit.
FIG. 11 is a schematic illustration of another embodiment for connecting the preferred rigid member of the rein to the bit.
FIGS. 12A and 12B are a schematic illustrations of another embodiment for connecting the rigid member of the rein to the bit, which may be employed with either the preferred rigid member, or the rigid member comprising two leather layers.
FIGS. 13A, 13B and 13C are schematic illustrations of an embodiment of a flat rein having rigid members for connecting the rein to the bit in a sandwich configuration.
FIG. 14 is a schematic illustration of an embodiment of a flat rein having two or more layers, in which at least two layers are separated at the bit end for connecting the rein to the bit in a sandwich configuration.
DETAILED DESCRIPTION OF THE INVENTION
The invention provides reins that, unlike conventional braided romal reins, do not terminate in oval loops. Rather, the reins of the invention terminate in rigid connectors that are an integral part of the rein at the bit end, for directly connecting the reins to the end rings of the bit. The reins of the invention eliminate the need for an intervening connecting piece and, therefore, eliminate the problems associated with loose connecting joints in conventional romal rein/connector design. Although the reins are described herein with particular reference to braided romal reins, one skilled in the art will be sufficiently instructed by the embodiments of the invention to be able to apply the teachings to all types of romal reins and split reins, without undue experimentation.
A romal rein of the invention is schematically illustrated in FIG. 5. A length of rein 20 terminates in two bit ends 21, each of which comprises a flexible member 22 and a rigid member 27. The rigid member 27 has a first end (not shown) that extends into and is in tight contact with the interior of the flexible member 22 such that the rigid member 27 is firmly bound by the flexible member and is integral with the rein in a continuous construction. The rigid member 27 has a second end 30 that has a connector portion 50 for attachment to one of two end rings 6 of a bit (not shown). Because traditional romal reins are made of leather, it is preferred that the elements of the rein of the invention, including the rigid member and/or the flexible member, also employ leather. However, imitation leathers (e.g., plastics) that fulfill the criteria for these elements as described herein, may also be used in the invention.
In each of the preferred embodiments described below, the rigid member comprises at least three layers, i.e., two thin, lightweight layers of leather (e.g., about 1/16 inch thickness, preferably 4 oz. leather) and one or more thin (e.g., 1/16 inch thickness or less) reinforcing layers of material(s), such as plastic coated cotton webbing, vinyl coated nylon material, and the like. The layers are secured to each other by sewing, glueing, or other means of attachment known to those skilled in the art. The reinforcing layer is the major source of the strength and stiffness of the rigid member which, as defined above, has a strength and stiffness that is approximately equivalent to the strength and stiffness of an 8 ounce (oz.) piece of leather normally used in strap goods, such as reins and bridles. In several of the preferred embodiments, the layers of the rigid member are longitudinally separated either at the connecting portion for attachment to the end ring of the bit, or for forming a sandwich around the end of the core of the rein.
Other, less preferred embodiments of the invention are also described below wherein the rigid member comprises two thicker, heavier leather layers, without a reinforcing layer, that provide the required strength and stiffness.
Because reins are manufactured in a wide variety of lengths and thicknesses, the length and width of the rigid members are variable and may be determined for each kind of rein according to aesthetic and other criteria used by those skilled in the art.
Several preferred embodiments of the construction of the bit end of the rein are illustrated in FIGS. 6A, 6B, and 6C. In each of the embodiments, the flexible member 32 has a first end 33 and a second end 34 and an outer wall 35 that defines a flexible tubular interior 36. A length of rein 20 has a core end 38 that extends into the first end 33 of the flexible member 32 and is in tight contact with the flexible tubular interior 36. A rigid member 37, having a first end 39 and a second end 40, is positioned at the second end 34 of the flexible member 32. The second end 40 of the rigid member 37 extends outwardly from the second end 34 of the flexible member 32 and has a connector portion (not shown in these figures) for attachment to end ring of a bit (located beyond the arrow). The first end 39 of the rigid member 37 extends into and is in tight contact with the flexible tubular interior 36 of the flexible member 32.
By definition above, the flexible member comprises an outer "wall" that defines the flexible tubular interior that tightly encloses and secures the core and rigid member ends. For example, such a construction could be formed by tightly binding a flexible cord (e.g., cotton, plastic, and the like) or thin, lightweight strands of leather (e.g., 1 oz. to 2 oz. leather) around the core and rigid member ends or, more preferably, by tightly braiding a flexible cord or thin strands of leather around the ends. An example of a flexible member is a terminal braided leather barrel of a conventional braided leather romal rein.
In preferred embodiments of the invention, illustrated in FIGS. 6A and 6B, the rigid member 37 comprises at least three attached layers, i.e., two thin outer layers of leather 41, 42 and one or more inner reinforcing layers 43. In this embodiment, the two thin layers of leather 41, 42 are preferably approximately equal in thickness, and are preferably pieces of about 4 oz. leather. Leather weights and their corresponding thicknesses are known to the skilled artisan. For example, a piece of 4 oz. leather is about 1/16 inch thick. Leathers used for strap goods, such as split reins and bridles, are typically 6 oz. to 8 oz. leathers, having a thickness of about 1/4 inch to about 3/8 inch. The thick leather used for saddles is typically 10 oz. to 14 oz.; whereas thin, flexible leathers used for laces or for braiding are typically 1 oz. to 2 oz. leathers.
In the preferred embodiments, the inner reinforcing layer(s) 43 is the major component for adding strength and stiffness to the rigid member, such that the combination of the three or more layers has a strength and stiffness approximately equivalent to the strength and stiffness of an 8 oz. piece of leather. There are many known types of materials that can provide the required strength and stiffness including thin, rigid thermoplastic and thermoset plastics, strong reinforcing nylon or cotton webbing, plastic coated webbing material, and the like, or combinations of these. A suitable reinforcing material for use in the invention is a heavy nylon webbing coated with vinyl, with the name "Biothane", manufactured by BioPlastics Company, Inc., North Ridgeville, Ohio. The use of one layer of Biothane with two 4 oz. strips of leather is sufficient to provide the desired strength and stiffness. One layer of Biothane is approximately 1/16 inch thick.
The thickness of the reinforcing layer required to provide the requisite strength and stiffness to the rigid member depends on the inherent strength and stiffness of the selected reinforcing material. Several layers of the reinforcing material may be required. Thus, the thickness of the resulting rigid member may vary from about 3/16 inch or less, to about 1/2 inch or more. As will become apparent from the embodiments of the invention described below, the thickness of the rigid member will determine which of the embodiments may be employed. Preferably, the rigid member is as thin as possible.
In the embodiment illustrated in FIG. 6A, the reinforcing layer(s) 43 extends within the rigid member 37 to a point at or near the junction with the core end 38 of the length of rein 20. The two outer layers 41, 42 of the rigid member 37 extend beyond the end of the reinforcing layer 43 and the core end 38 and sandwich the length of the rein for a variable distance "d" beyond the core end 38. The distance "d" can be determined by one skilled in the art according to the attachment means illustrated in FIG. 7, wherein the layers of the rigid member can be stitched and/or glued, bound, or otherwise attached to the core, thus securing the rigid member directly to the core of the rein.
In the embodiment illustrated in FIG. 6B, the reinforcing layer(s) 43 remains associated with at least one of the two outer layers 41, 42 of the rigid member 37, and extend(s) in conjunction with the outer layer to participate in the sandwich of the length of the rein for the distance "d". The means of attachment to the core may also be as illustrated in FIG. 7.
In the embodiment illustrated in FIG. 6C, the end of the rigid member including the two outer layers 41, 42 and the reinforcing layer 43 do not extend beyond the end of the core of the rein. Instead, the rigid member end and the core end each extend into and are in tight contact with the tubular interior of the flexible member for a distance sufficient to secure the length of rein within the interior of the flexible member. The distance is determined by such variables as the diameter and flexibility of the core end, the thickness and rigidity of the layers of the rigid member, the tightness of the binding that forms the outer wall of the flexible member and defines the flexible tubular interior, the length and thickness of the outer wall of the flexible member, and the like.
FIG. 8A, 8B and 8C illustrate less preferred embodiments of the rigid member that do not employ a reinforcing layer. Instead, the rigid member 137 in these embodiments comprises two or more layers of leather 141, 142, which together provide the required stiffness and strength. For example, one layer may be 8 oz. leather and the other layer 2 oz. leather (e.g., FIG. 8A); both layers may be 6 oz. leather or 8 oz. leather, or combinations of these, or the like (e.g., FIGS. 8B and 8C). The layers may extend to form a sandwich around the core end 138 of the length of the rein 120 within the flexible member 132, as illustrated in FIGS. 8A and 8B and be secured to the core end as illustrated in FIG. 7. Alternatively, the end of the rigid member may terminate at or near the core end 138 of the rein, as illustrated in FIG. 8C, and the core end 138 and the end of the rigid member 137 extend into the flexible tubular interior 136 of the flexible member 132 for a distance sufficient to secure them in the flexible member, the distance being variable as described above for the embodiment of FIG. 6C.
Although it is possible, in the embodiments illustrated in FIGS. 8A, 8B and 8C, to use two layers of heavier 6 oz. or 8 oz. leather (each layer typically 1/4 inch to 3/8 inch thick), without a reinforcing layer, the resulting sandwich around the core of the rein is 2 to 3 times larger than that of the preferred embodiment of the invention, and the resulting flexible member 132 that encloses the sandwich may be much larger than that of the preferred embodiment. Thus, this embodiment of the invention is less preferred if the larger flexible member is aesthetically undesirable.
Embodiments of the second end and connector portion of the rigid member are illustrated in FIGS. 9 through 12. In each of these embodiments, the preferred rigid member comprises at least three layers, including the reinforcing layer, described above.
In a preferred embodiment of the connector portion of the rigid member illustrated in FIGS. 9A and 9B, a tight connection is provided between the connector and the end ring of the bit. In this embodiment, the rigid member 52 comprises at least three layers, i.e., two thin layers of leather 54, 56, and at least one reinforcing layer 57, as described above in FIGS. 6A, 6B and 6C. At the connector portion 58 of the rigid member 52, the two leather layers 54, 56 are longitudinally separated from each other. The reinforcing layer 57 remains attached to one of the leather layers. (If more than one reinforcing layer is employed, it may be remain attached to either one of the leather layers). Each of the separated layers 54/57 and 56 has an opening 60 therethrough for passage of a fastener 62, as illustrated for layer 54/57 in FIG. 9C. The fastener may be as simple as a cord (not shown), such as a leather cord, for tying the separated layers to the end ring. However, the fastener 62 is preferably a bolt arrangement, such as one having interlocking male and female portions for securing the separated layers 54/57 and 56 to the end ring 64 of the bit 66, such that the end ring 64 is sandwiched between the separated layers 54/57 and 56 and the bolt passes through the end ring 64. Such a bolt arrangement may be a typical nut and bolt. However, a preferred fastener for this embodiment of the invention is a chicago screw. When the male and female ends of the fastener are joined, the two layers of the rigid member form a tight connection with the end ring of the bit (FIG. 9B).
The embodiment of the connector portion illustrated in FIGS. 9A, 9B and 9C is also suitable in embodiments of the invention employing a rigid member that comprises two layers of leather without a reinforcing layer, such as the embodiments illustrated in FIGS. 8A, 8B and 8C.
FIGS. 10A, 10B, 10C and 11 illustrate other embodiments of the connector portion 58 of the rigid member 52. In each of these embodiments, the rigid member comprises a strap 70 having a strap end 72 for passage through the end ring of a bit (not shown) to form a loop 74. The strap end 72 is then fastenable to the rigid member by a fastener. Many different types of fasteners are suitable for use to fasten the strap end, and such fasteners are known to those skilled in the art. The illustrated fasteners are a chicago screw 76 (FIGS. 10A, 10B, 10C), a buckle (FIG. 11) or any other fastener known to those skilled in the art, such as a snap fastener (not shown).
In another embodiment of the connector portion 58 of the rigid member 52, illustrated in FIGS. 12A and 12B, the connector portion comprises a rigid snap end fastener 80 integrally attached to and extending from the rigid member, for snapping onto the ring of the bit (not shown).
In another embodiment of the invention, flat split or romal reins are provided by which the bit end of the rein may be attached to the flat rein without the presence of a flexible member, as illustrated in FIGS. 13A, 13B and 13C. A tight connection between the end ring 100 of the bit 97 and the rein is also provided. In this embodiment, each of at least two rigid members 90 has an end 92 integrally secured to the length of flat rein 94 and a connector end 96 extending from the length of rein 94. Each connector end 96 has an opening 98 therethrough for passage of a fastener 99. For connecting the rein to the end ring 100 of the bit 97, the end ring is sandwiched between the two rigid members and secured by the fastener 99 that passes through the end ring and each of the rigid members. The fastener may be a cord for tying the rigid members and the end ring together, but preferably is a bolt arrangement, such as that described above, which may be a nut and bolt, but preferably is a chicago screw, wherein the bolt passes through each of the layers and the end ring of the bit. As illustrated in FIGS. 13B and 13C, the rigid members may be connected to the flat rein by stitching 91 and/or gluing (not shown) and/or tying, or by a fastener 93 known to those skilled in the art, such as a snap fastener or a chicago screw, or the like.
In another embodiment of the invention illustrated in FIG. 14, a flat rein 101 is provided which comprises two layers 102 and 104. At the connector end 96 of the rein, the two layers are longitudinally separated from each other to form two separated layers 102 and 104, each of which has an opening therethrough for passage of a fastener 99, the opening and the fastener being similar to those illustrated in FIG. 13B and 13C. The fastener is preferably a bolt arrangement described above, which may be a nut and bolt, but preferably is a chicago screw. For connecting the rein to the end ring 100 of the bit 97, the end ring is sandwiched between the two rigid members and the bolt passes through the end ring and each of the rigid members. Attentively, the fastener may be a cord for tying the two separated layers to the end ring.
While the invention has been described herein with reference to the preferred embodiments, it is to be understood that it is not intended to limit the invention to the specific forms disclosed. On the contrary, it is intended to cover all modifications and alternative forms falling within the spirit and scope of the invention. | A braided romal rein having a bit end that is directly attachable to a bit, without the need for a separate connecting piece, provides direct contact between the bit in the animal's mouth and the rider's hands. The bit end of the rein comprises a rigid member that is integral with the rein and which has a connector portion that can be tightly connected to the end ring of the bit. Because the entire length of the rein, including the portion that connects to the bit, is a continuous construction, the former problems of loose joints at the rein end and the bit end are eliminated. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the field of commercial laundry equipment. More particularly, the present invention relates to a feed system for an ironer, folder or the like providing for multiple serially-located stations or positions, each of which is effective to provide garments to the ultimate ironer or folder.
2. Description of the Prior Art
In laundry-handling systems, the clothing, after drying, is often provided for folding, ironing and packaging in large bundles. Often, the ironing, folding and completing of the laundering steps are effected by an individual operator being supplied with garments and feeding them one-at-a-time to the appropriate ironing or folding equipment. This is a vast improvement over the older systems where each individual was provided with a table or automatic ironer, etc., to operate.
An exemplary feeding system for the folders is disclosed in Carothers et al. U.S. Pat. No. 2,359,464. The Carothers system uses two conveyors, the second being mounted inside the first. Clean diapers are placed on the lower inside of the first or larger conveyor and individually removed by various individuals who fold the diapers. Any overflow from the folding operation is returned by the second conveyor, and the top of the first conveyor is used to return unacceptable diapers to a rewashing basket. The system, however, requires individuals at plural stations to fold each diaper.
In another system, in U.S. Pat. No. 1,813,229 to Constable, dirty clothes are fed to individual compartments on a conveyor line and are sequentially sorted by color and character into bundles in individual units. The steps are performed by separate operators. The resulting small bundles are netted and marked for washing by two more operators. Thus, each position on the conveyor performs a different function. Also, Blume in U.S. Pat. No. 3,327,942 discloses a plural-station conveyor system for sorting clothes into light, medium and heavy-soiled groups. The conveyor provides the clothes to a plurality of operators who pick up individual articles and deposit them on three other conveyors which are designated for the light, medium and heavy-soil characteristics. Thus, in Blume, plural serially-arranged sorting stations, each performing the same function, are provided.
In the sorting art relating to other types of items, various transverse feed systems are known. For example, Young et al. in U.S. Pat. No. 3,733,236 disclose a single station reversible conveyor system which feeds meat to a scale and then transversely wraps, seals and marks the weighed item. Nevills in U.S. Pat. No. 1,624,175 utilizes a gear type of system to separate and individually feed pieces to a conveyor operating in a longitudinal direction.
Also, Sylvester et al. U.S. Pat. No. 3,019,583, and Shanklin et al. U.S. Pat. No. 4,035,983 both disclose single-item feed from a station to a transversely operated belt. Shanklin et al deal with a wrapping or sealing operation and do not disclose plural feed stations. Sylvester et al deal with a system for heat-sealing packages that are, at least, slightly irregular.
There is clearly a need in the art for a system to rapidly feed individual articles, such as towels, shirts, etc., to ironing and folding machines. A commercial ironer, in particular, is in need of any associated system which can increase the throughput of the ironer. The ironer is among the more expensive machines in a commercial laundry operation. A single ironer may be run with five lanes in parallel; that is, five girls feeding articles into the ironer at the inlet end and five separate folders associated with the ironer at the inlet or outlet. Such an arrangement not only allows a single machine to be used in conjunction with more feeders and more folders, but it also allows a mix in the types of items being processed through the folder at the same time. For example, napkins or other items requiring a french fold may be sent through a french fold lane, whereas other items requiring perhaps a quarter or half fold may be sent through another lane adapted to fold the items accordingly. In such an arrangement as now known in the art, the speed of processing items in ironing and folding the finished goods is essentially limited by the number of lanes which can be operated in parallel.
SUMMARY OF THE INVENTION
The present invention provides a system for feeding an ironer with a plurality of independently operable feeders, each of which may be utilized by plural operators. The use of independent feeders allows for maximizing the output of an ironer. Since plural stations are used, each line can be operated independently so that a break-down of one line will not terminate the whole ironing operation and different ironing operations can be effected at the same time. Thus, for instance, different towels having different folding and ironing requirements could be continuously ironed with one machine.
In operation, a conventional ironer is provided with a plurality of multiple station feeders. The feeders may be provided with articles to be fed by a common conveyor or separate conveyors, depending upon whether different articles are to be ironed or not. Each feeder is provided with at least two stations, either one or both of which may be used at any given time. A conveyor system is provided adjacent each station to supply, e.g., towels to each operator. The operator picks up an item to be ironed by its two adjacent corners and reaches over a feeder conveyor which may be a narrow belt, such as an ordinary V-belt, draping the article over the conveyor in the process. When the operator reaches a touch bar, which is selectively positioned, the operator releases the article and allows it to drape over the feeder conveyor. The same steps are taken by the second operator at the second station such that articles are placed on the one conveyor with increased speed and with appropriate spacing.
In an alternative embodiment, the articles are conveyed to an optional smoothing brush which is operatively interconnected with a switch and a sensor so that the item is smoothed and straightened and the brush is turned off just prior to reaching the end of the item. A nip roller is also provided to hold the item during the brushing operation.
If vertically aligned, the article is then passed between a pair of rollers, each fitted with a conveyor belt, and is reoriented to the horizontal by the belts which are twisted such that the inlet is vertically oriented and the outlet is horizontally oriented. The article is then ready for ironing. Depending upon the size and nature of the articles, a single narrow V-belt may be utilized to convey the item from the touch bar at the operator station to the reorienter, or a pair of spaced-apart narrow conveyor belts may be utilized. Also, a wider conveyor may be used. The reorienter may be used with a pair of narrow V-belts to facilitate flattening the article by a blade and spreader spaced between the feeder and the ironer.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the present invention may be had from a consideration of the following detailed description, taken in conjunction with the accompanying drawings in which:
FIG. 1 is a simplified partial plan view of the overall multi-station feeder embodying the invention;
FIG. 2 is a side elevational view of one of the feeder units;
FIG. 3 is a section taken along line 3--3 of FIG. 2, showing one embodiment;
FIG. 4 is a schematic plan view of one feeder showing a second embodiment;
FIGS. 5A and 5B are top and side views, respectively, of a reorientation portion of the apparatus of FIG. 1; and
FIGS. 6A and 6B are top and side views, respectively, of a french folder which may be used with the system of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1, the basic structure of one particular arrangement of the present invention is shown schematically. In this figure, input or supply conveyors such as 10 are utilized to transport laundry items to each of the stations operated by the operators 14. The operators pick articles from supply conveyor 10 and drape them across their adjacent feeder conveyor 18. At each station, an operator 14 is provided with an adjustable touch bar 20.
In this manner, each operator 14, working at her own speed, places articles one at a time across a conveyor 18. In doing so, the operator picks up an article by its two end corners, reaches across the conveyor 18 to contact the touch bar 20 and immediately releases the article. The touch bar 20 is adjustable, and is set in position in accordance with the laundry articles being processed to be properly positioned on the conveyor 18.
The feeder conveyor 18 may be in the form of a V-belt as in Lane 1 and is driven to have its upper side moving from left to right as shown in FIG. 1. At the right-hand end of the conveyor 18 of Lane 1 is a pair of conveyor feed rollers 28, 30 which are associated with orienting conveyor belts 32, 34 (see FIG. 5A).
As will be described hereinafter, feeder conveyor 18 may take various shapes, depending upon the items to be ironed and the desired eventual folded shape of the items. As shown, each of the plural station feeders, indicated generally by 24, is independently operable and may be on line individually, independent of the other feeders and of the ironer, indicated generally as 26.
Completing the description of the overall system generally depicted in FIG. 1, an inlet conveyor 25 is shown adjacent inlet folders 27A and 27B, and an outlet conveyor 29 is shown at the right-hand end of the ironer 26 for transporting ironed laundry articles out of the ironer for stacking or, in the case of Lane 1, to a further folder 30 for a final folding operation of goods in Lane 1.
The articles, after being draped by the operators, are smoothed, aligned and brushed, as will be described hereinbelow by reference particularly to FIGS. 2-4, and then reoriented horizontally for ironing. This is effected by the article exiting feeder conveyor 18 at orienting conveyor feed rollers 28 and 30, as shown in FIGS. 5A-5B. Roller 28 positions lower orienting belt 32 and second roller 30 positions upper orienting belt 34. Belts 32 and 34 are twisted through a 90° angle and thus the articles exit each feeder 24 horizontally adjacent upper orienting belt exit roller 36 and a lower orienting belt exit roller 98. The articles are thus horizontally fed into ironer 26 at first ironer roller 38 by feed rollers 40. In this manner, the articles are serially fed to plural operators, each of which functions independently, are automatically vertically folded in half, reoriented horizontally or parallel to the axis of the ironer roller and fed to the ironer in one continuous operation wherein each feed unit may be independently operated.
FIG. 2 shows the details of another particular arrangement in accordance with the invention in which a supply conveyor 10 is substantially aligned with the feeder conveyor 18 and in which two operator positions are provided side-by-side. In FIG. 2, articles 42 are provided for the operators, not shown, by supply conveyor 12 which is provided with side supports 44 and positioned by rollers 46, one of which is driven by a motor, not shown. The feeder 24 comprises a frame used to support supply conveyor 12 and to mount touch bars 50. Each operator is provided with a touch bar and each bar is adjustable through pivoting mounting brackets 52 and an adjustable retainer, shown in FIG. 4, which is selectively positioned in one of orifices 54 in the touch bar. In this manner, the operator obtains an article 42 from supply conveyor 12, holding it at its corners, reaches over feeder conveyor 18, which is positioned by rollers 56, to touch the bar 50 and releases the article. A towel 58 is shown in position after release, in FIG. 2, draped over feeder conveyor 18. Feeder conveyor rollers 56 are driven by an electric motor, not shown. Towel 58 is then carried by feeder conveyor 18 in the direction indicated by the arrow to nip roller 60 which is used to hold it in position after it has passed selectively positionable electric eye 62, which is connected to switch 64. Electric eye 62 is positioned between the two portions of the towel, below the level of roller 56, and senses the distance towel 58 hangs downward to determine appropriate alignment. If the towel has been improperly draped, switch 64 initiates operation of electric motor 66 which drives brush 68 through shaft and gear arrangement 70. Nip roller 60 is used to hold the towel in a steady position after this vertical alignment.
The article or towel then passes under second electric eye 74, which senses the presence of the towel and initiates rotation of brush 76 which is rotated by electric motor 72, operated through switch 78 which is interconnected with electric eye 74. As shown, brush 76 rotates in a counterclockwise direction, looking downward, and smoothes towel 58 for entry into the reorienting apparatus depicted in FIGS. 5A and 5B. Electric eye 74 is positioned to stop rotation of brush 76 just prior to the end of towel 58 so that the brush does not catch on the fringe on the towel.
As shown in FIG. 3, a section taken along lines 3--3 of FIG. 2, support bracket 48 is provided with supply conveyor support 80, touch bar support 82 and feeder conveyor support 84. The feeder conveyor embodiment depicted in FIG. 3 is the single inverted V-belt utilizing a narrow belt 86 and wheel 56 on support 88. The arrangement of brush 68 and electric eye 62 is depicted herein as well. V-belt support 88 also provides the requisite draping for towel 58 which is shown in position just prior to release by the operator at touch bar 50, and, in phantom, after release and appropriate draping over support 88 and the belt 86.
In FIG. 4, a plan view corresponding to FIG. 3 but illustrating a slightly different embodiment, dual conveyor belts 92, 94 are shown. In this figure, support bracket 48 is provided with support member 84, to which is connected the conveyor belt support base 90 mounting the first and second V-belts 92 and 94 for transporting articles draped over them by the operator. In this form, articles of a larger size may be appropriately draped for folding in half prior to ironing or, alternatively, a blade member 96 mounted between the two V-belts 92, 94 may be used to spread openly articles draped over the belts 92, 94 for admission to the ironer in an open, flat horizontal orientation. As the article passes over the member 96 it is picked up by rollers 97a, 97b and fed into the ironer 26.
Additionally, in FIG. 4, touch bar 50 rests on support 82 and is adjustable through pivot arms 52. The touch bar is retained in position by adjustable retainer 98 being placed in a mating relationship with one of orifices 54 to select the distance that touch bar 50 extends away from support 48, and the reach needed by the operator prior to release of the article.
Optional reorientation portion of the apparatus of the present invention is further depicted in FIGS. 5A and 5B. In these figures, single V-belt on roller 86 supplies articles to upper orienting belt 34 and lower orienting belt 32. The belts are positioned about rollers 28 and 30 so that the towel enters between the upper and lower belts and is grasped firmly along the totality of its folded width. Belts 32 and 34 are retained in a close relationship and twisted to a horizontal or co-planar relationship with ironer 26 at the exit from the reorienter, which is formed by exit rollers 36 and 98. Thus, by the apparatus of the present invention, gravity is utilized to position the towel both easily and rapidly in a half-folded position. The towel is then adjusted to insure accurate ironing, smoothed, and rotated from a vertical orientation to a horizontal orientation for initial folding by folder 27B and ironing in ironer 26. This transverse feed, in combination with the touch bar and the remaining apparatus of the present invention, provides a significant improvement in speed and quality of ironing work. The resulting system allows for plural independent feeds to an ironer, plural stations for each train and simple easy accurate operation of an ironing system.
In an alternative embodiment depicted in FIGS. 6A and 6B, a french folder such as 27A of FIG. 1 is used in place of or with the reorientation apparatus. In this apparatus, woven belting is utilized for the feed conveyor, and the articles are positioned by the use of a touch bar as in the prior systems. However, in this operation, feed conveyor 100 terminates at roller 102 and the article is positively fed to the french folder through nip roller 104 and guide 106. The french folder 27A is preferably formed of elongated rollers 108 which are provided with plural gripping conveyors 110 to grasp the article and convey it toward ironer 26. As the article is conveyed toward ironer 106, it comes in contact with first guide 112 which initiates folding of one side of the article by curling it over on itself. After this is initiated, the opposite side of the article is folded over by second french folder guide 114. The article then exits the french folding section between rollers 116 which are rotated by conveyors 110 and enters ironer 26. In this manner, the plural station feeders of the present invention may be utilized to french fold articles prior to ironing.
Although there have been described above specific arrangements of a multi-station feeder for a commercial ironer or folder in accordance with the invention for the purposes of illustrating the manner in which the invention may be used to advantage, it will be appreciated that the invention is not limited thereto. Accordingly, any and all modifications, variations or equivalent arrangements which may occur to those skilled in the art should be considered to be within the scope of the invention as defined in the appended claims. | A multi-station laundry feeder including supply apparatus for a plurality of article conveyors, multiple stations at each conveyor, and an article transporting conveyor utilizable by the multiple stations for transversely placing articles on the transporting conveyor. The operators remove individual articles from the supply conveyor, drape them across the transporting conveyor, touching an adjustable bar which is positioned to automatically appropriately align the articles, and release them. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
Embodiments of the invention described herein pertain to the field of computer software. More particularly, but not by way of limitation, one or more embodiments of the invention enable systems to apply a set of rules to determine if two or more data objects are similar in accordance with that the defined set of rules. Subsequent processes make use of the similarity information. Examples are the merging of similar objects to one resulting object and reporting using aggregated information.
2. Description of the Related Art
Modern businesses have a need to utilize stored business data to make effective business decisions. When the data in these systems is not shared and made consistent, inefficiencies occur. Achieving consistent data across multiple distributed heterogeneous systems is difficult. Establishing effective communication links between disparate systems is a prerequisite to making the data consistent, but does not alone solve the problem. Even when data is effectively shared throughout an organization, problems still arise in that over the course of time the data may exist in different forms and models. Since the achievement of data consistency is difficult it is common for companies to maintain data in independent realms. For example, because of the difficulties associated with merging data, some companies independently maintain data for each of their different corporate divisions and only utilize such data for business decisions relevant to a particular corporate division. The maintenance of independent systems often occurs during mergers and acquisitions where company systems are almost certainly heterogeneous and typically utilize radically different structures and data models.
To solve the data consistency problem and leverage the commonalities of data for the benefit of the company, companies typically seek to coordinate interaction between heterogeneous systems by identifying similar and overlapping data and then coordinating the integration of such data in a way that ensures the data stays consistent across different systems. Effectively accomplishing such coordination is difficult at best and tends to lead to organizational inefficiencies. One approach some organizations use is to maintain what is known as master data. Master data may be thought of as the definitive version of a data object. Solutions for coordinating the data, i.e., storing, augmenting and consolidating master data, are generally primitive and lack matching capabilities. Moreover, the fact that master data may exist does little to provide information technology personnel with insight about the process used in determining if an object matches another object.
Failing to successfully coordinate master data objects yields data object redundancies and inconsistencies that disrupt the business decision-making process and increase the overall cost of doing business. Furthermore, customer service suffers from incomplete data requiring customers to call multiple places within the same company to obtain the required information. In some cases the failure to efficiently service customers causes enough frustration that it begins to result in decreased customer loyalty and leads to a loss of customers.
Because of the limitations described above there is a need for a system and method that can effectively coordinate master data objects across an enterprise.
SUMMARY OF THE INVENTION
One or more embodiments of the invention enable systems to implement a rule-based approach to data object matching that enables the system to determine if two or more objects are similar. Once a set of two or more objects is determined to be similar, the system can merge the object set into one master data object or do any other further processing based on the matching result. The rules define what conditions are required to consider two or more objects as being similar or equal.
A certainty or confidence may be specified and then associated with each rule. Examples of the different indicators of certainty include, but are not limited to “automatic”, “manual high probability”, “manual medium probability”, and “manual low probability”. For example, the certainty “automatic” specifies that the objects can be considered matches and no additional manual verification is needed. The certainty “manual low probability” specifies that there is a low probability that the objects are truly matches and that a manual verification is needed.
Matching rules may be grouped by priority in such a way that if any matches are found in one priority group the matching process stops. If matches are not found, the next highest priority group of rules is processed.
Hierarchical matching rules may be specified that are able to express similarity of objects considering structured objects containing sub-objects in a hierarchical manner.
If no matching rule is defined a default rule may be applied. The ability to apply a default rule is particularly useful in embodiments of the invention that requires all fields of an object to be used for matching (e.g., two objects match if they are absolutely identical).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates an architectural view of a system utilizing an embodiment of the invention.
FIG. 2 illustrates a flow chart showing an embodiment of the invention comprising rule based matching.
FIG. 3 illustrates a flow chart showing an embodiment of the invention comprising priority rule based matching.
FIG. 4 illustrates a flow chart showing an embodiment of the invention comprising priority and hierarchical object rule based matching.
FIG. 5 illustrates a flow chart showing an embodiment of the invention comprising priority and hierarchical rule based matching with automatic and manual certainty testing.
FIG. 6 illustrates a flow chart showing an embodiment of the invention comprising priority and hierarchical rule based matching with automatic certainty testing followed by a manual certainty testing phase.
DETAILED DESCRIPTION OF THE INVENTION
A system and method for rule-based data object matching will now be described. In the following exemplary description numerous specific details are set forth in order to provide a more thorough understanding of embodiments of the invention. It will be apparent, however, to an artisan of ordinary skill that the present invention may be practiced without incorporating all aspects of the specific details described herein. In other instances, specific features, quantities, or measurements well known to those of ordinary skill in the art have not been described in detail so as not to obscure the invention. Readers should note that although examples of the invention are set forth herein, the claims, and the full scope of any equivalents, are what define the metes and bounds of the invention.
FIG. 1 illustrates an architectural view of a system utilizing an embodiment of the invention. Master Data Server 100 comprises an application layer 101 that interfaces with users authorized to view master data. The application layer makes use of adapters 106 that bridge the networks to the disparate databases 107 , 108 , 109 and 110 . The adapters may make use of communications technologies such as robust message queuing to ensure that data is reliably transferred. Each adapter may be customized to interface to a specific system or database. Data integrator 102 is utilized by application layer 101 to integrate data from the disparate sources and is configured with cleansing 103 , matching 104 , and mapping 105 modules. Matching module 104 is configured to implement one or more embodiments of the invention. Modifications to data in database 108 for example may be extended to the other databases via mapping module 105 while cleansing module 103 may be utilized to perform initial cleansing or periodic cleansing of data to ensure the master data is appropriately harmonized. Regardless of the functions of the other modules, matching module 104 is charged with the task of performing matches on whatever data objects are presented to it.
Entry of rules is accomplished via an interface such as a text based interface or a graphical user interface that allows a user to point and click in order to create and modify rules graphically. Any interface that enables the entry of rules is in keeping with the spirit of the invention.
FIG. 2 illustrates a flow chart of the rule based matching process as it occurs in accordance with one or more embodiments of the invention. Processing starts at step 200 by executing a rule or by data mining a set of target objects to match against at step 201 . For instance, the system can obtain a group of active objects or instantiate a set of target objects for subsequent processing. A rule is obtained at step 202 and this rule may be a default rule that compares all fields of a source and target object if no user defined rule is specified. The rule is executed and thus the objects are compared at step 203 . If there is a match, the flow of control passes to step 206 . If there are more objects to compare as determined at step 205 , then the process repeats at 201 .
FIG. 3 illustrates a flow chart of an approach to priority rule based matching. In this embodiment of the invention processing starts at 300 with objects obtained at step 301 . The next highest priority rule is obtained at step 302 and this rule may be a default rule that compares all fields of a source and target object if no user defined rule is specified. The objects are compared at step 303 and if there is a match, the flow of control passes to step 307 . If there are more rules to process as determined at step 305 , then the flow of control passes to step 302 . If there are more objects to compare as determined at step 306 , then the process repeats at step 301 . When there are no more objects to process, control passes to step 307 without producing a match.
FIG. 4 illustrates a flow chart of an embodiment of the invention that utilizes a priority and hierarchical approach to perform rule based matching of objects. In this embodiment of the invention, processing starts at step 400 with objects obtained at step 401 . Objects obtained at step 401 may comprise related objects such as sub objects of other objects in the repository, sub objects of other objects in the same process chain and/or sub objects of the current object itself. Hence when processing is applied against a set of objects it is also applied as needed to sub objects and/or related objects. The next highest priority rule is obtained at step 402 and this rule may be a default rule that compares all fields of a source and target object if no user defined rule is specified. The objects are compared at step 403 and if there is a match, the flow of control passes to done step 408 . If there are more rules to process as determined at step 405 , then the flow of control passes to step 402 . If there are more sub objects to compare as determined at step 306 , then sub objects are further traversed at step 401 . For instance, if the parent objects match the sub object matching initiates. If there are more objects to compare as determined at step 407 , then the process repeats at step 401 . When there are no more objects to process, control passes to step 408 without producing a match.
FIG. 5 illustrates a flow chart of the invention that utilizes a priority and hierarchical rule based approach to matching with automatic and manual certainty testing. In this embodiment of the invention, processing starts at step 500 with objects obtained at step 501 . Objects obtained at step 501 may comprise related objects such as all sub objects of other objects in the repository, all sub objects of other objects in the same process chain or all sub objects of the current object itself. The next highest priority rule is obtained at step 502 and this rule may be a default rule that compares all fields of a source and target object if no user defined rule is specified. The objects are compared at step 503 and if there is a match, the flow of control passes to the certainty test at step 509 . If the certainty value of the match is automatic then control flows to done step 508 . If the certainty value of the match is manual, then the user is queried to determine if the match is valid or not at step 510 . If the user confirms a valid match at step 511 , then flow of control passes to step 508 . If the user determines that there is a false match at step 511 , then flow of control passes to step 505 in order to check for more rules. If there are more rules to process as determined at step 505 , then the flow of control passes to step 502 . If there are more sub objects to compare as determined at step 506 , then sub objects are further traversed at step 501 . If there are more objects to compare as determined at step 507 , then the process repeats at step 501 . When there are no more objects to process, control passes to step 508 without producing a match.
FIG. 6 illustrates a flow chart of the invention that utilizes a priority and hierarchical rule based approach to matching with automatic and manual certainty testing. In contrast to the embodiment illustrated in FIG. 5 , the manual certainty testing is performed subsequent to the automatic certainty testing. In this example the user decision is not part of the matching but part of the subsequent processing of the matching result which is independent of the matching itself. Objects obtained at step 501 may comprise related objects such as all sub objects of other objects in the repository, all sub objects of other objects in the same process chain or all sub objects of the current object itself. The next highest priority rule is obtained at step 502 and this rule may be a default rule that compares all fields of a source and target object if no user defined rule is specified. The objects are compared at step 503 and if there is a match, then the match result is saved at 600 for subsequent manual processing. If there is no match at 503 , then processing continues for all rules at 505 . If there are more rules to process as determined at step 505 , then the flow of control passes to step 502 . If there are more sub objects to compare as determined at step 506 , then sub objects are further traversed at step 501 . If there are more objects to compare as determined at step 507 , then the process repeats at step 501 . When there are no more objects to process, control passes to step 601 where saved matches are retrieved (if there are no matches then processing completes and this is not shown as an output from 601 for ease of illustration). If the certainty of the match is set to automatic, then the next match is retrieved at 601 . If the certainty value of the match is manual, then the user is queried to determine if the match is valid or not at step 510 . If the user confirms a valid match at step 511 , then the match is saved as a true match at 603 to determine if there are more saved matches to check. If there are more matches to check control passes to 601 where the next saved match is retrieved. If there are no more matches to process then the process ends at 508 .
A graphical user interface may be utilized to input the rules and a parser may provide a mechanism for validating the syntax of the rules. Text based or any other type of interface may also be used in order to allow a user to enter rules.
The operators for use in the rule based matching are described in the following tables:
Source-field Modification Operators:
These operators are applied to the source-field.
Operator
Description
LEFT(field, n)
Extract the left n characters from field
RIGHT(field, n)
Extract the right n characters from field
SUBSTRING(field, start-pos, n)
Extract n characters from field starting
with start-pos
ADD_PREFIX(field, string)
Adds a prefix-string to the source field
ADD_SUFFIX(field, string)
Adds a suffix-string to the source field
Operators for Comparing Source and Target:
These operators generally comprise three parameters, the two values and a fuzziness parameter. The fuzziness parameter is optional and if not specified yields a rule with no fuzziness utilized in a match using the rule. The default value for fuzziness is 0 which means that no fuzziness is specified by the rule. The fuzzy evaluation may consider sounds-like, transposition of letters, doubling of a letter, adjacent-on-keyboard or any other algorithm for specifying near matches to signify true matches.
If the operators only comprise one field, or one field and an optional fuzziness value, then both target and source fields have the same name.
If the target-value exists normalized, the source-value is automatically normalized before any of the comparing operators is called. The normalized target-value is used for comparison.
Operator
Description
EQUAL(field-source, field-target,
(modified) source and target are
fuzziness, compare)
equal and both are not null
COMPARE (fuzziness)
comparison operation
(e.g., distance, sounds
like, adjacent on keyboard, etc . . .)
CONTAINS(field-source, field-
(modified) source is contained
target, fuzziness, compare)
in target and both are not null
STARTS_WITH(field-source,
target starts with (modified) source
field-target, fuzziness, compare)
and both are not null
ENDS_WITH(field-source, field-
target ends with (modified) source
target, fuzziness, compare)
and both are not null
NULL(field, source/target)
field of source or target is null
NORMALIZE(field-source, field-
normalize a source and/or target field
target)
if either is specified, (for example
for a text field make all
characters upper case).
The examples shown below contain often one field value only. If this is the case, the field name of source and target are the same.
Logical Operators.
The following logical operators can be used to build up complex rules
Operator
Description
exp1 AND exp2
Logical AND of expression1
and expression2
exp1 OR exp2
Logical OR of expression1
and expression2
NOT(exp)
Logical NOT of expression
Sub-objects (e.g. addresses or material segments) related objects (e.g. a vendor of a product) are addressed using the OBJECT operator.
For matching it is assumed that one (sub) object at a time is compared to either all sub objects of other objects in the repository, all sub objects of other objects in the same process chain or all sub objects of the current object itself.
If no matching rules for sub objects are defined the sub objects should not be used for determining matching results.
The following parameters are used in matching sub objects specified within the OBJECT-BEGIN and OBJECT-END operator pair, for example:
OBJECT-BEGIN(FIELD, SELECTION, ANY/ALL)
OBJECT-END
Parameter
Description
SELECTION
Selects a subset of the fields relevant for
matching e.g. for a plant dependent sub object
the selection plant = 1000
ANY
If any (one or more) sub objects of the current
object matches the sub objects of the other
object the sub objects match.
ALL
If all sub objects of the current object match the
sub objects of the other object the sub objects
match
The following examples show various combinations of operators for performing various matches.
Example 1 shows three rules that may be performed in the order shown thereby providing a priority for the rules. The example shows an automatic certainty rule that will result in a positive match if both the target and source objects have the same values for DUNS (Data Universal Numbering System) and TAX (e.g., tax identification number) respectively. In the next highest priority rule, a high certainty manual rule that allows a user to verify that a match exists for a source or target object that has a NULL value for TAX if both the source and target objects have the same DUNS value. Finally, the next highest priority rule specifies the converse test with respect to the last described rule, i.e., if both source and target objects have the same value for TAX and either one has a NULL value for DUNS then the object is probably the same and is left for the user to decide manually.
EXAMPLE 1
AUTO: EQUAL(DUNS) AND EQUAL(TAX)
MANUAL(high): EQUAL(DUNS) AND (NULL(TAX, source) OR NULL(TAX, target))
MANUAL(high): EQUAL(TAX) AND (NULL(DUNS, source) OR NULL(DUNS, target))
Example 2 shows two rules with some data manipulation commands. First, the PARTNUMBER is normalized in both the source and the target. In one or more embodiments of the invention the command as specified may operate on only the source unless a comma is placed before the field name meaning that the source field would not be normalized while the target value would be normalized. Next the leftmost 20 characters of the PARTNUMBER are extracted, then an automatic certainty rule is specified requiring both source and target to contain the PARTNUMBER. The next rule begins with a command to extract the rightmost 18 characters from the PARTNUMBER, the field of which is already normalized as per the first command in the rule group. A manual certainty rule is then specified if the 18 rightmost PARTNUMBER characters match the target field PARTNUMBER.
EXAMPLE 2
MODIFY: NORMALIZE(PARTNUMBER)
MODIFY: LEFT(PARTNUMBER, 20)
AUTO: CONTAINS(PARTNUMBER)
MODIFY: RIGHT(PARTNUMBER, 18)
MANUAL(medium): CONTAINS(PARTNUMBER)
Example 3 shows two rules. First an automatic certainty rule is specified if both source and target object have equal DUNS values AND the specified sub objects related to ADDRESS in the source or target match their normalized POSTAL_CODE and CITY and STREET and NUMBER. In addition, a manual high certainty rule follows that specifies that sub objects related to the ADDRESS, namely POSTAL CODE and CITY and STREET must be equal for the user to manually confirm that the objects are indeed a match.
EXAMPLE 3
AUTO: EQUAL(DUNS) AND
OBJECT-BEGIN(ADDRESS, *, ANY)
NORMALIZE(POSTAL_CODE)
EQUAL(POSTAL_CODE) AND EQUAL(CITY) AND EQUAL(STREET) AND EQUAL(NUMBER).
OBJECT-END(ADDRESS).
MANUAL(high): OBJECT-BEGIN(ADDRESS, *, ANY).
(EQUAL(POSTAL_CODE) OR EQUAL(CITY)) AND EQUAL(STREET)
OBJECT-END(ADDRESS)
Example 4 shows a variation of the above rule where a SELECTION has been made for a plant number (PLANTNR) equal to 100. I.e., for a plant dependent sub object, the selection plant=100 specifies what sub objects should be used in the match.
EXAMPLE 4
AUTO: EQUAL(GTIN).
OBJECT-BEGIN(PLANTDATA, PLANTNR=100, ALL)
AUTO: EQUAL . . .
OBJECT-END
Example 5 shows a manual medium certainty rule wherein the PARTNUMBER of the source being equal to the GTIN of the target satisfies the rule, OR the PARTNUMBER of the source and the UPC of the target satisfies the rule, OR both the source and target PARTNUMBERS are equal.
EXAMPLE 5
MANUAL(medium): EQUAL(source=PARTNUMBER, target=GTIN) OR EQUAL(source=PARTNUMBER, target=UPC) OR EQUAL(source=PARTNUMBER, target=PARTNUMBER)
Example 6 shows a manual high certainty rule that is satisfied when the DESCRIPTION field of the source CONTAINS the GTIN field of the target.
EXAMPLE 6
MANUAL(high): CONTAINS(source=DESCRIPTION, target=GTIN).
U.S. patent application Ser. No. 09/577,268 entitled “Timeshared Electronic Catalog System And Method” filed May 23, 2000, U.S. Pat. No. 6,754,666 entitled “Efficient Storage And Access In A Database Management System” filed Aug. 21, 2000, U.S. patent application Ser. No. 09/643,316 entitled “Data Indexing Using Bit Vectors” filed Aug. 21, 2000, U.S. patent application Ser. No. 09/643,207 entitled “Data Editing And Verification User Interface” filed Aug. 21, 2000, U.S. patent application Ser. No. 09/960,902 entitled “Method And Apparatus For Structuring, Maintaining, And Using Families Of Data” filed Sep. 20, 2001, U.S. patent application Ser. No. 10/022,056 entitled “Method And Apparatus For Transforming Data” filed Dec. 12, 2001, U.S. patent application Ser. No. 09/960,541 entitled “Method And Apparatus For Dynamically Formatting And Displaying Tabular Data In Real Time” filed Sep. 20, 2001, U.S. patent application Ser. No. 10/172,572 entitled “Method And Apparatus For Generating And Utilizing Qualifiers And Qualified Taxonomy Tables” filed Jun. 13, 2002, U.S. patent application Ser. No. 10/990,293, entitled “Accelerated System And Methods For Synchronizing, Managing, And Publishing Business Information” filed Nov. 15, 2004, U.S. patent application Ser. No. 10/990,292 entitled “System And Method For Dynamically Constructing Synchronized Business Information User Interfaces” filed Nov. 15, 2004, U.S. patent application Ser. No. 10/990,294 entitled “System And Method For Dynamically Modifying Synchronized Business Information Server Interfaces” filed Nov. 15, 2004, are all hereby incorporated herein by reference.
While the invention herein disclosed has been described by means of specific embodiments and applications thereof, numerous modifications and variations could be made thereto by those skilled in the art without departing from the scope of the invention set forth in the claims. | Rule based data object matching to determine if two or more objects are similar to allow the objects to be merged into one master data object. The rules explicitly state what conditions are required to consider two or more objects equal. The certainty of the rule may be specified. Examples for the certainty are automatic, manual high, medium and low probability. For example, the certainty “automatic” specifies that the objects can be considered matches and no additional manual verification is needed. The certainty “manual low probability” specifies that there is a low probability that the objects are matches and that a manual verification is needed. Matching rules may be grouped by priority. If matches are not found, the next highest priority group of rules is processed. Hierarchical matching rules may be specified that are able to express similarity of objects considering structured objects containing sub-objects in a hierarchical manner. | 6 |
CROSS REFERENCE TO PRIOR APPLICATION
This is a U.S. national stage of application No. PCT/EP2008/005909, filed on Jul. 18, 2008. Priority is claimed on Germany, Application No.: 10 2007 038 848.0, filed: Aug. 16, 2007 the content of which is incorporated here by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a coil former for a linear motor stator for an automatic door, the linear motor stator having a coil arrangement, which, upon appropriate activation, is able to produce an interaction with a linear motor rotor, which causes thrust forces.
2. Description of the Related Art
Sliding doors with linear motors are known from the documents DE 40 16 948 A1, DE 196 18 518 C1 and WO 94/013055 A1. The basic arrangement of the shown linear motors suggests that they are individually manufactured in an expensive process and that a series production is not accessible or difficult to realize.
SUMMARY OF THE INVENTION
It is an object of the present invention to develop a linear motor or parts thereof for an automatic door such that the linear motor is easier to manufacture, wherein this should be accomplished in particular through automation of at least some parts of the production.
The inventive coil former for a linear motor stator for an automatic door has a body for the reception of a winding wire to form a coil and at least one flange terminating the body at a front side, wherein the linear motor stator has a coil arrangement, which upon appropriate activation, is able to produce an interaction with a linear motor rotor, which causes thrust forces. The inventive coil former is characterized in that at least one flange of the coil former has at least one wire reception, adapted to receive a predetermined length of the winding wire and to at least partially release it again.
This inventive configuration provides that the coils to be installed in a coil strand of the linear motor stator in a first arrangement, namely a coiling arrangement, can be coiled in an uninterrupted process by an automatic winding machine and thereupon be brought to the manufacturing site of the linear motor stator in a second arrangement, namely an equipping arrangement, without severing the winding wire. This means that the collectively wound coils are already linearly connected to each other and that, there are no connection points between the individual coils of such a coil strand. Thereby, in addition to allowing for automated winding of the coils of one coil strand, a higher reliability is guaranteed.
Thus, according to the invention, the at least one wire reception is preferably provided to receive the winding wire before and after coiling the body, and, after having terminated a collective consecutive uninterrupted coiling of several coil formers disposed next to each other in a coiling arrangement, to at least partially release it again such that a predetermined free wire length is given between wound coil formers, which length results from the released portion of the winding wire received by the wire reception and a portion of winding wire, which remains between two coil formers when being coiled consecutively onto them, such that the several collectively wound coil formers can be brought to the manufacturing site of the linear motor stator to an equipping arrangement which is different from the coiling arrangement, without having to sever the winding wire.
In this case, the predetermined free wire length is preferably dimensioned such that several, in particular three coil arrangements, which each have one uninterrupted winding wire, can be disposed in the linear motor stator in an interlaced manner. This means that between two individual coils of such a coil arrangement respectively one or several coils of one or several other coil arrangements are disposed. Due to the inventive configuration of the coil former, during the coiling process, it is not only possible for the individual coils of one coil arrangement to be oriented in a different way as during the assembly process, i.e. like in the completed linear motor stator, without severing the winding wire, but also to provide such a free wire length between the individual coils, that means wound coil formers, which length allows the individual coils of a coil arrangement not to be located directly next to each other, but next to coils of different coil arrangements of the linear motor stator. On account of consecutive activation of the different coil arrangements, an interaction is then produced with a linear motor rotor, which causes thrust forces.
According to one embodiment of the invention, the wire reception of the coil former has preferably at least one holding device that is able to release at least one portion of the winding wire received by the wire reception without having to overcome a release resistance. Due to such a holding device, the winding wire can be received during the automated coiling process and, once the coiling process of the coil arrangement is terminated, it can be readily released again in a straightforward manner.
The holding device preferably has at least one nose protruding beyond the flange, which is provided with at least one holding device, along or around which nose the winding wire can be guided. This is a particularly simple possible configuration of the inventive wire reception, which allows for an automated coiling of several coil formers disposed next to each other and complies with the requirement to be able to release the winding wire after terminating the coiling process without having to overcome a release resistance.
Preferably, the at least one nose has a guiding area, along or around which the winding wire can be guided, and a support area, which can absorb a force acting on the nose and originating from the guiding area. This configuration allows in a particularly simple and material-saving configuration to guarantee the strength of the nose such that the nose can absorb the forces, which act on the latter during the coiling process, during the removal from an automatic winding machine and during subsequent equipping of a linear motor stator, without being destroyed, for example sheared off.
As an alternative or in addition to such a nose, the holding device according to the invention may preferably have a groove, along which the winding wire can be guided. Hereby again an automated winding as well as a release of the winding wire is possible without having to overcome a release resistance, once the coiling process is terminated.
In the inventive coil former, the wire reception preferably has a reception guide, which is disposed on the entry side, in order to facilitate guiding of the winding wire within the wire reception. In this case, the disposition on the entry side particularly means that, during the winding process, the winding wire at first enters the reception guide prior to continue within the wire reception. Such a reception guide disposed on the entry side makes the winding wire enter in each case the wire reception after terminating the winding process of the body, even in case of existing manufacturing tolerances.
Preferably, the reception guide consists of a recess of the at least one flange, whereby the flange has a surface with reduced material thickness, which represents a particularly simple configuration to form the reception guide by making the flange thinner, the winding wire being guided along an edge generated between the thinner area and the normal thickness of the flange. This configuration contributes to material saving in a simple manner.
The recess of the at least one flange, by which the flange has a surface with reduced material thickness, preferably achieves a direct and linear guidance from an entry side of the wire reception to the holding device. On account of this configuration, a particularly simple automated coiling is made possible.
The inventive coil former preferably has a clamping device, which is disposed at the at least one flange, which flange has at least one wire reception to define one end of the coil and to not to release a winding wire received therein or to not to release it without having to overcome a release resistance. By means of such a clamping device, according to one embodiment of the invention, it is preferably guaranteed that, once the winding process of the coil arrangement is terminated, when at least partially releasing the winding wire received by the wire reception, the coil wound onto the body does not readily unwind again.
It is furthermore preferred that a direction, in which the winding wire is guided by the clamping device, is parallel to a direction in which the body is coiled. In this preferred embodiment, the clamping device, with its exit side, adjoins the entry side of the wire reception. After coiling the body, the winding wire enters the wire reception through the clamping device. A defined number of windings of the coil wound onto the body is hereby guaranteed, which number does not change once the winding is completed, because the end of the coil winding is held by the clamping device, and thus is not uncoiled during the release of the winding wire located within the wire reception. Furthermore, the parallel guidance of the winding wire in the clamping device with regard to the coiling direction of the body guarantees that a particularly simple coiling of the coil former can be carried out by an automatic winding machine.
Preferably, the clamping device consists of a wire guide and two barbs, whereby a winding wire can be inserted, with little or no resistance at all, past the barbs into the wire guide and it can not be removed from the wire guide or only be removed against the release resistance, against the action of the barbs. This configuration allows for an automated introduction of the winding wire into the wire guide and guarantees that the winding wire introduced into the wire guide can not be removed from the wire guide, for example in case of manually equipping the linear motor stator, thus allowing to keep the defined length of the wound coil.
It is furthermore preferred that the wire guide has a rounding on the exit side, along which a winding wire coming out of the clamping device is guided. This configuration prevents the winding wire from kinking, when winding the coil former and also when equipping the linear motor stator.
Preferably, the inventive coil former has a wire feed assistance, which is disposed at least at one flange, which has a wire reception, in order to define a start of the coil. Due to such a wire feed assistance, the winding wire, which is introduced into the wire reception of a coil former or with which the winding process of a coil arrangement has been started, is reliably introduced into the following, respectively the first coil former such that the coil start is defined and the winding wire is guided onto the body. All the above, in conjunction with the definition of the coil end, makes sure that the wound coil has a predetermined number of windings.
Preferably, in the inventive coil former, the at least one flange, which has a wire reception, is configured rotationally symmetric with regard to a winding axis of the coil former such that altogether two wire receptions are provided thereat. This allows for a particularly simple equipping of the automatic winding machine, in particular, if the at least one flange and/or the body have a rectangular shape, because in this case, during the equipping process, the orientation of the coil former requires less attention.
In the inventive coil former, the body and the at least one flange terminating the body on the front side, preferably have a break-through for a coil core, whereby several coil formers can be fixed on one winding mandrel for a collective consecutive coiling, which mandrel is passed through their break-throughs. This allows for fixing all coil formers of at least one coil strand on one winding mandrel guided through their break-throughs and for a collective coiling without having to sever the winding wire. On account of configuring the break-through in such a manner that the reception of both a coil core and the winding mandrel is possible, the equipping of the automatic winding machine with coil formers to be coiled can be done in a particularly simple way, because the relatively large break-through of the body, provided for the coil core, likewise serves for the reception and orientation of the coil former in the winding machine.
Preferably, the at least one flange of the inventive coil former has a guiding device, abutting coil cores, which are located directly next to each other, the coil cores' corresponding flanges being located in one plane, and aligned with each other in a defined manner. Due to this inventive preferred feature, inventive coil formers, located within the equipping arrangement, are aligned with each other in a defined manner without having to necessarily perform an additional alignment of the individual coils located on the coil formers of one or several coil strands.
Preferably, the at least one guiding device has a cut-out configured in the at least one flange, into which a projection of a directly adjacent coil former in an equipping arrangement is able to engage. Considering material saving aspects, a guiding device can be formed in a simple way.
It is furthermore preferred that the projection is formed by the holding device. In this way an element, used during the automated coiling process for defining the free wire length, can serve for aligning the coil formers in the equipping arrangement and thus fulfil two functions.
The inventive coil former for a linear motor stator for an automatic door is used, according to the invention, preferably for driving at least one door leaf of a sliding door, which is preferably configured as an arched sliding door or as a horizontal sliding wall. In addition to this application, it may be used for building a linear motor stator for driving gate leaves or in feeding devices, handling equipment or transport systems.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will now be described in more detail, reference being made to the embodiments, in which:
FIG. 1 a is a perspective view of a first embodiment of an inventive coil former from above;
FIG. 1 b is a perspective view of the coil former shown in FIG. 1 a from below;
FIG. 2 is seven of the coil formers shown in FIG. 1 in a coiling arrangement;
FIG. 3 is three coil strands with seven respectively coil formers in an equipping arrangement;
FIGS. 4 a to 4 e are configurations of magnetic keepers, on which the inventive coil formers are disposed in the equipping arrangement;
FIG. 5 a is a perspective view of a second embodiment of an inventive coil former from above;
FIG. 5 b is an elevation view of the coil former shown in FIG. 5 a;
FIG. 5 c is a perspective view of the coil former shown in FIG. 5 a from below;
FIG. 6 a is a perspective view of a third embodiment of an inventive coil former from above;
FIG. 6 b is a perspective view of the coil former shown in FIG. 6 a from below;
FIG. 7 a is an elevation view of the coil former shown in FIG. 5 a including the marked tool separation; and
FIG. 7 b is an elevation view of the coil former shown in FIG. 6 a including the marked tool separation.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 a is a first embodiment of an inventive coil former for a linear motor stator for an automatic door in a perspective view from above, i.e. with an illustration of the exterior side of the one flange 3 of the coil former, which in this case has two wire receptions 4 , 5 , which receive a predetermined length of a winding wire and are able to release it again at least partially. In this embodiment, the inventive coil former has an essentially cuboid body 1 for receiving the winding wire on its exterior side and has two flanges 2 , 3 terminating the body 1 on the front sides. In an elevation view, the cross-section of the flanges 2 , 3 has an essentially rectangular basic shape, which projects beyond the front sides of the cuboid body 1 . A break-through 8 extends through the body 1 and through the flanges 2 , 3 , terminating the front side of the body, for the reception of a coil core in an installed linear motor stator, respectively for the attachment of the coil former on a winding mandrel during the coiling process.
In the illustrated first embodiment, one of the flanges 2 , 3 , terminating the body 1 on the front side, namely the flange 3 shown at the top of FIG. 1 a , has a first wire reception 4 , 5 , in order to receive the winding wire after the coiling process of the body 1 and prior to the coiling process of a following coil former. In this embodiment, the flange 3 , provided with the first wire reception 4 , 5 , has a second wire reception 4 , 5 which, with regard to a winding axis defined by the break-through 8 , is offset by 180° with regard to the first wire reception 4 , 5 . If needed, the second wire reception 4 , 5 may serve as the reception of a predetermined length of the winding wire prior to the coiling process of the body 1 . In alternative configurations, the flange 3 , provided with the wire receptions 4 , 5 , may have one or more than two wire receptions. Furthermore, the flange 2 , which in this embodiment is not provided with a wire reception, may also have one or several wire receptions, in order to allow for an even simpler equipment of the automatic winding machine and/or for the reception of longer wire lengths of the winding wire.
Each wire reception 4 , 5 , in the shown embodiment of the inventive coil former, consists of a holding device 4 and of a reception guide 5 . The reception guide 5 achieves that the winding wire, entering the wire reception 4 , 5 , actually enters the latter and does not continue to be wound onto the body 1 . In the illustrated embodiment, the reception guide 5 consists of a slanted surface, by which the flange 3 tapers. Due to the slanted surface, one corner of the flange 3 is flattened to a triangular shape such that the winding wire, entering wire reception 4 , 5 , is more readily guided away from the body 1 to the exterior onto the flange 3 . In this embodiment, the holding device of the wire reception 4 consists of a nose of the wire reception 4 , protruding beyond the flange 3 , around which the winding wire is placed after the coiling process of the body 1 and after being guided through the reception guide 5 .
Situated in front of the reception guide 5 in terms of the technical winding, a clamping device 6 , through which the winding wire runs prior to being received by the reception guide 5 , is provided, incorporated into the flange 3 . The clamping device 6 does not release the winding wire received therein during the winding process, nor does it release it without overcoming a release resistance. This serves to secure the coil end of the coil wound onto the body 1 , after removing the completely wound coil arrangement from the automatic winding machine during the equipment of the linear motor stator, when the winding wire is removed from the wire reception 4 , 5 .
In this embodiment, the inventive coil former furthermore has a wire feed assistance 7 , in the shape of a nose protruding beyond the flange 3 and of an inclination, which is incorporated into the nose and defines a starting position of the coil, wound onto the body 1 . The winding wire, entering the first coil of a coil arrangement, is guided at a defined position along the wire feed assistance towards the body 1 and is then wound onto the body 1 with a predetermined number of windings, until being received by means of the clamping device 6 in such a way by the wire reception 4 , 5 , that at first it passes a guide of the reception 5 and is subsequently received by the holding device of the wire reception 4 , in this case by the nose of the wire reception 4 protruding beyond the flange 3 . Subsequently, the winding wire, again in a defined position, is guided along the wire feed assistance 7 of the next coil former in order to be coiled onto the body 1 thereof. This process is continued until all coil formers of the coil arrangement are wound.
In this embodiment, the inventive coil former has a guiding device 9 in the shape of a recess provided in the flange 3 , into which the nose of the wire reception 4 of the holding device of an adjacent coil former can engage such that the adjacent coil formers are aligned with each other in a defined manner.
In the embodiment shown not only the wire receptions 4 , 5 , but also the clamping device 6 , the wire feed assistance 7 and the guiding device 9 are correspondingly configured twice in the flange 3 .
FIG. 1 b shows the coil former, of FIG. 1 a from below, i.e. in a view onto the exterior side of the flange 2 , which is not provided with the wire receptions 4 , 5 and terminates the body 1 on the front sides. It can be seen, that the break-through 8 likewise extends through this flange 2 .
FIG. 2 shows seven inventive coil formers in a coiling arrangement according to the first embodiment shown in FIG. 1 , i.e. stacked on top of each other in such a way that, with their break-throughs 8 , they can be fitted onto a winding mandrel, the respective flange 3 of a coil former, provided with two wire receptions resting upon a flange 2 of an adjacent coil former, which flange is not provided with the wire receptions 4 , 5 .
FIG. 3 shows three coil strands, consisting respectively of seven wound coil formers, in an arrangement, with flanges 3 located in one plane and abutting each other and being provided with respective wire receptions 4 , 5 , in which the nose 4 of the holding device respectively engages in the guiding device 9 of an adjacent coil former. Non-hatched coil formers, respectively coil formers having the same hatching belong to one coil strand and, during the winding process, had been arranged according to FIG. 2 .
FIGS. 4 a to 4 e are several configurations of magnetizable keepers, on which the inventive coil formers are disposed in the equipping or equipment arrangement. FIG. 4 a is a configuration made from solid material. FIG. 4 b is a laminated configuration, in which the keeper consists of one laminated stack of the same individual laminations. FIG. 4 c shows a laminated keeper, in which individual laminations are used, which are offset with regard to each other, wherein the individual lamination layers, stacked on top of each other, alternatingly consist of two or three individual laminations. FIG. 4 d is a keeper consisting of bent wires. The keeper shown in FIG. 4 d may be formed likewise as one-piece as shown in FIG. 4 e or multiple pieces as shown in FIG. 4 c.
During manufacturing, the keepers are equipped with the wound coil formers and subsequently they are placed into a casting trough, before filling the casting trough with a synthetic resin.
FIGS. 5 a to 5 c show a second embodiment of an inventive coil former. In this case, FIG. 5 a shows a perspective view of the coil former from above and FIG. 5 c is a perspective view of the coil former shown in FIG. 5 a from below. Unlike the coil former shown in FIG. 1 , here the nose 4 has a support area 4 b , which is disposed with regard to a guiding area 4 a , along which the winding wire is guided, on the rear side of the nose 4 , and gives the nose 4 a better protection against shearing-off during the winding process or against other similar loads. Essentially, the support area 4 b is an enlargement of the nose 4 , which, at the bottom of the nose 4 by which the nose 4 is connected to the flange 3 , is reinforced and configured tapering towards the tip of the nose 4 .
FIG. 5 b is a top elevation view of the coil former shown in FIG. 5 a , in which an offset v of the nose 4 , more precisely of the guiding area 4 a of the nose 4 , with regard to a vertical centre line M is drawn in, the free wire length between two individual coils being defined by offset v.
The guiding device, consisting of a recess 9 , is adapted to the shape and position of the nose 4 , i.e. has a locating edge 9 a adapted to the support area 4 b , against which the support area of an adjacent coil former in the equipping arrangement bears, and which aligns the two adjacent coil formers with each other.
Furthermore, the clamping device is illustrated in detail in the FIGS. 5 a and 5 c . In particular a wire guide 6 a of the clamping device 6 can be seen, into which the winding wire 10 is introduced. The introduction is done by preferably passing through between two barbs 6 b of the clamping device 6 , which provides a simple introduction without much resistance. Instead of two barbs 6 b , likewise only one barb 6 b can be provided. An opposite side, at which usually the second barb 6 b would be found, is configured essentially flat. With such barb arrangements, a removal of the winding wire 10 from the wire guide 6 a cannot be done or can only be done while overcoming a release resistance. The release resistance is generated on account of a distance of the one barb 6 b to its opposite side, respectively of the two opposite barbs 6 b to each other, which distance is smaller when being compared to the exterior diameter of the winding wire 10 . On the exit side, the clamping device is provided with a rounding 6 c to prevent the winding wire from accidentally being bent during the winding process.
As another difference to the first embodiment shown in FIG. 1 , in the second embodiment of the inventive coil former, the reception guide 5 for the wire reception is not provided, in order to not to weaken the flange 3 in this area.
FIG. 6 a is a perspective view of a third embodiment of the inventive coil former from above and FIG. 6 b is a perspective view of the coil former shown in FIG. 6 a from below. Unlike the second embodiment shown in FIG. 5 , the reception guide 5 of the wire guide is not omitted, but enlarged and rectilinearly extending from the exit of the clamping device 6 to the nose 4 such that a winding wire, exiting the clamping device, is directly guided to the holding device of the wire reception, namely the nose 4 .
FIG. 7 a is an elevation view of the coil former shown in FIG. 5 a with a marked tool separation. FIG. 7 b is an elevation view of the coil former shown in FIG. 6 a with the marked tool separation. These tool separations T designate the separation line between two parts of an injection mould, by which the respective coil former is manufactured. The shape of the respective coil former and the separation line are chosen such as to be able to utilize a bipartite injection mould, except for the required tool to form the cavity for the reception of the keeper. So to speak one half of the injection mould can be moved frontally, i.e. in the drawings in vertical direction. For this purpose, the respective tool separation T extends for the major part across the respective break-through 8 and otherwise vertically through the side walls of the essentially cuboid body 1 and of the essentially rectangular flanges 2 , 3 , which are provided with the clamping devices 6 , wherein the tool separation T intersects these side walls respectively in the area of the clamping devices 6 . The thereby created offset with regard to a horizontal centre line is compensated for by a diagonally connection in the area of the break-through 8 .
This type of tool separation T represents a cost advantage, on the one hand in the utilization of only two halves, and on the other hand in that machines, which are able to bring the injection moulds close to the machine and to move them away under different angles, are very expensive.
The inventive coil former allows thus for automated coiling with a winding wire, for example enamelled copper wire, for manufacturing a coil strand, wherein a wire feed assistance 7 in the shape of a projection with a feed inclination is provided at the coil former. Furthermore, the inventive coil former has preferably a clamping device 6 in order to fix the last wire winding. For achieving the correct wire length between the coils, a wire reception 4 , 5 is provided, and a break-through 8 is provided at the interior side of the coil former for the reception and fixing of core laminations of a magnetic keeper. Due to the configuration of the flanges 2 , 3 terminating the body 1 at the front sides and protruding beyond the body 1 and likewise beyond the terminated wound coils, an electrical insulation of the winding from the core laminations is achieved, which laminations preferably form the magnetizable keeper.
The inventive coil former is preferably manufactured as a injection moulding part, a plastic material having good injection moulding features is used, for example natural PA6-30H. The material should be continuously heat resistant up to 130° C. and flame resistant.
For example respectively seven coil formers are combined into one coil strand. For this purpose, the coil formers are fixed one on top of the other on a winding mandrel, as shown in FIG. 2 , and are automatically coiled in a single operational step. The wire is guided via the introduction inclination of the wire feed assistance 7 towards the bottom of the coil former, i.e. the exterior side of the body 1 , and the last winding of each individual coil automatically engages in the clamping device 6 at the edge of the coil former, i.e. on the flange 3 provided with the wire reception 4 , 5 , and is thereby fixed. Upon transition from one individual coil to the next one, a free wire length, of for example 35 mm is realized, in order to be able to subsequently dispose the coil in a predetermined pattern, with interlaced individual coils of the coil strands. For this purpose, the wire reception 4 , 5 is mounted in the shape of a protuberance or nose at the flange 3 provided with the wire reception 4 , 5 .
As an alternative to this nose, likewise a cut-out or groove can be provided.
The wire length received by the wire reception is preferably measured such that respectively two more individual coils can be mounted between adjacent coils of a coil strand, such as illustrated in FIG. 3 .
Thus, while there have shown and described and pointed out fundamental novel features of the invention as applied to a preferred embodiment thereof, it will be understood that various omissions and substitutions and changes in the form and details of the devices illustrated, and in their operation, may be made by those skilled in the art without departing from the spirit of the invention. For example, it is expressly intended that all combinations of those elements and/or method steps which perform substantially the same function in substantially the same way to achieve the same results are within the scope of the invention. Moreover, it should be recognized that structures and/or elements and/or method steps shown and/or described in connection with any disclosed form or embodiment of the invention may be incorporated in any other disclosed or described or suggested form or embodiment as a general matter of design choice. It is the intention, therefore, to be limited only as indicated by the scope of the claims appended hereto. | A coil former for a linear motor stator for an automatic door having a coil arrangement, which, upon appropriate activation, is able to produce an interaction with a linear motor rotor, which causes thrust forces, with a body for the reception of a winding wire to form a coil, and at least one flange terminating the body at the front side, wherein the at least one flange of the coil former has at least one wire reception, which is able to receive a predetermined length of the winding wire and is able to, at least partially, release it again. | 8 |
PRIORITY CLAIM
[0001] This application claims the benefit of U.S. Provisional Application No. 62/278,773, filed Jan. 14, 2016, the disclosures of which is incorporated by reference in its entirety.
BACKGROUND
[0002] Tabletop games, such as board games and card games, are generally well known. Many are games of chance, where a player's success rests on luck of dice rolls or hands of cards. Others are games of skill, such as chess. Many games include aspects of both luck and skill, such as poker.
[0003] Other tabletop games test players' physical skills. Table shuffleboard involves players sliding weighted pucks along a long and smooth table with the aim of having their pucks stop in designated scoring areas. Such a game, however, has the drawback of requiring specific equipment and a considerable amount of space.
[0004] Other games of physical skill have been created with reduced equipment and space needs. For example, a game “Nickels” involves players sliding nickel coins on a table surface. Nickels was a simple gambling game where two players would each place a nickel on a playing surface and take turns trying to slide their respective nickel into their opponent's nickel. Once a player tapped its opponent's nickel three times, that player would take the opponent's nickel. Nickels, however, was not known to have additional rules. As a very simple game, players may quickly lose interest in Nickels.
[0005] Slightly more complicated tabletop games of physical skill, such as paper football have grown in popularity. Paper football involves a piece of paper folded into a small triangle that is slid or flicked across a table. Paper football gameplay typically involves rules loosely based on American football, including a kickoff to start the game, rules for advancing the paper football down the table or “field,” and rules for scoring.
[0006] A need remains for additional tabletop games of skill and methods of playing tabletop games of skill that offers players challenges, entertainment, and portability without requiring extensive and expensive equipment.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 illustrates a method of playing an exemplary embodiment of a coin flicking game.
[0008] FIG. 2A illustrates exemplary starting positions for a battle in a coin flicking game.
[0009] FIG. 2B illustrates exemplary movement of a coin in a coin flicking game.
[0010] FIG. 2C illustrates an exemplary successful turn in a coin flicking game.
[0011] FIG. 2D illustrates an exemplary unsuccessful turn in a coin flicking game where the coins do not tap.
[0012] FIG. 2E illustrates an exemplary unsuccessful turn in a coin flicking game where the coins kiss.
[0013] FIG. 2F illustrates an exemplary unsuccessful turn in a coin flicking game where a flick results in a coin leaving the playing surface.
[0014] FIG. 3A illustrates an exemplary measuring apparatus used to determine exemplary starting positions for a battle in a coin flicking game.
[0015] FIG. 3B illustrates an exemplary flicking motion used by a player during play of a coin flicking game.
[0016] FIG. 4 illustrates a method of playing an exemplary embodiment of a coin flicking game where each player starts with multiple coins.
[0017] FIG. 5 illustrates an exemplary bracket showing how players advance and win an exemplary embodiment of a coin flicking game.
[0018] FIG. 6 illustrates an exemplary coin used to play exemplary embodiments of the coin flicking game.
[0019] While embodiments of a coin flicking game and methods for playing a coin flicking game are described herein by way of examples and embodiments, those skilled in the art recognize that the disclosed coin flicking game is not limited to the embodiments or drawings described herein. The drawings and descriptions are not intended to be limited to the particular form disclosed. Rather, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the appended claims. Any headings used herein are for organizational purposes only and are not meant to limit the scope of the description or the claims. As used herein, the word “may” is used in a permissive sense (i.e., meaning having the potential to) rather than the mandatory sense (i.e., meaning must). Similarly, the words “include,” “including,” and “includes” mean including, but not limited to.
DETAILED DESCRIPTION
[0020] Various embodiments are disclosed herein of a coin flicking game and a method of playing a coin flicking game. Embodiments provide a game of skill in which players take turns flicking a coin so that it slides across a smooth surface toward an opponent's coin. The game involves at least two players, and each player may start with the same number of coins. Players score points by flicking their coin so that it taps against their opponent's coin. Players advance in the game by tapping their opponent's coin multiple times and eventually capturing opponents' coins. The player that captures all opponents' coins ultimately wins the game.
[0021] FIG. 1 illustrates an exemplary process 100 of playing an embodiment of a coin flicking game. At step 102 , the order of players is selected. Typically the game is played by four or more players, but alternative embodiments may allow for fewer or more players, as discussed below. Each player may start with a single coin. Once the order of players is selected, at step 104 the first two players are up to play against each other. Each turn in which two players play head-to-head may be referred to a “battle.” In each battle, both players start with a score of 0.
[0022] To start a battle, at step 106 each of the first two players puts a coin in the start position. As shown in FIG. 2A , the start positions of a first coin 220 and a second coin 230 may be across a table surface 210 from each other. Table surface may be any flat and smooth playing surface, such as a top of a table or counter. In certain embodiments, each player may simply position its coin relatively close to an edge of table surface 210 . For example, first coin 220 may be placed in proximity to edge 212 and second coin 230 may be placed in proximity to edge 214 . Alternatively, FIG. 3A illustrates an exemplary embodiment in which players may use a measuring apparatus 310 to consistently space a first coin 320 from a second coin 330 at the start of a battle. Measuring apparatus may be, for example, made of string or twine. Embodiments using measuring apparatus 310 may provide for consistent spacing at the start of each battle and consistent spacing independent of the size or shape of the playing surface.
[0023] At step 108 , the first player flicks its coin at second player's coin. FIG. 3B illustrates an exemplary flicking motion 344 in which a player uses a finger, such as index finger 342 of hand 340 to flick an edge of a first coin 320 in direction 322 toward a second coin 330 . Embodiments may include rules that discourage a player from moving its coin in any fashion other than a flicking motion 344 . For example, if a first player uses the top of the coin to drag the coin or if the player slides its finger to bump the coin rather than making a flicking motion 344 , then the battle may be started over.
[0024] At step 110 , the players determine whether the first player's coin successfully tapped the second player's coin. As shown in FIG. 2B , when the first player flicks first coin 220 , it slides along table surface 210 in a direction 222 . For a successful turn, the first coin 220 must tap the second coin 230 at step 110 , and that tap must be hard enough for the first coin 220 and second coin 230 to separate at step 112 . FIG. 2C illustrates an example successful turn for the first player where the first coin 220 is flicked in direction 222 such that it contacts the second coin 230 and the second coin 230 separates from the first coin 220 in direction 232 . If the first coin 220 taps the second coin when flicked, then step 110 is satisfied and the process 100 proceeds to step 112 . If the first coin 220 also separates from the second coin 230 , then the second step is satisfied and the process 100 proceeds to step 114 .
[0025] By successfully having its coin tap and separate from the second player's coin, the first player's score increments by one at step 114 . In order to win a battle, a player must successfully flick their coin so that it both taps and separates from their opponent's coin three times. Thus, at step 116 if the first player's score has not been incremented to three, the process returns to step 108 and first player again flicks its coin 220 toward 230 in an attempt to have the coins tap and separate. In a preferred embodiment the first player may flick its coin 220 from where it lies at the end of the prior flick. However, in alternative embodiments the players may reset both coins in the starting positions after a successful turn. If the first player successfully flicks its coin 220 into the second player's coin 230 on three consecutive flicks, then at step 118 the first player wins the battle and at step 120 the first player picks up both the first coin 220 and the second coin 230 . At step 122 , if the first player has picked up all of the coins from all players, then the first player wins the game at step 128 . If at step 122 it is determined that other players still have coins, then at step 124 the next two players are up and at step 106 the next two players each put a coin on the start position.
[0026] The first player may also have an unsuccessful flick that results in the second player having a turn. For example, at step 110 , if the first coin does not tap the second coin, then at step 126 the score is reset to zero and at step 130 it is the second player's turn to flick its coin toward the first player's coin. FIG. 2D shows an example of a flick in which first coin 220 moved in direction 222 but did not contact second coin 230 . Such a turn would result in it being the second player's turn, and the second player would then have an opportunity to flick the second coin 230 at the first coin 220 . The first player may also have an unsuccessful flick if, at step 112 , the first coin does not separate from the second coin. FIG. 2E shows an example of a flick in which the first coin 220 moved in direction 222 and contacted second coin 230 , but the coins remain in contact and do not separate. This may be referred to as a “kiss.” At step 112 , if the coins do not contact hard enough to separate, then at step 126 the score is reset, the coins are returned to their starting positions, and at step 130 the second player has a turn to flick its coin.
[0027] If the first player does not win the battle on its first turn, then the second player has a turn as set forth in steps 130 through 148 . The players will continue to take turns until one of the players wins the battle by successfully flicking its coin so that it contacts the opponent's coin and the coins separate three times in a row. As each player wins a battle, that player collects the opponent's coin. Players continue to battle each other in order until a single player has all of its opponents' coins.
[0028] At times during the game, a flick may result in a coin leaving the playing surface. For example, FIG. 2F illustrates an example turn in which a player flicks first coin 220 in direction 222 causing first coin 220 to tap second coin 230 in direction 232 and off of the table surface 210 . If either player flicks one or more coins off the table, the players place their coins in the starting position, as shown in FIG. 2A , and the battle starts over. Thus, while FIG. 2F illustrates the opponent's coin leaving the playing surface after the coins tap, the battle will also start over if the first player's coin misses its opponent's coin and leaves the playing surface off any side.
[0029] FIG. 4 illustrates an exemplary process 400 similar to process 100 described above, however in process 400 each player starts with multiple coins and each pair of players battle each other repeatedly until one of the players captures all of the other player's coins. Players may each start with the same number of coins. In such embodiments, if a first player wins a battle but at step 424 the first player does not have all of the second player's coins, then at step 426 the same two players start another battle. However, if at step 424 the first player has all of the second player's coins (or at step 452 the second player has all of the first player's coins), then at step 430 (or step 456 ) the next two players are up for the next battle.
[0030] FIG. 5 illustrates an exemplary bracket showing how players advance and win an exemplary embodiment of a coin flicking game. In a preferred embodiment, a coin flicking game starts with eight coins divided evenly across four players. A first player and a second player compete in a first battle. The first two players may continue to battle until either the first player or the second player has picked up all of its opponent's coins. The winner of the first set of battles will advance to the third set of battles. The next two players may compete in a second set of battles. In other words, the third and fourth players over all in the game may be the first and second players in the second set of battles. The player that eventually picks up all of its opponent's coins will win the second set of battles and advance to the third set of battles. In the third set of battles, the winners of the first two sets of battles (i.e., the winner of the battle between the first two players and the winner of the battle between the second two players) may compete, and the game will continue until one of the players picks up all of its opponents' coins. Alternative embodiments may allow players to advance differently. For example, embodiments may provide round-robin stage before the player play in an elimination tournament as illustrated in FIG. 5 .
[0031] Embodiments of coin flicking games may be played with coins configured to slide well on a smooth playing surface, such as coin 600 shown in FIG. 6 . For example, coins used to play the coin flicking game may be aluminum and may have a smooth surface 602 (the underside not sown in FIG. 6 ) on at least one side to reduce friction when sliding along a playing surface. The side 604 not configured to slide over a playing surface may include a logo 606 . The coins may be substantially cylindrical in shape with a diameter of about 0.75 inches and thickness of less than 0.1 inch. Embodiments of a coin flicking game may alternatively be played with currency, such as United States pennies, nickels, or quarters.
[0032] Embodiments of a coin flicking game disclosed herein are described as requiring a player to tap another player's coin three consecutive times in order to win a battle. Alternative embodiments, however, may have other requirements. For example, embodiments may only require two consecutive taps to win a battle to speed up a game or three or more consecutive taps to win a battle to make the game more challenging. Still other embodiments may not require taps to be consecutive.
[0033] Further, embodiments of a coin flicking game disclosed herein describe, for example in steps 112 and 126 of FIG. 1 and in FIG. 2E , that when a player's coin taps another player's coin but without sufficient force for the coins to separate after the tap (i.e., the player's coin “kisses” the other player's coin), the score is reset and the coins are returned to the start position. In alternative embodiments, if a first player's coin kisses the second player's coin, it may be the second player's turn and the second player may flick the coins from the kissing position. In such an alternative embodiment, that second player's first flick may count as a score because the coins initially are touching and the flick will result in the coins being separated. The second player then would only need two more successful turns to win the battle.
[0034] Embodiments have been disclosed herein. However, various modifications can be made without departing from the scope of the embodiments as defined by the appended claims and legal equivalents. | A coin flicking game apparatus and method of playing include a first coin having a smooth surface on a first side configured to slide on a playing surface; and a second coin having a smooth surface on a first side configured to slide on the playing surface; wherein a first player and a second player play the coin flicking game by: placing the first coin in a first starting position on the playing surface and placing the second coin in a second starting position on the playing surface; taking turns flicking their respective coins at their opponents coins with the goal of tapping their opponents coins a predetermined number of consecutive times. | 0 |
BACKGROUND
[0001] 1. Technical Field
[0002] The present disclosure generally relates to support stands and, particularly, to a stand to support a notebook computer.
[0003] 2. Description of Related Art
[0004] Due to small size and light weight, notebook computers are easy to carry and use in a variety of occasions. However, people feel uncomfortable in using a notebook computer, especially when no appropriate place (for example when they are on the bed or outdoors) to support the notebook computer is available.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 is an exploded, isometric view of an exemplary embodiment of a stand.
[0006] FIG. 2 is an assembled, isometric view of the stand of FIG. 1 .
[0007] FIG. 3 is an isometric view of the stand of FIG. 2 in a use state.
[0008] FIG. 4 is similar to FIG. 3 , but showing a different state.
DETAILED DESCRIPTION
[0009] Referring to FIG. 1 , an exemplary embodiment of a stand includes a supporting panel 40 , two first rotating members 10 , two second rotating members 20 , two carrying members 30 , two blocking members 50 , two positioning members 55 , a connecting member 60 , and two supporting members 70 .
[0010] The supporting panel 40 is rectangular, and defines a plurality of vents 42 for heat dissipation.
[0011] Each first rotating member 10 is a long, rectangular post. The first rotating member 10 includes a top wall 12 , a first sidewall 14 and a second sidewall 15 opposite to the first sidewall 14 , perpendicularly extending from two opposite sides of the top wall 12 . A plurality of fastening holes 16 is defined in the first rotating member 10 , along a longitudinal direction of the first rotating member 10 , and through the first sidewall 14 and the second sidewall 15 . The top wall 12 defines a fastening hole 120 in a center of the top wall 12 . A post 140 perpendicularly extends from the first sidewall 14 , adjacent to a first end of the first rotating member 10 . The second sidewall 15 longitudinally defines a sliding slot 18 , adjacent to a bottom wall of the first rotating member 10 opposite to the top wall 12 . The first rotating member 10 defines a screw hole (not shown) in the bottom wall (not shown), adjacent to a second end of the first rotating member 10 opposite to the first end. The connecting member 60 is generally a lath. Two first rotating members 10 are connected with each other by the connecting member 60 , forming a U-shaped frame.
[0012] Each second rotating member 20 is a long, rectangular post. The second rotating members 20 each include two opposite sidewalls 22 . The second rotating members 20 each define an opening 24 through the sidewalls 22 . The second rotating members 20 each define a pivot hole 26 in a first end thereof, through the sidewalls 22 . Two posts 240 extend from a top wall and a bottom wall bounding each opening 24 , adjacent to a second end of each second rotating member 20 opposite to the first end. A positioning block 25 extends from a lateral sidewall bounding each opening 24 , adjacent to the second end of the second rotating members 20 and between the posts 240 .
[0013] Each carrying member 30 is a rectangular post capable of being received in the opening 24 . A top wall and a lower wall of the carrying member 30 each define a pivot hole 32 , corresponding to the posts 240 of the second rotating members 20 .
[0014] Each blocking member 50 is generally L-shaped. The blocking members 50 each include a fixing tab 52 and a blocking tab 54 perpendicularly extending from one end of the fixing tab 52 .
[0015] Each positioning member 55 is generally L-shaped. The positioning members 55 each include a positioning tab 56 and a connecting tab 57 perpendicularly extending from one end of the positioning tab 56 .
[0016] Each supporting member 70 includes a retractable shaft 71 , and an adjusting button 72 to adjust a length of the shaft 71 . A distal end of the shaft 71 forms a threaded portion (not shown). The adjusting button 72 extends through the shaft 71 , to resist against a retractable portion of the shaft 71 to position the retractable portion.
[0017] Referring to FIG. 2 , in assembly, the first rotating members 10 attaches to opposite sides of the supporting panel 40 , with the sides of the supporting panel 40 slidably received in the sliding slots 18 . The carry members 30 are received in the openings 24 of the second rotating members 20 . The posts 240 rotatably engage in the pivot holes 32 . The posts 140 rotatably engage in the pivot holes 26 , rotatably connecting the first rotating members 10 to the second rotating member 20 . The connecting tabs 57 of the positioning members 55 are inserted into the fastening holes 120 of the first rotating members 10 , to fix the positioning members 55 to the first rotating members 10 . The blocking tabs 54 of the blocking members 50 extend through two corresponding fastening holes 16 of the two first rotating members 10 , to block a bottom of the supporting panel 40 . The fixing tabs 52 of the blocking members 50 resist against the first sidewalls 14 of the first rotating members 10 . The threaded portion of the two shafts 71 engage in the screw holes of the first rotating members 10 , to fix the supporting members 70 to the first rotating members 10 .
[0018] Referring to the FIG. 3 , in use of the stand, a portable device, such as notebook computer 100 , is placed on the supporting panel 40 . The length of two supporting members 70 is adjusted via operation of the adjusting button 72 , to change the angle between the second rotating members 20 and the first rotating members 10 , to adjust an used angle of the notebook computer 100 . The supporting panel 40 slides along the sliding slots 18 , to adjust the used height of the notebook computer 100 . The blocking tabs 54 of the blocking members 50 resist against a front side of the notebook computer 100 , the positioning tabs 56 of the positioning members 55 resist against a top of the notebook computer 100 .
[0019] Referring to FIG. 4 , in another use of the stand, the two supporting members 70 are disassembled from the first rotating members 10 . The carrying members 30 rotate towards each other to align and contact with each other. The first rotating members 10 rotate to be parallel with the second rotating members 20 . The blocking tabs 54 resist against the front side of the notebook 100 , the positioning tabs 56 resist against the top of the notebook 100 . Therefore, it is very easy to carry the notebook computer 100 by carrying the carrying members 30 . In the process of carrying the carrying members 30 , the positioning blocks 25 position the carrying members 30 .
[0020] In other embodiments, two first rotating members 10 and the connecting member 60 can be integrally formed.
[0021] It is to be understood, however, that even though numerous characteristics and advantages of the present disclosure have been set forth in the foregoing description, together with details of the structure and function of the disclosure, the disclosure is illustrative only, and changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the disclosure to the full extent indicated by the broad general meaning of the terms in which the appended claims are expressed. | A stand includes a supporting panel, two first rotating members attached to opposite sides of the supporting panel, two second rotating members rotatably mounted to first ends of the first rotating members, and two supporting members mounted to second ends of the first rotating members to support the two first rotating members. An angle forms between the first and second rotating members at the first ends, because of the supporting member. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to inert gas hazard suppression assemblies used to protect areas or rooms such as computer equipment rooms from hazards, and especially fire. More particularly, the invention relates to such systems, as well as pressure modulating inert gas valves forming a part thereof, where multiple high-pressure inert gas cylinders are used, with each cylinder having a valve unit operable to deliver relatively low pressure inert gas at a generally constant pressure throughout a significant period of time during which gas is delivered, thereby providing effective hazard suppression without the need for high-pressure gas handling and distribution equipment or pressure reducing orifice plates that are typical of prior inert gas hazard suppression systems. Each valve unit includes a spring assembly biasing the unit to an open, gas-flow position as well as a gas flow modulating circuit which maintains the gas pressure around the desired output pressure over a substantial part of the gas delivery cycle.
2. Description of the Prior Art
Hazard suppression systems have long been employed for protecting rooms or areas containing valuable equipment or components, such as computer rooms. Traditionally, these systems have made use of one or more of the Halon suppressants. These Halon suppressants are ideal from a hazard suppression viewpoint, i.e., they are capable very quickly suppressing a hazard, can be stored at relatively low pressures, and the quantity of suppressant required is relatively small.
However, in recent years the adverse environmental effects of the Halon has become evident and of considerable concern. Indeed, these issues are so significant that many governmental agencies have banned any further use of Halon. In Europe for example, even existing Halon systems are being replaced by systems using other inert gases such as nitrogen, argon, carbon dioxide and mixtures thereof.
In an exemplary European fire suppression system based on the use of Halon as a suppressant agent, a vessel with a nominal capacity of 150 liters filled with liquified Halon is rated to protect a volume of approximately 17,000 cubic feet. The entire piping of a Halon system need be no more than schedule 40 pipe. Where it is desired to replace a Halon installation with an inerting gas system, or in new installations based on an inerting gas, the standards require that the sufficient inert gas be delivered to a predetermined protected area so that the inert gas occupies approximately 40% by the volume of the room. This lowers the oxygen level within the room to something on the order of 10-15%, which starves the fire of oxygen. At least 95% of the requisite amount of inert gas must be delivered to the protected room in a period of 60 seconds. At the same time, the inert gas preferably should be chosen so that people can be in the room after gas delivery for a period of as much as five minutes.
A European inert gas fire suppression system when configured to replace a previous Halon system or as a new installation having a rating, which is equivalent to the exemplary 17,000 cubic foot Halon protection system referenced above, will require 10 high-pressure inert gas vessels as a replacement for the single Halon vessel. The requirement for a far larger number of inert gas storage vessels in a gas inerting fire suppression system as compared with the storage vessel requirements of a Halon system is because each inert gas vessel must be of significantly greater wall thickness and therefore as a practical matter must be significantly smaller. For example, a typical 80 liter inert gas cylinder will have a wall thickness of about 16 millimeters, be about 25 centimeters in diameter and 190 centimeters in length. The single, in this instance, 150 liter Halon vessel of the example, will be 40 centimeters in diameter and 100 centimeters in length. It is therefore obvious that on the basis that as many as 10 times as many inerting gas vessels are required as compared with a required number of Halon vessels for a particular installation that the space requirements for inerting vessels are much greater.
Because inerting gas is stored as a gas rather than a liquid at very high pressures, e.g., 300 bar, compared with the much lower 25 bar pressure in a typical Halon storage vessel, a manifold pipe must be provided that is connected to all of the inerting gas cylinders, which is capable of withstanding simultaneous release of the high-pressure gas from the storage cylinders for direction of the gas to the piping distribution system of the fire suppression system. The manifold pipe must be at least schedule 160 piping to accommodate the high pressure. A pressure letdown orifice plate is provided at the end of the manifold, which also must be capable of withstanding the 300 bar inerting gas pressure.
Thus, in an instance where an existing Halon system is to be retrofitted using high-pressure inerting gas, not only are a significantly greater number of suppressant agent storage vessels required as explained, but in addition, there is the need for a schedule 160 manifold connected to all of the storage cylinders, and in conjunction with a high-pressure orifice plate to reduce the gas pressure to a level that can be handled by the existing schedule 40 pipe. The schedule 160 pipe needed is manifestly more expensive than schedule 40 pipe and there will be a requirement for approximately 0.3 meters of schedule 160 pipe for each inert gas vessel. Similarly, the same requirement obtained in connection with a new installation.
Accordingly, there is a real and unsatisfied need in the art for improved hazard suppression systems which can make use of relatively low pressure non-Halon inert suppression gas with existing Halon system piping (or low cost, overall low pressure piping in the case of new systems) while at the same time exhibiting the performance characteristics required for rapid hazard suppression.
SUMMARY OF THE INVENTION
The present invention overcomes the problems outlined above and provides an improved hazard suppression system capable of effectively suppressing hazards such as fire through use of relatively low pressure inert gas cylinders together with specially designed cylinder-mounted discharge valves capable of delivering the gas at generally constant pressure levels throughout a majority of the time of gas delivery. In this way, use can be made of existing piping systems designed for Halon suppressants, or in the case of new systems less expensive piping and distribution hardware may be employed.
In prior high-pressure inert gas systems employing a high-pressure letdown orifice plate, release of gas from the storage cylinders for discharge from the manifold pipe through the orifice plate resulted in very high initial gas flow rates, which declined rapidly to a very low gas flow rate. As an adjunct to the initial high discharge rate of the inerting gas into the protected area, a room vent had to be provided of sufficient area to accommodate the initial gas flow. In the present instance, moderation of the gas discharge flow rate permits provision of a vent area approaching a 30% smaller flow area.
Generally speaking, a hazard suppression system in accordance with the invention for use in suppressing a hazard (e.g., typically fire) within a room or the like, comprises a plurality of pressurized gas cylinders each holding a supply of hazard-suppressing gas, with a valve unit operably coupled with each of said cylinders. A distribution assembly is connected with each of the cylinder-mounted valve units for delivery of gas to the protected room or the like. Each of the valve units has a valve body presenting an inlet adapted for coupling with a source of pressurized gas (namely a cylinder in the case of the overall suppression system) and an outlet adapted for coupling with a restricted gas receiver (the distribution assembly in the complete system). Further, a shiftable valve member having a passageway therein is located between said inlet and outlet of the valve body and is shiftable between a closed, gas flow-blocking position and an open position permitting flow of gas from said source to said receiver.
Each of the valve units has a spring operably coupled with the shiftable valve member for biasing the member toward the open position of the valve unit. Additionally, separate first and second operating surface areas form a part of the valve member; the first area is exposed to the pressurized gas whereas the second area is exposed to the pressurized gas through the member passageway. These first and second surface areas are oriented and correlated relative to the valve body to normally maintain the member in the closed position thereof against the bias of the spring. The valve unit is designed to present a modulating gas chamber formed between at least a part of the second surface area and adjacent portions of the valve body. Moreover, a modulating gas passage is formed in the valve body and communicates the valve unit outlet and the modulating gas chamber. An actuator is operably coupled with the modulating gas passage to normally block communication between the valve unit outlet and the modulating gas chamber. ,said actuator operable upon actuation thereof to open said passage and thereby drain gas from said modulating chamber through said passage to reduce the gas pressure within the modulating gas chamber and permit movement of said member to the open position thereof under the influence of gas pressure exerted against the first surface area. A gas flow restriction is located in the passageway and is operable to substantially limit the flow rate of gas between the modulating gas chamber and the passageway. The first and second surface areas of the shiftable valve member, the modulation chamber, the modulating gas flow passage, and the spring are correlated so that gas from the source is delivered to the receiver at a generally constant pressure over a substantial part of the time gas flows from the source to the receiver. This is accomplished by recurring flow of the gas into and out of the modulation chamber through the modulating gas flow passage.
The complete hazard suppression system also normally includes a sensor assembly operable to sense a hazard within the protected room or the like and, in response thereto, to actuate each of the valve unit actuators. In the case of a fire suppression system, the sensor would normally be in the form of a smoke detector. This would be electrically coupled with a solenoid valve controlling a pilot gas source. When a fire is sensed, the solenoid valve is opened allowing flow of the pilot gas to the valve units in order to actuate the latter.
The gas pressure within the cylinders, which is stored nominally at 300 bar, is released through a respective modulating valve at a constant pressure of about 20 to 50 bar at a relatively constant flow rate. Notwithstanding this relatively low controlled release pressure and flow rate, the systems of the invention are capable of supplying adequate suppression gas to the protected area within established time constraints. This represents a significant economic advantage.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of a hazzard suppression system in accordance with the invention, shown in a configuration for protecting a computer room or the like;
FIG. 2 is a fragmentary isometric view of an inert gas cylinder equipped with a valve unit in accordance with the invention;
FIG. 3 is a top elevational view of the preferred valve unit;
FIG. 4 is a side elevation view of the preferred valve unit;
FIG. 5 is a vertical sectional view taken along line 5 — 5 of FIG. 3 and illustrating the details of construction of the preferred valve unit;
FIG. 6 is a sectional view taken along line 6 — 6 of FIG. 5 ;
FIG. 7 is a sectional view taken along line 7 — 7 of FIG. 5 ;
FIG. 8 is a sectional view taken along line 8 — 8 of FIG. 5 ;
FIG. 9 is a vertical sectional view similar to that of FIG. 5 , but depicting the valve unit in its open, discharge position;
FIG. 10 is a sectional view taken along line 10 — 10 of FIG. 9 ;
FIG. 11 is a fragmentary sectional view of a portion of the valve body forming a part of the preferred valve unit;
FIG. 12 is a pressure versus time graph illustrating the decaying pressure characteristics of a conventional, non-modulated valve unit during discharge of very high-pressure inert gas;
FIG. 13 is a pressure versus time graph illustrating a typical pressure waveform obtained using a valve unit in accordance with the invention during discharge of relatively low pressure inert gas; and
FIG. 14 is a flow diagram illustrating the operation of the preferred valve unit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning now the drawings, a hazard suppression system 20 is schematically illustrated in FIG. 1 . The system 20 is designed to protect an enclosed room 22 which may house computer equipment or other valuable components. Broadly speaking, the system 20 includes a plurality of high-pressure inert gas cylinders 24 each equipped with a valve unit 26 . Each valve unit 26 is connected via a conduit 28 to a manifold assembly 30 . As illustrated, the assembly 30 extends into room 22 and is equipped with a plurality of nozzles 32 for delivery of inert gas into the room 22 for hazard suppression purposes. The piping making up the system 30 may be conventional schedule 40 pipe as opposed to the heavy-duty schedule 160 manifold piping and pressure letdown orifice plate required of prior systems of this character. The overall system 20 further includes a hazard detector 34 which is coupled by means of an electrical cable 36 to a solenoid valve 38 . The latter is operatively connected to a small cylinder 40 normally containing pressured nitrogen or some other appropriate pilot gas. The outlet of valve 38 is in the form of a pilot line 42 which is serially connected to each of the valve units 26 . As depicted in FIG. 1 , the plural cylinders 24 may be located within an adjacent room or storage area 44 in proximity to the room 22 .
FIG. 2 illustrates a cylinder 24 , which is conventionally a heavy-walled upright metallic cylinder having an outlet neck 46 . The inert gas within the cylinder (usually nitrogen, argon, carbon dioxide and/or mixtures thereof) is at relatively high-pressure on the order of 150-300 bar, and preferably on the order of 300 bar. The valve unit 26 is threaded into neck 46 (see FIG. 5 ) and includes an upright valve body 48 supporting an actuator 50 , pressure gauge 52 and rupture disc assembly 54 ; additionally, the valve unit includes an internal shiftable piston-type sealing member 56 ( FIG. 5 ) As explained more fully hereafter, the valve unit 26 is designed so that inert gas from cylinder 24 is delivered to manifold assembly 30 at a generally constant pressure lower than the pressure within the associated cylinder over a substantial part of the time that gas flows from the cylinder.
In more detail, the valve body 48 is of tubular design and has an externally threaded tubular inlet port 58 which is threadably received by neck 46 , a discharge port 60 adapted for coupling to a conduit 26 , a vent port 61 adjacent port 60 , and a stepped through bore 62 communicating with the ports 58 , 60 and 61 and an uppermost spring chamber 64 . The bore 62 is configured to present (see FIG. 5 ), from bottom to top, an annular sealing ridge 66 , radially enlarged region 68 , annular shoulder 70 , annular relieved zone, shoulder 74 , and threading 76 leading to chamber 64 .
The body 48 also has an extension 78 presenting a bore 80 designed to receive the inner end of actuator 50 . For this purpose, an O-ring 82 is provided within bore 80 as well as bolt connectors 84 for retaining the actuator 50 therein. A pair of passageways 86 and 88 communicate with bore 80 as best seen in FIG. 6 . The passageway 86 extends from bore 80 into communication with discharge port 60 (FIG. 11 ). Bore 88 is dead-end bore but communicates with a passage 90 extending to threaded opening 92 which receives a plug 93 . A conventional Shrader valve 94 forming a part of the overall actuator 50 is seated within passageway and is normal blocking relation to the passage 90 . The valve 94 includes an uppermost actuator pin 96 . Another passage 95 is provided to extend from opening 92 to relieved zone 72 .
Valve body 48 also includes a threaded bore 98 adapted to receive the connection end of gauge 52 . The bore 98 houses a Shrader valve 99 which is in an always-open condition when gauge 52 is installed. The bore 98 also communicates with another threaded bore 100 which receives rupture disc assembly 54 . A sensing bore 102 is provided within the body 48 and extends from bore 98 to inlet port 58 , thereby causing pressure within cylinder 24 to communicate with gauge 52 and also bore 100 .
The assembly 54 comprises a threaded, somewhat T-shaped member 104 with a central relief passage 105 positioned within bore 100 . The inboard end of member 100 includes s conventional dome-shaped rupture disc 106 in normal blocking relationship to relief passage 105 . It will be appreciated, however, that if the cylinder 24 experiences an overpressure condition, such is communicated through sensing bore 102 and serves to rupture disk 106 ; this immediately vents the cylinder through the passage 105 .
The actuator 50 includes a main actuator body 108 , an actuator cap 110 , and an internal shiftable piston 112 . The body 108 has a lowermost necked-down portion 114 seated within bore 80 , and a central opening 116 with an inboard, radially expanded region 117 . A vent passage 118 communicates with the opening 116 as shown. The upper end of the body 108 is internally threaded as at 120 . The cap 110 is threaded into the upper end of body 108 and has a piston chamber 122 as well as a cross passage 124 ; the latter receives the pilot line 42 as seen in FIG. 6 . Piston 112 is generally T-shaped in cross-section with a latterly extending shank 126 and outer piston head 128 . Shank 126 carries a sealing O-ring 130 and a position retainer 132 , the latter extending into region 117 so as to limit the range of motion of the piston 112 . The head 128 also carries a sealing O-ring 134 . The inboard end of shank 126 is configured to engage the upper end of Shrader valve actuating pin 96 as will be explained.
The sealing member 56 is positioned within valve body 48 and is selectively shiftable therein during operation of valve unit 26 . Referring to FIG. 5 , the sealing member 56 includes four primary components extending from bottom to top, namely a piston seal holder 136 , bottom insert 138 , inner body section 140 and upper, outer body section 142 .
The piston seal holder 136 includes a lower section 144 in facing relationship to bore 62 as well as an annular rib 146 . A sealing ring 148 is disposed between section 144 and rib 146 . A series of openings 149 are provided through holder 136 and merge to form a through passage 149 a . The bottom insert 138 is in the form of annular body presenting an upper radially outwardly extending flange 150 which abuts shoulder 70 of valve body 48 . The insert carries a peripheral sealing ring 152 . The inner body section 140 is threadably coupled to the upwardly projecting section of holder 136 and supports a series of vertically spaced apart sealing rings 152 - 158 . Additionally, the section 140 has a pair of vertically spaced flanged segments 160 , 161 and an upper end provided with an internally threaded bore 162 . The section 140 has a central passageway 164 which communicates with passage 149 a. A port 166 extends from passageway 164 to a point just above flange segment 160 , and another upper port 168 extends from passageway 164 to a point just about flange segment 161 . A grub screw 169 is positioned within port 168 and serves to permit slow passage of gas therethrough from passageway 164 , while substantially blocking reverse flow into the passageway 164 .
Outer body section 142 is of tubular construction and is threaded into valve body threading 76 so as to remain stationary. The section 142 has a central through bore 165 receiving inner body section 140 and external sealing rings 170 , 172 . It will also be observed that the section 142 presents a pair of shoulders 174 , 176 , and has a lateral passageway 178 which communicates with relieved zone 72 .
The complementary design of the inner and outer body sections 140 , 142 defines a pair of annular chambers which are important for the operation of valve unit 24 . Thus, an equalization chamber 180 is provided between the upper face of flange segment 160 and shoulder 174 , and a modulation chamber 182 is defined between the upper face of flange segment 161 and shoulder 176 .
The shiftable segments of sealing member 56 (i.e., piston seal holder 136 and interconnected inner body section 140 ) are supported by means of a spring assembly 184 located within spring chamber 64 . In particular, a wave spring 186 is seated within the chamber and has at the upper end thereof an annular retainer disk 188 , the latter carrying a peripheral sealing ring 190 . A bolt 192 , seated on washer 194 , extends downwardly through disk 188 and is threadably received within bore 162 . It will be appreciated that spring assembly 184 serves to urge or bias holder 136 and section 140 upwardly as viewed in FIG. 5 , that is towards the valve open position of the unit 26 .
Operation
It will be understood that valve unit 26 is normally in the static standby valve closed position thereof depicted in FIGS. 5-8 . In this condition, the sealing member 56 is shifted downwardly as viewed in FIG. 5 so that sealing ring 148 comes into sealing engagement with ridge 66 . This is accomplished by virtue of the correlation between the first operating surface area S 1 presented by seal holder 136 , the second operating surface area S 2 presented by the sum of the equalization chamber effective surface area S 2 E (see FIG. 8 , where S 2 E is the exposed portion of the face of flange 160 ) and the modulation chamber effective surface area S 2 M (see FIG. 7 , where S 2 M is the exposed face of flange 161 ), and the force exerted by spring assembly 184 . That is, in the closed, static position of the valve unit 26 , a valve opening force is exerted against sealing member 56 in the form of pressure from the cylinder 24 is exerted against operating surface area S 1 through inlet port 58 , and the effect of spring assembly 184 . However, this opening force is counterbalanced and exceeded by a valve closing force exerted against operating surface S 2 (the sum of S 2 E and S 2 M), by virtue of passage of pressurized gas through the valve member via passage 149 a, passageway 164 and ports 166 , 168 to the equalization and modulation chambers 180 , 182 , respectively. It will be understood in this regard the grub screw 169 within port 168 permits slow passage of gas through port 168 while substantially preventing rapid reverse flow of gas from the modulation chamber 182 back into passageway 164 .
In the valve close position, the actuator 50 ( FIG. 6 ) is in its standby condition, that is, the piston 112 is elevated and Shrader valve 94 is in a flow-blocking relation relative to passage 90 .
The operation of system 22 during a hazard suppression will now be described. In this discussion, reference will be made to the specific components of the system, and also to FIG. 14 , which is a flow diagram of the system operation intended to facilitate an understanding of the invention.
In the event of a hazard condition such as a fire in room 22 , the sensor 34 (e.g., a smoke detector) operates (Step 196 ) and sends an opening signal to solenoid valve 38 (Step 198 ). Compressed gas (usually nitrogen) then passes through pilot line 42 (Step 200 ) so as to actuate each of the valve units 26 respectively coupled to the corresponding cylinders 24 (Step 202 ). Turning to FIG. 10 , upon introduction of pilot gas through line 32 , the piston 112 is shifted downwardly so that the inboard butt end thereof engages and shifts actuating pin 96 of Shrader valve 94 . As a consequence, the passage 90 is opened. When this occurs, gas flows from modulating chamber 182 into and through a modulating passage made up of annular relieved zone 72 , passage 95 , opening 92 , and passage 90 to discharge port 60 (Step 204 ). At this point, the valve opening force exerted by gas pressure against surface area S 1 and the spring assembly 184 is sufficient to move the sealing member 56 to the valve open position depicted in FIGS. 9-10 . Therefore, gas from the cylinder 24 passes from inlet port 58 through discharge port 60 , conduit 28 , manifold 30 and nozzles 32 (Step 206 ).
As indicated previously, a problem with prior discharge valves in the context of high-pressure hazard suppression systems is the tendency of such valves to exhibit a pronounced pressure decay pattern as illustrated in FIG. 12 . This characteristic decay pattern results in an initial “burst” of inert gas delivery owing to the high pressure of the gas (on the order of 200 bar or around 3000 psi) with exponential decline in pressure during the course of remaining gas discharge. While these prior systems are capable of delivering adequate volumes of inert gas within the hazard suppression time frame, use of the high-pressure gas cylinders entails considerable expense in terms of piping and related gas handling and distribution hardware.
This problem is overcome by the present invention which exhibits the general pressure wave form of FIG. 13 , i.e., gas is delivered at a generally constant pressure lower than the pressure of gas within the cylinder 24 , but over a substantial period (at least about 50%, more preferably at least about 75%) of the time during which gas is discharged by the valve unit 26 . This type of pressure waveform enables release of gas at a much lower inert gas pressure, on the order of from about 10 to about 100 bar, or from around 150 to 1500 psi, and as a consequence use can be made of low-cost gas handling and distribution equipment, often the existing equipment in systems heretofore employing Halon as suppressants. In a preferred system, the release pressure is about 50 bar.
Specifically, as gas from the cylinders 24 is initially delivered to the discharge port 60 , a back pressure is generated within the valve unit which causes gas from the cylinder to travel back through the above-described modulating passage comprising passage 90 , opening 92 , passage 95 , relieved zone 72 and into modulating chamber 182 . This serves to move the sealing member 56 back toward the closed position of the valve unit. This in turn creates a restriction to gas flow from the cylinder 24 , which continues until the pressure within discharge port 60 is reduced. Thereupon, gas from the modulation chamber 182 flows along the described modulating passage to the discharge port. This back and forth gas flow pattern along the modulating passage recurs throughout a majority of the time gas flows from the cylinders 24 . The result is a pressure modulation of gas flow from the cylinder 24 to create the generally horizontal portion of the FIG. 13 wave form. Towards the end of discharge of gas from the cylinder 24 , the spring force exerted from assembly 184 becomes greater than the sum of the forces exerted in the equalization and modulation chambers, so that the spring becomes the sole operating element in the valve unit and the latter remains full open until gas discharges completely. It will be understood in this respect that while FIG. 13 depicts an essentially straight line, constant pressure condition with a rapid tail-off at the end of gas discharge, in practice the wave form would exhibit fluctuations generally around the straight line portion of the straight line.
The modulation operation of unit 26 is illustrated in FIG. 14 within the dotted line box 208 , in the form of a logic diagram. Thus, in Step 210 , if the cylinder force (i.e., the force exerted by the cylinder gas against surface area S 1 ) plus the spring force (i.e., the force exerted by spring assembly 184 ) equals the counterforce exerted against second surface area S 2 (the sum of the S 2 E and S 2 M surface areas) in the equalization and modulation chambers 180 , 182 , the system is balanced, Step 212 . If the cylinder force plus the spring assembly force is less than the counterforce (Step 214 ), the sealing member is moved toward the valve closed position thereof (Step 216 ), to restrict the flow of gas from the cylinder. If the cylinder force plus the spring force is greater than the counterforce (Step 218 ), then the sealing member is moved toward the valve open position (Step 220 ). This modulation continues by the effective determination of the cylinder force, spring force and counterforce (Step 222 ) until, in Step 218 , the spring force is greater than the counterforce exerted through the equalization and modulation chambers (Step 224 ). At this point, the spring assembly fully extends (Step 226 ), which is generally corresponds to the downwardly directed “knee” portion of the FIG. 13 wave form. This completes the system operation Step 228 . | A relatively low pressure inert gas hazard suppression system ( 20 ) is provided which is designed to protect a room ( 22 ) or the like from the effects of fire or other hazard. The system ( 20 ) includes a plurality of pressurized inert gas cylinders ( 24 ) each equipped with a valve unit ( 26 ); each valve unit ( 26 ) is in turn coupled via a conduit ( 28 ) to a delivery manifold ( 30 ). The respective valve units ( 26 ) are operable to deliver gas from the cylinders ( 24 ) at a generally constant pressure (usually around 10-100 bar) throughout a substantial portion of the time of gas delivery, to thereby provide effective hazard suppression without the need for expensive high-pressure gas handling and distribution hardware and a reduction in room venting area due to lower room over-pressurization. Each valve unit ( 26 ) has a valve body ( 48 ) and a shiftable piston-type sealing member ( 56 ). Gas pressure from the cylinder ( 24 ) and a spring assembly ( 184 ) biases the member 56 to the valve open position, this being counterbalanced by gas pressure within equalization and modulation chambers ( 180, 182 ) provided in the valve unit ( 26 ). When a hazard is detected, the valve units ( 26 ) are actuated by draining of gas from the modulation chambers ( 182 ), allowing gas flow from the cylinders ( 24 ). As gas discharge proceeds, gas flows into and out of the modulation chambers ( 182 ) so as to achieve the desired generally constant pressure gas output. Near the end of gas discharge, the spring assembly ( 184 ) becomes predominant and holds the valve unit ( 26 ) open until all gas is discharged. | 5 |
This application is a divisional of Ser. No. 09/339,710 now U.S. Pat. No. 6,247,045, filed Jun. 24, 1999, which is herein incorporated by reference.
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates to an improved data processing system and in particular to a method for sending messages. Still more particularly, the present invention relates to a method and apparatus for sending private messages to selected recipients from a single message.
2. Description of Related Art
The Internet, also referred to as an “internetwork”, is a set of computer networks, possibly dissimilar, joined together by means of gateways that handle data transfer and the conversion of messages from the sending network to the protocols used by the receiving network (with packets if necessary). When capitalized, the term “Internet” refers to the collection of networks and gateways that use the TCP/IP suite of protocols.
The Internet has become a cultural fixture as a source of information, entertainment, and communications. Many businesses are creating Internet sites as an integral part of their marketing efforts, informing consumers of the products or services offered by the business or providing other information seeking to engender brand loyalty. Many federal, state, and local government agencies are also employing Internet sites for informational purposes, particularly agencies which must interact with virtually all segments of society such as the Internal Revenue Service and secretaries of state. Providing informational guides and/or searchable databases of online public records may reduce operating costs. Further, the Internet is becoming increasingly popular as a medium for commercial transactions.
In addition to being a source of information, the Internet also provides a communications medium. The Internet has become the most popular computer network used by consumers and businesses to send and receive electronic mail, also referred to as “e-mail”. The Internet allows users to readily send and receive e-mail to and from computers around the world. Each user typically has a unique Internet e-mail address (e.g., steve@ibm.com). A user with an e-mail account and a computer capable of connecting to the Internet can easily send and receive e-mail over the network.
E-mail allows a person to quickly and easily send textual messages and other information, such as, for example, pictures, sound recordings, and formatted documents electronically to other e-mail users anywhere in the world. An e-mail user will typically create a message using an e-mail program running on a computer connected to a computer network through a modem. The message will include an e-mail “address” for the intended recipient. When the user has finished entering the message, the user may “send” the message to the intended recipient. The e-mail program then electronically transmits the message over the computer network. The recipient, using an e-mail program running on the recipient's computer, can then “receive” the message.
A user may send messages to multiple recipients through various fields, such as “TO:” and “CC:”, in an e-mail program. When composing a message for a large group or recipients, the user may need to send a private message to a recipient within the group of recipients. In such an instance, the user generates a message for recipients within the group other than those that are to receive the private message. Then, the user generates another message for the recipient that is to receive a private message. If a second recipient within the group of recipients is to receive another private message, the user must generate yet another message. Such a process can be tedious and time consuming depending on the number of recipients that are to receive private messages.
Therefore, it would be advantageous to have an improved method and apparatus for sending private messages in an e-mail message.
SUMMARY OF THE INVENTION
The present invention provides a method, system, and program for use within a data processing system for sending messages. A plurality of recipients is identified for an electronic message. A number of different sections are designated within the electronic message for separate receipt by each of a number of recipients within the plurality of recipients. Responsive to an indication to send the electronic message, an electronic message is automatically generated for each of the number of recipients, wherein the message of a given recipient within the number of recipients excludes sections within the number of sections designated for other recipients within the number of recipients, i.e., involves only those sections within the number of sections identified for the given recipients.
BRIEF DESCRIPTION OF THE DRAWINGS
The novel features believed characteristic of the invention are set forth in the appended claims. The invention itself, however, as well as a preferred mode of use, further objectives and advantages thereof, will best be understood by reference to the following detailed description of an illustrative embodiment when read in conjunction with the accompanying drawings, wherein:
FIG. 1 depicts a pictorial representation of a distributed data processing system in which the present invention may be implemented;
FIG. 2 is a block diagram depicting a data processing system that may be implemented as a server in accordance with a preferred embodiment of the present invention;
FIG. 3 is a block diagram illustrating a data processing system in which the present invention may be implemented;
FIG. 4 is a block diagram of an e-mail program depicted in accordance with a preferred embodiment of the present invention;
FIG. 5 is a diagram illustrating functions for processing e-mail messages depicted in accordance with a preferred embodiment of the present invention;
FIGS. 6A and 6B are examples of private messages processed depicted in accordance with a preferred embodiment of the present invention;
FIGS. 7A and 7B are additional examples of private message processing depicted in accordance with a preferred embodiment of the present invention;
FIGS. 8A-8D are examples of messages depicted in accordance with a preferred embodiment of the present invention;
FIG. 9 is a flowchart of a process for editing and designating objects depicted in accordance with a preferred embodiment of the present invention; and
FIG. 10 is a flowchart of a process used to generate messages for recipients from a single message depicted in accordance with a preferred embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to the figures, FIG. 1 depicts a pictorial representation of a distributed data processing system in which the present invention may be implemented. Distributed data processing system 100 is a network of computers in which the present invention may be implemented. Distributed data processing system 100 contains a network 102 , which is the medium used to provide communications links between various devices and computers connected together within distributed data processing system 100 . Network 102 may include permanent connections, such as wire or fiber optic cables, or temporary connections made through telephone connections.
In the depicted example, a server 104 is connected to network 102 along with storage unit 106 . In addition, clients 108 , 110 , and 112 also are connected to a network 102 . These clients 108 , 110 , and 112 may be, for example, personal computers or network computers. For purposes of this application, a network computer is any computer, coupled to a network, which receives a program or other application from another computer coupled to the network. In the depicted example, server 104 provides data, such as boot files, operating system images, and applications to clients 108 - 112 . Clients 108 , 110 , and 112 are clients to server 104 . In the depicted examples, server 104 may contain an electronic mail system from which clients 108 , 110 , and 112 send and receive e-mail messages through e-mail programs or applications located on the clients. Distributed data processing system 100 may include additional servers, clients, and other devices not shown. For example, messages may be sent and received between server 104 and other servers (not shown) to distribute and receive messages from other clients (not shown).
In the depicted example, distributed data processing system 100 is the Internet with network 102 representing a worldwide collection of networks and gateways that use the TCP/IP suite of protocols to communicate with one another. At the heart of the Internet is a backbone of high-speed data communication lines between major nodes or host computers, consisting of thousands of commercial, government, educational and other computer systems that route data and messages. Of course, distributed data processing system 100 also may be implemented as a number of different types of networks, such as for example, an intranet, a local area network (LAN), or a wide area network (WAN). FIG. 1 is intended as an example, and not as an architectural limitation for the present invention.
Referring to FIG. 2, a block diagram depicts a data processing system that may be implemented as a server, such as server 104 in FIG. 1, in accordance with a preferred embodiment of the present invention. In the depicted examples, data processing system 200 is used as an electronic mail message server providing service to a number of clients. Data processing system 200 may be a symmetric multiprocessor (SMP) system including a plurality of processors 202 and 204 connected to system bus 206 . Alternatively, a single processor system may be employed. Also connected to system bus 206 is memory controller/cache 208 , which provides an interface to local memory 209 . I/O bus bridge 210 is connected to system bus 206 and provides an interface to I/O bus 212 . Memory controller/cache 208 and I/O bus bridge 210 may be integrated as depicted.
Peripheral component interconnect (PCI) bus bridge 214 connected to I/O bus 212 provides an interface to PCI local bus 216 . A number of modems may be connected to PCI bus 216 . Typical PCI bus implementations will support four PCI expansion slots or add-in connectors. Communications links to network computers 108 - 112 in FIG. 1 may be provided through modem 218 and network adapter 220 connected to PCI local bus 216 through add-in boards.
Additional PCI bus bridges 222 and 224 provide interfaces for additional PCI buses 226 and 228 , from which additional modems or network adapters may be supported. In this manner, server 200 allows connections to multiple network computers. A memory-mapped graphics adapter 230 and hard disk 232 may also be connected to I/O bus 212 as depicted, either directly or indirectly.
Those of ordinary skill in the art will appreciate that the hardware depicted in FIG. 2 may vary. For example, other peripheral devices, such as optical disk drives and the like, also may be used in addition to or in place of the hardware depicted. The depicted example is not meant to imply architectural limitations with respect to the present invention.
The data processing system depicted in FIG. 2 may be, for example, an IBM RISC/System 6000 system, a product of International Business Machines Corporation in Armonk, N.Y., running the Advanced Interactive Executive (AIX) operating system.
With reference now to FIG. 3, a block diagram illustrates a data processing system in which the present invention may be implemented. Data processing system 300 is an example of a client computer. In these examples, data processing system 300 may include any mail program or application for generating, sending, and receiving messages. Data processing system 300 employs a peripheral component interconnect (PCI) local bus architecture. Although the depicted example employs a PCI bus, other bus architectures such as Micro Channel and ISA may be used. Processor 302 and main memory 304 are connected to PCI local bus 306 through PCI bridge 308 . PCI bridge 308 also may include an integrated memory controller and cache memory for processor 302 . Additional connections to PCI local bus 306 may be made through direct component interconnection or through add-in boards. In the depicted example, local area network (LAN) adapter 310 , SCSI host bus adapter 312 , and expansion bus interface 314 are connected to PCI local bus 306 by direct component connection. In contrast, audio adapter 316 , graphics adapter 318 , and audio/video adapter 319 are connected to PCI local bus 306 by add-in boards inserted into expansion slots. Expansion bus interface 314 provides a connection for a keyboard and mouse adapter 320 , modem 322 , and additional memory 324 . SCSI host bus adapter 312 provides a connection for hard disk drive 326 , tape drive 328 , and CD-ROM drive 330 . Typical PCI local bus implementations will support three or four PCI expansion slots or add-in connectors.
An operating system runs on processor 302 and is used to coordinate and provide control of various components within data processing system 300 in FIG. 3 . The operating system may be a commercially available operating system such as OS/2, which is available from International Business Machines Corporation. “OS/2” is a trademark of International Business Machines Corporation. An object oriented programming system such as Java may run in conjunction with the operating system and provides calls to the operating system from Java programs or applications executing on data processing system 300 . “Java” is a trademark of Sun Microsystems, Inc. Instructions for the operating system, the object-oriented operating system, and applications or programs are located on storage devices, such as hard disk drive 326 , and may be loaded into main memory 304 for execution by processor 302 .
Those of ordinary skill in the art will appreciate that the hardware in FIG. 3 may vary depending on the implementation. Other internal hardware or peripheral devices, such as flash ROM (or equivalent nonvolatile memory) or optical disk drives and the like, may be used in addition to or in place of the hardware depicted in FIG. 3 . Also, the processes of the present invention may be applied to a multiprocessor data processing system.
For example, data processing system 300 , if optionally configured as a network computer, may not include SCSI host bus adapter 312 , hard disk drive 326 , tape drive 328 , and CD-ROM 330 , as noted by dotted line 332 in, FIG. 3 denoting optional inclusion. In that case, the computer, to be properly called a client computer, must include some type of network communication interface, such as LAN adapter 310 , modem 322 , or the like. As another example, data processing system 300 may be a stand-alone system configured to be bootable without relying on some type of network communication interface, whether or not data processing system 300 comprises some type of network communication interface. As a further example, data processing system 300 may be a Personal Digital Assistant (PDA) device which is configured with ROM and/or flash ROM in order to provide non-volatile memory for storing operating system files and/or user-generated data.
The depicted example in FIG. 3 and above-described examples are not meant to imply architectural limitations.
The present invention provides a method, apparatus, and instructions for customizing and addressing multiple messages within a single message editing session. At any time while composing a message, a user may address the message by entering individual recipients, or address list names in the message header using the message editor. The user may define a conditionally addressable message object through a number of mechanisms, such as, for example, setting color, font size, or font style, or any combination thereof. The mechanism to define a message object is called an object style. The depicted examples are illustrated using color as the object style. In the case in which color is used, each particular color may be associated with a particular address that is to receive the content marked with the color. The match between address color and message object color is used to determine which recipients receive which message objects. In the depicted example, uncolored text (black), hereafter referred to as base message text, is sent to all recipients by default.
Colored text in drawings, tables, images, and container-based documents are unaffected by the conditional message object selection. If color text has no effect, an overall style may be set to select drawings, tables, images, and container based documents to designate the documents. Content other than text also may be marked for sending to particular recipients. For example, attachments for documents or images and images within the message also may be selected for sending to particular recipients by marking the attachments or images with a color associated with the intended recipients.
To address or send a portion of a message, also referred to as a “message object”, to a particular set of recipients, the user changes the color, font size, or style of these recipient names in the address fields of the message header to match message object color, font size, or style. In addition, any predefined address list may be opened via the distribution list expand command, such as distribution list expand command 504 in FIG. 5, to individually set the object style for individual members of the address list. The list may be presented, for example, via a pop-menu. Subsequent to the execution of the command, the command sets the address list object style to the object style of the last member of the address list that was changed. This change indicates that at least one address within the address list is targeted for a private message.
When the mail message is sent, different messages are sent to recipients with differently colored addresses. The recipients only see the base message text plus any message objects with the same colors as their addresses. Thus, a blue recipient receives the black base message text, plus any blue message objects, while a recipient whose name appears only in black in the address list receives only the base (black text) message. In the depicted examples, a recipient whose name appears in a black, bold font will receive the base text and all message objects.
When a mail message is received, all recipients in the To: and CC: list are shown, in the original colors selected. Recipients in the BCC: list are not shown, as is customary. Base text and conditionally addressed message object appears in color in received messages. Private message objects not addressed to the receiver are not included in the message at all, and as a result can never be viewed by someone to whom the message was not sent.
As a visual convenience, either sender or receiver may temporarily view message objects all in base text format (Arial black normal, by default) for ease of reading or turning colored message object on and off at will. The same function works for other object styles. For example, if message objects are in italics, then this command removes italics everywhere, replacing it with base text format. In addition either the sender or receiver may temporarily view the base and message objects for any addressed color by simply selecting an option on a menu. Any sender or resender may remove all message object definitions for resending, or may forward or edit message object color. The default should be to leave message objects colored. As mentioned above, other object styles other than color may be used. For example, font type or font size may be used. Also, a combination of color and font could be the object style.
With reference now to FIG. 4, a block diagram of an e-mail program is depicted in accordance with a preferred embodiment of the present invention. E-mail program 400 in this example includes a message processing unit 402 which processes messages, such as message 404 , created and received by the user. Message processing unit 402 may be implemented by using currently available mail systems, such as Lotus Notes or CC Mail, which are available from Lotus Development Corporation. If message 404 is a message received by message processing unit 402 , the message may be stored in storage 406 .
Mail program 400 also includes mail displayer 408 , which is a graphical user interface (GUI) that is used to display message 404 . If the user edits or generates a message, these functions may be accomplished through mail editor 410 . Further, mail program 400 includes a conditional message processing program (CMPP) 412 , which includes the processes of the present invention used to generate content that is sent only to a selected recipient.
Using mail editor 410 , a user composes a message using styled addresses and styled text in the body of the message. The object style may be any type of graphical indication, such as, for example, color, font type, or font size. One style is reserved (black, bold) to designate any address which should receive all message objects unconditionally. Mail editor 410 may be any editor, which allows CMPP 412 to read the style of each object. In the depicted examples, an object in a message, also referred to as a “message object”, includes, for example, a paragraph, a heading, a drawing, a table, an image, or a container.
When the sender selects send or forward, CMPP 412 will read all recipient lists, such as, for example, TO:, CC:, or BCC:. CMPP 412 determines the number of unique recipient styles (i.e., fonts or colors) and creates outgoing message buffers 414 - 418 in memory or storage 406 . An outgoing message buffer is created for each recipient style and is used to store content for a message for the particular recipient. CMPP 412 assigns each unique recipient style to a single buffer. CMPP 412 also makes a list of all recipients listed with that unique style and stores the list in an address list, such as address list 420 in outgoing message buffer 418 . This address list 420 is used as the recipient list for outgoing message buffer 418 . The styles, TO:, CC:, or BCC: properties of the recipient are preserved in the message header in unique style field 422 in outgoing message buffer 418 .
CMPP 412 then reads the message from top to bottom, obtaining the type and style of each message object. If a message object has been marked as a global object, the message object is simply copied to all buffers for all recipients. Otherwise the object style of the object is read. If the object style of the object does not match any unique address style, the object is simply copied to all message buffers. If the style of the object matches a unique address style, then that object is copied to the buffer tagged with that style, preserving the object color, font, and style properties. When all message objects in the original message have been processed, CMPP 412 sends the content of each buffer as a separately addressed message, using message processing unit 402 . In the depicted example the status of each mail message is processed by the message processing unit 402 , not CMPP 412 . The original message may be stored in storage 406 for review by the user.
With reference now to FIG. 5, a diagram illustrating functions for processing e-mail messages is depicted in accordance with a preferred embodiment of the present invention. Table 500 illustrates various commands that may be employed by a user creating or editing a message. The commands illustrated in table 500 may be presented to a user in a number of ways. The commands may be accessed through a pull down menu or as a pop-up menu. Further, selected keyboard strokes or mouse buttons may be used to invoke different commands.
Recipient style 502 is a command used to set the style color, font, and font style of each recipient. When processed by a CMPP, such as CMPP 412 in FIG. 4 the text in fields TO:, CC:, or BCC: should have an object style set for each recipient to receive the selected text. This style is read by the CMPP at transmit time. Distribution list expand 504 is an option used to support conditional message object. If included, this command expands the distribution list into individual recipients, so that their conditional object styles can be set.
Color text 506 is a command used to set the style of message body text. It has the same requirements as recipient style above. Preview option in base text format 508 is a command that displays conditional text in black, normal type. Similar preview options may be used for other object styles. Preview option message object select 510 is a command to allow the user to preview a message for a single addressee. This option displays the base black text, plus any one style color, font, style for the addressee. This option simply redisplays the text, overriding any colors, other than the color, font, or style for the addressee, in the recipient box with black in the text. Included drawings, images, tables, and container-based objects are not affected by this command.
Toggle conditional message object 512 is a command that turns message object processing off (default) or on for messages. Usually a forwarded or reply-all message would include all message objects in original styles. However, a user may want to edit and forward a message with message object processing turned on. This command will result in recording the message object processing state off default, or on, for use by the CMPP. If message object processing is off, the message is sent without message object processing of any kind, and all recipients and message styles remain the same. If it is turned on, then the message object styles can be edited, and subsequent message object processing may generate multiple message texts, as usual.
Ignore object as message object 514 is a setup option used to determine which paragraph and object styles will not be processed as message objects. Normally, this option is set to include drawings, tables, images and containers. The list of ignored objects is simply recorded and made available to the conditional message processing program. The default should include common object names for drawings, tables, images and containers which contain objects which cannot be handled by the CMPP.
The create matching message object command 516 may be selected after highlighting the text. Double clicking the addressee changes the properties of the message object to match the addressee.
With reference now to FIGS. 6A and 6B, examples of private messages processed are depicted in accordance with a preferred embodiment of the present invention. The message includes a base or default color (black) that will be included to any recipient of the message. Portions of the message in other colors will only be sent to recipients associated or designated by the color.
In FIG. 6A, message 600 is a message originated by a user, Julie Key, sent to a recipient, Vicki Wolf. Message 600 includes a message object 602 which is a message object with distribution instructions. In this example, message object 602 is displayed in red. In FIG. 6B message 604 is a forwarded message containing message 600 with message object 602 being excluded. When Vicki Wolf forwards the message, none of the recipients have been designated with the color red to identify the recipients as ones to receive message object 602 .
Turning next to FIGS. 7A and 7B, another example of private message processing is depicted in accordance with a preferred embodiment of the present invention. In this example, user Julie Key composes a message for a staff distribution list with a copy to Vicki Wolf. Message 700 in FIG. 7A illustrates the message generated by the user and the message that would be viewed by Vicki Wolf. In this example, message object 702 is displayed in red. This message object is a private message intended only for Vicki Wolf and not to other recipients. In FIG. 7B, message 704 is an example of the message that would be received by other recipients. As can be seen, message object 702 is missing from message 704 .
With reference to FIGS. 8A-8D, examples of messages are depicted in accordance with a preferred embodiment of the present invention. In this example, the message is composed in a base or default color, such as black. All recipients will receive the part of the message that is in the base or default color. Changing the color in the message from the base or default color to another color will result in the text containing the changed color being sent to a recipient or recipients associated with that color.
In FIG. 8A, message 800 is a message composed by user Julie Key in which the base text message is directed towards developers. Different message objects are directed towards recipients Vance Worthingly, Douglas Buster, and Mike Foster. Message object 802 in this example is in blue and designated for Vance Worthingly. Message object 804 is displayed in red and is designated for Douglas Buster and Mike Foster. Further, on this example, message object 806 is displayed in bold and designated for the sender Julie Key as placed in the BCC field 808 . All of the recipients will receive the base message, but only the designated recipients will receive text objects that have been designated for them.
In FIG. 8B, message 810 is the message received by developers. The developers only receive the base message and none of the message objects. In FIG. 8C, message 812 is the message received by Vance Worthingly and includes message object 806 from message 800 composed by Julie Key. In FIG. 8D, Douglas Buster and Mike Foster both receive message 814 , which includes message object 804 . These two recipients, however, do not receive the other message objects because they have been designated for other recipients.
With reference now to FIG. 9, a flowchart of a process for editing and designating objects is depicted in accordance with a preferred embodiment of the present invention. The processes in FIG. 9 may be implemented using a text editor. The process begins by receiving user input (step 900 ). This user input may take various forms including, for example, text or selection of text for an object. A determination is made as to whether an object is to be created (step 902 ). If the determination is yes, the object is placed in a message and displayed (step 904 ) with the process returning to step 900 . Otherwise, a determination is made as to whether the user input is a designation of a message object (step 906 ). This designation may be, for example, a group of text, an image, or an attachment. In the depicted examples, the designation is made by changing the color of the message object from the base or default color to another color.
If the user has designated a message object, the message object is displayed (step . 908 ) with the process then returning to step 900 . Otherwise, a determination is made as to whether the user input is to send the message (step 910 ). If the user input is to send the message, the message is sent to the CMPP (step 912 ) with the process terminating thereafter. Otherwise, the process returns to step 900 .
With reference now to FIG. 10, a flowchart of the CMPP process used to generate messages for recipients from a single message is depicted in accordance with a preferred embodiment of the present invention. The process in FIG. 10 is initiated when the user has completed composing or editing a message and has decided to send the message. The process begins by identifying recipients (step 1000 ). Thereafter, styles are identified (step 1002 ). This step may be accomplished in a number of ways. For example, the recipient fields may be parsed to determine whether any of the recipients have been designated through a change in color from a base or default color. The default or base style is always present and additional styles may be present depending on designations made by the user. Alternatively, a list of recipients may be checked to determine if any of the recipients are unique recipients associated with a style that are to receive designated portions of the message.
Thereafter, an outgoing message buffer is created for each style (step 1004 ). Each recipient for a message style is stored within a list in the outgoing message buffer created for the style (step 1006 ). The identification of the style also is stored within the outgoing message buffer for the style. The message buffers are used to create a message for each unique addressee object style. These buffers also include a single buffer for a default style for recipients that will only receive the base message, identified by the base or default color.
A variable N is set equal to the number of unique styles identified (step 1008 ). Thereafter, the message is parsed for a message object to process (step 1010 ). A determination is then made as to whether an unprocessed message object is present (step 1012 ). If an unprocessed message object is present for processing, an index i is set equal to zero (step 1014 ). This index i is used as an index to identify styles for processing. The unprocessed message object is selected for processing (step 1016 ). Then, style i is compared to the style of the message object (step 1018 ). A determination is then made as to whether a match between style i and the message object is present (step 1020 ). If a match is present, the message object is copied to the buffer for style i (step 1002 ) with the process then returning to step 1012 .
If a match is not present, i is incremented by one (step 1024 ). A determination is then made as to whether i is equal to N (step 1026 ). If i is not equal to N, the process returns to step 1018 . Otherwise, the process returns to step 1012 to determine whether additional message objects are present for processing. If no additional unprocessed message objects are present, the messages in the outgoing message buffers are sent to a message processing unit 402 for distribution to the recipients (step 1028 ) with the process terminating thereafter.
Thus, the present invention allows for associating a public message with a private message avoiding addressing two messages to each recipient, one public and one private; and avoiding having to cross reference the private message to the public message. It is important to note that while the present invention has been described in the context of a fully functioning data processing system, those of ordinary skill in the art will appreciate that the processes of the present invention are capable of being distributed in the form of a computer readable medium of instructions and a variety of forms and that the present invention applies equally regardless of the particular type of signal bearing media actually used to carry out the distribution. Examples of computer readable media include recordable-type media such a floppy disc, a hard disk drive, a RAM, and CD-ROMs and transmission-type media such as digital and analog communications links.
The description of the present invention has been presented for purposes of illustration and description, but is not intended to be exhaustive or limited to the invention in the form disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art. The embodiment was chosen and described in order to best explain the principles of the invention, the practical application, and to enable others of ordinary skill in the art to understand the invention for various embodiments with various modifications as are suited to the particular use contemplated. | A method, system, and program for use in a data processing system for sending private messages from a single electronic message. A plurality of recipients is identified for an electronic message. A number of different sections are designated within the electronic message for separate receipt by each of a number of recipients within the plurality of recipients. Responsive to an indication to send the electronic message, an electronic message is automatically generated for each of the number of recipients, wherein the message of a given recipient within the number of recipients excludes sections within the number of sections designated for other recipients within the number of recipients. | 6 |
This is a division of U.S. patent application Ser. No. 10/628,290, filed Jul. 29, 2003 now U.S. Pat. No. 7,390,336, which is herein incorporated by reference in its entirety.
BACKGROUND
1. Field of the Invention
The present invention relates to Lithium Metal batteries. In particular, it is related to lithium metal batteries containing a polyimide-based electrolyte.
2. Background of the Invention
During the last ten years, lithium batteries of the primary and rechargeable type have been the object of a considerable number of research and development works. The intent was to develop a battery which is safe, inexpensive, having a large energetic content and good electrochemical performance. In this context, a plurality of a battery designs were developed to meet different applications, such as microelectronics, telecommunications, portable computers and electrical vehicles, to name only a few.
Electrochemical batteries or generators, whether rechargeable or not, are all made of an anode which can consist of a metal such as lithium and alloys thereof, or an insertion compound which is reversible towards lithium, such as carbon, a cathode which consists of an insertion compound which is reversible towards lithium such as transitional metal oxide, a mechanical separator and an electrolytic component placed in between the electrodes. The term electrolytic component means any material placed inside the generator and which is used as ionic transport except electrode materials in which the ions Li+ may be displaced. During the discharge or charge of the generator, the electrolytic component ensures the transport of ionic species through the entire generator from one electrode to the other and even inside the composite electrodes. In lithium batteries, the electrolytic component is generally in the form of a liquid which is called liquid electrolyte or a dry or gel polymer matrix which may also act as mechanical separator.
When the electrolytic component is in liquid form, it consists of an alkali metal salt which is dissolved in an aprotic solvent. In the case of a lithium generator, the more common salts are LIPF 6 , LIBF 4 and LiN(SO 2 CF 3 ) 2 and the polar aprotic solvents may be selected from propylene carbonate, ethylene carbonate, Y-butyrolactone and 1,3-dioxolane or their analogs to name only a few. At the level of the separator, the liquid electrolyte is generally impregnated in a porous polymer matrix which is inert towards the aprotic solvent used, or in a fiberglass paper. The use of a liquid electrolyte which is impregnated in an inert polymer matrix enables to preserve a sufficient ionic mobility to reach a level of conductivity of the order of 10−3 S/cm at 25° C. At the level of the composite electrodes, when the latter are made of an insertion material which is bound by a polymer matrix which is inert towards aprotic solvents, which have only little interaction with the latter, the liquid electrolyte fills the porosity of the electrode. Examples of batteries utilizing a liquid electrolytic component are found in U.S. Pat. Nos. 5,422,203; 5,626,985 and 5,630,993.
When the electrolytic component is in the form of a dry polymer matrix, it consists of a high molecular weight homo or copolymer, which is cross-linkable or non cross-linkable and includes a heteroatom in its repeating unit such as oxygen or nitrogen for example, in which an alkali metal salt is dissolved such as LiN(SO 2 CF 3 ) 2 , LiSO 3 CF 3 and LiCIO 4 . Polyethylene oxide is a good example of a polymer matrix which is capable of solving different alkali metal salts. Armand, in U.S. Pat. No. 4,303,748, describes families of polymers which may be used as electrolytic component in lithium batteries. More elaborated families of polymers (cross-linkable or non cross-linkable copolymers and terpolymers) are described in U.S. Pat. Nos. 4,578,326; 4,357,401; 4,579,793; 4,758,483 and in Canadian Patent No. 1,269,702. The use of a high molecular weight polymer enables to provide electrolytes in the form of thin films (of the order of 10 to 100 μm) which have sufficiently good mechanical properties to be used entirely as separator between the anode and the cathode while ensuring ionic transport between the electrodes. In the composite, the solid electrolyte serves as binder for the materials of the electrode and ensures ionic transport through the composite. The use of a cross-linkable polymer enables to utilize a polymer of lower molecular weight, which facilitates the preparation of the separator as well as the composite and also enables to increase the mechanical properties of the separator and, by the same token, to increase its resistance against the growth of dendrites when using a metallic lithium anode. As is well known in the art, repeated charge/discharge cycles can cause growth of dendrites on the lithium metal electrode. These dendrites can grow to such an extent that they penetrate the separator between positive and negative electrodes and create an internal short circuit. For this reason, metallic lithium anodes are used exclusively with solid polymer electrolyte separator sufficiently resistant and opaque to prevent dendrite growth from piercing its layer and reaching the positive electrode. Contrary to a liquid electrolyte, a solid polymer electrolyte is safer because it cannot spill nor be evaporated from the generator. Its disadvantage results from a lower ionic mobility obtained in these solid electrolytes which restricts their uses at temperatures between 40° C. and 100° C.
The gel electrolytic component is itself generally constituted of a polymer matrix which is solvating or non-solvating for lithium salts, aprotic solvent, and an alkali metal salt being impregnated in the polymer matrix. The most common salts are LiPF 6 , LiBF 4 , and LiN(SO 2 CF 3 ) 2 and the polar aprotic solvents may be selected from propylene carbonate, ethylene carbonate, butyrolactones, and 1,3-dioxolane, to name only a few. The gels may be obtained from a high molecular weight homo or copolymer which is cross-linkable or non cross-linkable or from a cross-linkable homo or copolymer. In the latter case, the dimensional stability of the gel is ensured by cross-linking the polymer matrix. Polyethers including cross-linkable functions such as alkyls, acrylates or methacrylates are good examples of polymers which may be used in formulating a gel electrolyte, such as described in U.S. Pat. No. 4,830,939. This is explained by their capacity to solvate lithium salts and their compatibility with polar aprotic solvents as well as their low cost, and ease of handling and cross-linking. A gel electrolyte has the advantage of being handled as a solid and of not spilling out of the generator as is the case with liquid electrolyte generators. Ionic transport efficiency is associated with the proportion of aprotic solvent incorporated in the polymer matrix. Depending on the nature of the polymer matrix, the salt, the plasticizing agent and its proportion in the matrix, a gel may reach an ionic conductivity of the order of 10−3 S/cm at 25° C. while remaining macroscopically solid. As in the case of a dry electrolyte, a gel electrolyte may be used as separator between the anode and cathode while ensuring ionic transport between the electrodes. In the composite electrode(s) of the generator, the gel electrolyte is used as binder for the materials of the electrode(s), and ensures ionic transport through the composite electrode(s). However, the loss of mechanical property resulting from the addition of the liquid phase (aprotic solvent) should generally be compensated by the addition of solid fillers, by cross-linking the polymer matrix whenever possible, or in some cases, when the proportion of liquid is too high, by using a porous mechanical separator which is impregnated with the gel which serves as electrolytic component in the separator.
The poor resistance of polyethers towards oxidation is however an important problem which is associated with the utilization of solid and gel electrolytes based on polyether as the electrolytic material in which the voltage in recharge may reach and even exceed 3.5V to 3.7 V. This results in an important loss of capacity of the generator which is caused by the more or less massive degradation of the polymer matrix during consecutive cycles of discharge/charge.
Gustafson et al. (U.S. Pat. No. 5,888,672) disclose a battery where the anode, the cathode, and the electrolyte each comprise a soluble, amorphous, thermoplastic polyimide. Since the polyimides are pre-imidized prior to the fabrication of the battery, there is no need to further cure them at high temperatures, thus reducing the risk of damaging the battery. The polyimide based electrolyte is resistant towards oxidation and capable of high ionic conductivity at or near room temperature. Nor is there a chance of incidental condensation as the battery temperature rises. In addition, since no further polymerization will occur, there are no by-products of the condensation reaction (water) to interact with the lithium salts. The battery of Gustafson et al. is said to be a dry cell.
In fabricating the battery, an electrolyte solution comprising a soluble, amorphous, thermoplastic polyimide solution and a lithium salt is prepared. The thermoplastic polyimide solution is prepared by mixing about 8% to about 20% by weight of a thermoplastic polyimide powder with about 80% to about 92% by weight of a solvent. About 20% to about 35% by weight of a lithium salt is dissolved in about 65% to about 80% by weight of a solvent to form a solution. The solution is then mixed with the thermoplastic polyimide solution to form the electrolyte solution. The electrolyte comprises from about 2% by weight to 10% by weight of soluble, amorphous, thermoplastic polyimide, from about 1% by weight to 12% by weight of the lithium salt and from about 78% by weight to 97% by weight of the solvent. An electrolyte layer is then formed by casting a film of the electrolyte solution which is fully dried in an oven at about 150° C. for about 30 to 60 minutes to create a dry, opaque, flexible, smooth, tough film. The polyimide based electrolyte solution is dried at the flash point of the solvent for the purpose of removing the solvent such that a dry electrolyte is obtained. The soluble, amorphous, thermoplastic polyimide may be any soluble, amorphous, thermoplastic polyimide known to those skilled in the art.
Laboratory tests have since demonstrated that a dried polyimide based electrolyte separator has poor ionic conductivity and as such is inadequate for battery applications with a metallic lithium anode. As described above, a lithium metal anode requires an electrolyte separator that presents enough mechanical resistance to prevent potential dendrite growths from piercing the electrolyte separator layer, reaching the positive electrode and causing a short circuit but it also requires a minimum of ionic conductivity to perform as an electrochemical generator.
Gustafson et al. (U.S. Pat. No. 6,451,480 issued Sep. 17, 2002) later on disclosed a Polyimide-based lithium-ion battery in which the anode and the cathode are prepared from an electrolyte polyimide binder solution comprising from about 9% by weight to about 15% by weight of a pre-imidized soluble, amorphous, thermoplastic polyimide powder dissolved in about 75% by weight to about 85% by weight of a polar solvent; and from about 6% by weight to about 12% by weight of a lithium salt and an electrolyte separator consisting of a typical separator film saturated with a liquid electrolyte solution of lithium salts dissolved in a variety of organic solvents such as ethylene carbonate mixed with dimethyl carbonate. A cell stack is assembled and placed in a container which is then filled with the electrolyte and sealed. Evidently, the ionic conduction is achieved by the solvent content of the electrolyte separator and of the composite anode and cathode. The cell is based on Li-ion technology using a liquid electrolyte and therefore cannot be combined with a metallic lithium anode as the high solvent content renders the electrolyte separator unable to prevent dendrites growth. Furthermore, the typical solvent used in Li-ion technology are unstable with metallic lithium anode; their resistance increasing with time.
Thus there is a need for an improved polyimide-based electrolyte having good ionic conductivity and capable of operating with a lithium metal anode.
BRIEF SUMMARY OF THE INVENTION
It is therefore an object of the present invention is to provide a polyimide-based electrolyte adapted for operation with a lithium metal anode.
Another object of the present invention to provide a polyimide-based battery adapted for operation with a lithium metal anode.
Another object of the present invention is to provide a process for making a polyimide-based battery having a metallic lithium anode.
As embodied and broadly described, the invention provides a battery comprising:
at least one metallic lithium anode; at least one cathode, and a polyimide-based electrolyte separator disposed between said at least one metallic lithium anode and said at least one cathode; the polyimide-based electrolyte separator comprising a soluble, polyimide, a lithium salt, and from about 10% by weight to about 60% by weight of solvent.
As embodied and broadly described, the invention further provides an electrolyte comprising a soluble, polyimide, a lithium salt, and from about 10% by weight to about 60% by weight of solvent
As embodied and broadly described, the invention further provides a process for preparing a battery, the process comprising the steps of:
a) preparing a metallic lithium or lithium alloy sheet; b) preparing a cathode slurry comprising an insertion compound; an electronic conductive filler; a lithium salt and an ionically conductive electrolyte binder; c) preparing an electrolyte solution comprising a soluble, polyimide, a lithium salt, and from about 10% by weight to about 60% by weight of solvent; d) applying said cathode slurry onto a current collector to form a cathode film; e) applying said electrolyte solution onto said cathode film to form an electrolyte separator; f) applying said metallic lithium or lithium alloy sheet onto said electrolyte separator to form an electrochemical cell.
The present invention concerns a new concept of polyimide-based electrolytic component having an electrolyte comprising at least one solvent and at least one alkali metal salt, with specific amounts of solvents, to optimize the properties of conductivity of the polyimide-based electrolyte and the mechanical properties of the polyimide-based electrolyte separator towards metallic lithium anode to prevent dendrites growth.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and other advantages will appear by means of the following description and the following drawings in which:
FIG. 1 is a schematic cross-sectional view of a battery according to one embodiment of the present invention;
FIG. 2 is a graph illustrating the relationship between the discharge capacity of a polyimide-based electrochemical cell and the solvent content of the polyimide-based electrolyte; and,
FIG. 3 is a schematic cross-sectional view of a bi-face configured electrochemical cell according to one embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a schematic cross-sectional view of a battery 11 according to one embodiment of the present invention. In particular, the battery 10 comprises at least one lithium metal anode 12 , at least one composite cathode 14 , at least one electrolyte separator 16 disposed between each lithium metal anode 12 and each composite cathode 14 . The lithium metal anode 12 comprises a thin sheet of metallic lithium or alloy thereof. The composite cathode comprises of a mixture of an active material such as a transitional metal oxide; an electronic conductive filler such as carbon black; and an ionically conductive electrolyte polymer binder comprising a lithium salt. The electrolyte polymer binder may be an electrolyte polyimide binder comprising an alkali metal salt or a polyether binder also comprising an alkali metal salt. The composite cathode 14 is supported by a metal current collector 18 typically made of thin aluminum foil. The electrolyte separator 16 comprises a soluble polyimide swollen with 10% weight to 40% weight of a solvent and at least one alkali metal salt preferably a lithium salt. % by weight of solvent is calculated as the weight of solvent divided by the total weight of electrolyte which includes polyimide, alkali metal salt and solvent.
The alkali metal salt(s) may be for example salts based on lithium trifluorosulfonimide described in U.S. Pat. No. 4,505,997, LIPF 6 , LiBF 4 , LiSO 3 CF 3 , LiCIO 4 , and LiSCN, etc. The nature of the salt is not a limitation of the present invention.
The solvent(s) may for example be selected from N,N-methylpyrrolidinone (NMP), Y-butyrolactone, and sulfamides of formula; R 1 R 2 N—SO 2 —NR 3 R 4 , in which R 1 , R 2 , R 3 and R 4 are alkyls having between 1 and 6 carbon atoms and/or oxyalkyls having between 1 and 6 carbon atoms or combinations thereof. Preferably the solvent or combination of solvents is (are) polar aprotic solvent(s). The nature of the solvent is not a limitation of the present invention.
The active material of the cathode may be selected from cobalt oxide, nickel oxide, nickel cobalt oxide, nickel cobalt aluminum oxide, manganese oxide (LiMn 2 O 4 ) or their analogs for so-called 4 V cathodes or among cathodes of less hand 4 V such as phosphates or other polyanions of transition metals such as LiFePO 4 , Nasicon structures also including V 2 O 5 , LiV 3 O 8 and MnO 2 . The nature of the active material is not a limitation of the present invention.
As previously mentioned, the electrolyte separator 16 comprises a soluble polyimide swollen with 10% weight to 40% weight of a solvent and at least one alkali metal salt preferably a lithium salt. The soluble polyimide may be any soluble polyimide known to those skilled in the art. Specific examples include but are not limited to: MATRIMID XU5218 commercially available from Ciba-Geigy; ULTEM 1000P commercially available from General Electric; LaRC-CP1, LaRC-CP2, and LaRC-Si available from Imitec, Inc., Schenectady, N.Y. The soluble polyimides used in the present invention are fully imidized and are usually powder in form.
In order to produce a film, coating, or a slurry from the polyimide, the polyimide powder must first be dissolved in a solvent such as N,N-methylpyrrolidinone (NMP) and Gamma-butyrolactone to name a few in order to form a polyimide solution. Note that the polyimides dissolve in these solvents. In addition, large amounts of lithium salts can be dissolved in these polyimide solutions without disturbing the polymer matrix. The polyimide solution is then partially dried at a temperature suitable to evaporate excess solvent in order to obtain a polyimide solution containing between 10% and 40% by weight of solvent and form a polyimide based electrolyte.
In order to operate with a lithium metal anode, it is imperative that the solvent content in the polyimide based electrolyte be such that the electrolyte layer 16 remains a compact separator capable of maintaining an efficient barrier at the surface of the lithium metal anode 12 against dendrite growth. In a preferred embodiment, the electrolyte comprises from about 10% by weight to about 60% by weight of the soluble polyimide, from about 5% by weight to about 20% by weight of the lithium salt and from about 10% by weight to about 60% by weight of solvent. In a more preferred embodiment, the electrolyte comprises from about 20% by weight to about 50% by weight of the soluble polyimide, from about 5% by weight to about 20% by weight of the lithium salt and from about 20% by weight to about 40% by weight of solvent.
As illustrated in FIG. 2 , the ideal compromise between discharge capacity (ionic conductivity) and the polyimide based electrolyte's mechanical resistance is reached at levels of between about 15% by weight to about 40% by weight of solvent. In this range, the polyimide based electrolyte has good ionic conductivity at 25° C. and is sufficiently firm to prevent dendrites growths at the surface of the metallic lithium anode. As shown in FIG. 2 , the extracted capacity at a specific C-rate is directly proportional to the percentage by weight of solvent in the polyimide electrolyte. The relation between discharge capacity and percentage by weight of solvent in the electrolyte is almost linear however the polyimide based electrolyte assumes more solid mechanical properties at levels of solvent content below 60% and ideally below 40% by weight. At 20% to 40% by weight of solvent, the polyimide based electrolyte exhibits excellent ionic conductivity yet its matrix is firm and compact enough to inhibit dendrites growths at the surface of the metallic lithium anode. In light of this relation, the solvent content in the polyimide electrolyte may be modulated as a function of the application of the polyimide-based battery. For example, an application requiring a low discharge current (low C-rate), the polyimide electrolyte of the battery may contain less solvent than for application requiring high discharge current (high C-rate) such that the solvent content in the polyimide electrolyte may be optimized. It however remains within the specific range of 10% to 60% by weight and preferably within the specific range of 15% to 40% by weight.
In one specific embodiment of the invention as shown in FIG. 3 , a cathode layer 14 is coated or otherwise layered on both sides of a thin metal current collector 18 . Each cathode layer 14 comprises an electrochemically active material such as a transitional metal oxide (LiCoO 2 ; LiMnO 2 ; LiNiO 2 ; LiV 3 O 8 ; Li 4 Ti 5 O 12 ; V 6 O 13 ; V 2 O 5 ; and LiMn 2 O 4 and their equivalents); an electronic conductive filler such as conductive carbon, carbon black, graphite, and graphite fiber; and an ionically conductive electrolyte polymer binder. The ionically conductive electrolyte polymer binder preferably comprises a lithium salt and comprises either a polyether based mono, ter or co-polymer or a pre-imidized soluble, polyimide powder. The lithium salt and the polymer are soluble in any polar solvent known to those of ordinary skill in the art.
A polyimide based electrolyte separator 16 comprising about 45-60% by weight of the soluble polyimide, about 10-15% by weight of the lithium salt and about 20-40% by weight of a solvent preferably a polar aprotic solvent, is then coated onto each cathode layer 14 to form a bi-face configured half-cell. To complete the electrochemical cell, a lithium or lithium alloy metal anode 12 is finally positioned over each polyimide based electrolyte separator 16 .
The cathode layer 14 and the polyimide based electrolyte separator 16 may also be coated or otherwise applied onto polypropylene support films separately and then laminated together as is well known in the art.
When preparing the polyimide based electrolyte, a solution is first prepared with an excess of solvent to ensure proper mixing of the polyimide powder and the lithium salt. Next, the solution may be either dried to obtain a specific content of solvent (20-40%) prior to coating or laminating onto the cathode layers 14 of the cell 10 or the polyimide based electrolyte may be coated or laminated with its excess solvent and thereafter dried to obtain a specific solvent content such as 20-40% by weight as described above.
In an alternative embodiment of the invention, the polyimide powder and a lithium salt are first dissolved in the solvent to form a polyimide solution. To the polyimide solution is added a cross linkable co-monomer and optionally a cross-linking initiator. The polyimide solution is then either partially dried prior to assembly or assembled with excess solvent as described above. Once layered onto each cathode layer 14 , cross-linking of the polyimide electrolyte is carried out thermally, by UV radiation or with electron beam (EB). The cross-linked polyimide electrolyte has improved mechanical resistance over the non-cross-linked electrolyte.
In fabricating a battery, a lithium metal based anode 12 , a separator film 16 , and a cathode 14 are assembled in alternate layers to form a cell stack. The separator film 16 needs to be positioned between the anode 12 and the cathode layers 14 to prevent shorting in the cell. The cell may be monoface or bi-face and may be stacked in prismatic, folded, wound, cylindrical, or jelly rolled configuration as is well known to those skilled in the art. Once the cells stack is formed, pressure is preferably applied to the cells stack and maintained. The pressurized cells stack is placed in a container wherein the pressure on the stack is maintained. The cells stack must be assembled using pressure to improve interlayer conductivity. The pressure is maintained when the cells stack in placed into a battery container.
In a further alternative embodiment of the invention, a separator film may be used as a barrier between each anode and cathode layer. The separator film is a freestanding film comprised of an organic polymer, such as polypropylene. Examples of such films include but are not limited to Kynar FLEX from Atochem North America; and CELGARD 3401 from Polyplastics Co., Ltd. The freestanding separator film is either partially soaked with a solution of polyimide based electrolyte with the specific solvent content within the preferred range or the freestanding separator film is saturated with a solution of polyimide based electrolyte having excess solvent and partially dried to obtain the desired percentage by weight of solvent.
The manufacture of the battery is completed after the cell is placed in the package, as described earlier. At this point the battery can be charged to store an electric charge and it is then ready for use.
The above description and drawings are only illustrative of preferred embodiments which achieve the objects, features and advantages of the present invention, and it is not intended that the present invention be limited thereto. Any modification of the present invention which comes within the spirit and scope of the following claims is considered part of the present invention. | The present invention relates to Lithium Metal batteries. In particular, it is related to lithium metal batteries containing a polyimide-based electrolyte. The present invention concerns a new concept of polyimide-based electrolytic component having an electrolyte comprising of at least one solvent and at least one alkali metal salt, with specific amounts of solvents, to optimize the properties of conductivity of the polyimide-based electrolyte and the mechanical properties of the polyimide-based electrolyte separator towards metallic lithium anode to prevent dendrites growths. | 7 |
BACKGROUND OF THE INVENTION
The present invention relates to three dimensional autostereoscopic displays. Such autostereoscopic displays can be made from a high frame rate two dimensional display and a device which makes the picture on the two dimensional display visible from different directions.
To display an autostereoscopic three dimensional image, a series of views of the object to be imaged are required. These might be captured by, for example, surrounding a solid object with an array of conventional cameras.
With such systems, each view in the series is put up on the two dimensional display in turn and made visible from a particular general direction. If the series is repeated quickly enough that the human eye perceives no flicker, the apparent effect is a display whose image content will depend on from where the human eye looks. By appropriate matching of view to direction of viewability, it is possible to recreate the three dimensional image on the display.
One way of making such a display is to use a cathode ray tube as the two dimensional display, and a lens and a shutter as the device which limits the field of view of the picture on the display.
The lens forms a virtual image of the cathode ray tube. The shutter, which reduces the field of view of the image, is positioned adjacent to the lens.
If the position of the aperture in the shutter can be changed rapidly, the angle from which the image can be seen may be varied as different pictures are presented in turn for display on the CRT screen. Each picture can be the view of some scene taken from a chosen viewpoint. So long as the picture for each direction is repeated sufficiently frequently, typically at least 50 Hz, and the shutter is stepped in sequence with the view on the CRT display, then different views will be seen from different positions and a three dimensional image will be observed. There are several alternative optical and image forming arrangements that are operationally equivalent to the description given above. Implementations can consist of 2 dimensional image forming devices made from an LCD or from a CRT. The shutter can be made from an LCD. The arrangement can place the shutter between the image forming device and the observer or can position the image forming device between the shutter and the observer. The light can be collimated or non-collimated. In a presently preferred implementation, the image forming device is a CRT and a viewing lens is added between the viewer and the shutter to narrow the pencils of rays passing through the aperture into near-parallel beams.
A number of devices for producing a colour 3D display employing the above principles have been proposed. One such way of making a colour three dimensional display is to have a colour CRT. However conventional colour CRT's are not bright because they incorporate shadow masks. Since the shuttering system absorbs a lot of light the CRT in this system needs to be bright, requiring a great deal of power, and brighter than available by current masking techniques.
Another way of making a colour three dimensional display is to use dichroic mirrors to combine the images from one red, one green and one blue CRT. The problem is that, at least in current three dimensional displays, the imaging lens is large, and there is little space for dichroic mirrors. Furthermore, it becomes necessary to register the CRTs so that the position of each pixel is the same on each CRT. The whole system is bulky, heavy and expensive because three times as many components are needed.
The bulk and expense of three CRT's can be avoided by using one CRT with a white phosphor, then filtering the emitted light so that rays of each of the primary colours are transmitted in turn. The disadvantages of this approach are that the CRT needs to operate three times faster than otherwise, it needs to be brighter than otherwise, and a filter which can switch between the primary colours is required.
A filter which switches between the primary colours has been made for a colour two dimensional display. It might seem that the obvious way to make a colour three dimensional display would be to place this filter over the front of the three dimensional display. Colour images might be produced on a black/white three dimensional display by placing a filter against the front which switches through the primary colours. The problem is that the liquid crystal of which present switching colour filters are made cannot switch quickly enough.
When the filter is used on a two dimensional display the CRT displays the three primary colour components of the picture one by one. Ideally the filter should change colour in the time interval between the end of the display of one primary colour and the beginning of the display of the next. This time interval is short and even on the two dimensional display the filter is not fast enough for this purpose.
In fact the filter is divided into horizontal bands which can be switched independently. The idea is that as the CRT electron beam writes each picture from the top of the screen to the bottom, the horizontal bands of the filter are also switched one by one, from top to bottom. Provided each band begins switching immediately after lines adjacent to it have decayed, there is sufficient time to complete switching before the adjacent lines are written with new information.
This solution works for the two dimensional display, but the frame rate of the CRT in the three dimensional display is much higher. There is therefore less time before each line is rewritten, and this time is insufficient for the filter to switch.
An alternative to using a switching colour filter would be to make a wheel comprising a red, green and blue filter and spin this in front of the screen. This might work with a two dimensional display because the wheel need only spin at 60 Hz. With a three dimensional display with 8 views, for example, the wheel would have to spin at 480 Hz, this would be impractical.
The presently available switching colour filters are slow because they are based on slow-switching liquid crystals. The liquid crystals in the shutter used in the three dimensional display switch much more quickly. It has been suggested that it might be possible to configure the shutter to switch each slit through each of the primary colours in turn before closing that slit and opening the next. Colour images might be produced on a black/white three dimensional display by making the shutter filter the primary colours in turn while each slit is open. Unfortunately, shutters which work in this way are not available at present.
It is useful to consider if a pair of spinning wheels could be configured to behave like a colour-switching shutter. Such a system is discussed in "Wireless World, February 1942--Stereoscopic colour TV". In a system with a wheel with a slit spinning so as to scan the slit in the focal plane of the collimating lens, with a colour wheel placed adjacent to this slit, the colour wheel spinning at a higher rate so that at each slit position light is filtered to produce each of the primary colours.
The problem with this proposed system is that the shutter slit does not move from position to position, but is always moving. So the slit will be at a slightly different position as each of the colour filters passes it. This will produce a registration problem, there will be positions at which an eye will see, for example, the red component of one view superposed on the blue and green components of a different view. This would be quite unsatisfactory.
SUMMARY OF THE INVENTION
According to the present invention there is provided a polychromatic three dimensional display comprising:
a first image source;
a second image source, the second image source being adapted to reduce selectively the field of view of the first image source to generate thereby a time multiplexed three dimensional autostereoscopic image; and
a switching colour filter disposed adjacent to the second image source and comprising a plurality of regions each switchable between different colours to enable colour modulation of the generated image.
Preferably the first image source is a spatial light modulator, and the second image source is a scanning light source which selectively illuminates the first image source from one of a plurality of positions. Alternatively, the first image source is a monochrome or white phosphor cathode ray tube or similar device, and the second image source is a shutter comprising a plurality of independently activated apertures.
Preferably, there is also provided an imaging lens positioned between the two image sources. The imaging lens may be either single or multi-element, and allows greater optical design freedom, together with the possibility of producing large images from components of reduced size.
A collimating lens may also be provided to provide a viewer with collimated light to improve the autostereoscopic effect of the display.
The filter may include a rotatable disc comprising a plurality of differently coloured regions, but is preferably comprises a plurality of regions that are individually switchable between a plurality of colours. With this latter arrangement, for displays where the second image source is a shutter, there may also be provided control means for controlling the activation of the switching colour filter strips and shutter apertures so that each strip starts switching to the next colour immediately after the termination of the view which passes light through that strip.
Preferably the colour filter has portions corresponding the three primary colours.
BRIEF DESCRIPTION OF THE DRAWINGS
One example of the present invention will now be described with reference to the accompanying drawings in which:
FIG. 1 is a schematic diagram showing the basic principles of an autostereoscopic three dimensional display;
FIG. 2 is a diagram showing a prior art example of a monochrome autostereoscopic three dimensional display;
FIG. 3 is a colour adaptation of the display of FIG. 2;
FIG. 4 is a prior art polychromatic autostereoscopic three dimensional display employing a spinning disc;
FIG. 5 is a schematic diagram of a first example autostereoscopic polychromatic three dimensional display according to the present invention;
FIG. 6 is a schematic diagram of a second example autostereoscopic polychromatic three dimensional display according to the present invention; and
FIG. 7 is a schematic diagram of a third example autostereoscopic polychromatic three dimensional display according to the present invention.
DESCRIPTION OF THE INVENTION
FIG. 1 shows the basic concept of a known three dimensional display. Pictures of an object are formed by cameras 3 ranged round the object 2 and pointing at it from different directions. One picture at a time is reproduced on the display 1. The display 1 can confine the direction from which this picture is visible. It does this so that the direction of visibility matches the direction of the camera from which the picture is received. Other pictures are shown from other cameras 3 in a similar manner. Once a picture from each of the cameras 3 has been shown, the sequence is repeated. The rate of repetition is such that the display of each picture to each direction will appear continuous to an observer 4 inspecting the display from different angles.
Whenever collimated light illuminates the observer 4, he will see the picture on the display. However each of the observer's eyes will be illuminated by collimated light travelling in different directions. So each eye will see a different picture. The three dimensional image displayed will therefore be of the type described with reference to FIG. 1.
In the prior art system of FIG. 2, a cathode ray tube (CRT) 5 is used as an image source. Light from the image source 5 passes through an imaging lens 6 and an aperture 7 in a shutter 8. The shutter 8 comprises an array of independently activated apertures 7. The light then passes through a collimating lens 9 to be viewed by an observer. A different aperture 7 is opened for each of the images that are displayed on the image source 5, so that a viewer perceives each of the images to be from a source of a different position and a monochrome three dimensional display is produced.
FIG. 3 shows the monochrome three dimensional display of FIG. 2 adapted to be used a colour three dimensional display by the additional of a colour filter 10. The colour filter 10 switches between the three primary colours in turn, and the sequence of images displayed in the image source 5 is repeated three times, once for each of the primary colours. As mentioned above, such a system has the serious problem that a switching times of the image source 5, shutter 8 and particularly the colour filter 10 must be very small so that no flicker is observed by the viewer.
In the prior art system of FIG. 4, the moving slit shutter 8 is provided by a spinning disc, and the colour is produced by the rotation of a spinning disc 11 that is divided into three portions, each of the portions being coloured according to one of the three primary colours. In this example, the filter disc 11 is spun at high speed to produce three supposedly identical images in the three primary colours, which are perceived by an observer to be a single image of combined colour. Unfortunately, as the slit 7 is continuously moving, the three coloured images will be perceived to be coming from slightly different positions, so that they will not overlap perfectly and a full three dimensional effect will not be produced.
In the first example of the present invention shown in FIG. 5, the display has a first image source 5, which is a spatial light modulator provided by a liquid crystal display or similar device. The device also includes a scanning light source 8 and spinning disk filter 12. There is also provided an imaging lens 6, which is not essential, but which provides greater component design freedom. In operation the first image source 5 displays a series of images of an object from different viewpoints, and, for each image displayed, a different portion of the light source is activated, illuminating the image from one direction and making it appear to come from a different position. As with the prior art examples, with each of the images being produced at a rate at which the eye perceives no flicker, an autostereoscopic display is produced. However, as there is provided a colour filter 12 between the light source 8 and image source 5, a series of colour modulated images will be presented to a viewer. The colour filter 12 must spin at a speed which ensures that the illuminating light is modulated to the correct colour for the image being presented, but as only one of the light sources 8 is activated at any one instant, the rotation of the colour filter 12 can follow the activation of the individual light sources 8, providing a complete series of images for a first colour, and enabling the filter 12 to have rotated to the next colour by the time that each of the sources 8 has been activated. This greatly reduces the necessary spinning speed for the filter.
FIG. 6 shows a second example of the present invention which employs very similar principles to that of the first example, but which, in place of the spinning colour filter 12 has a colour filter comprising a plurality of individually switchable regions 13. Each of these regions 13 can be switched between one of a number of colours, in this example red, green and blue. An example of a device with such characteristics is a NU 700S colour shutter from Tectronix Ltd. In this example, the light source 8 and image source 5 operate in a similar fashion to that of the first example, but the filter is aligned with the individual light sources. In operation, each of the regions 13 of the filter 12 is activated to change colour immediately after its corresponding light source has been de-activated, so that the time period in which each region must change to the next required colour is maximised. This enables the employment of a filter with a reduced switching speed for each of its regions.
In the example of the present invention shown in FIG. 7, a first image source 5, imaging lens 6, shutter 8 and collimating lens 9 are provided, in addition, a switching colour filter 12 is also provided. The imaging lens 6 and collimating lens 9 are not essential to the invention, but, as mentioned above, enable greater design freedom and components of reduced size to be employed. The switching colour filter 12 is positioned between the imaging lens 6 and the shutter 8 and, as with the second example, comprises an array of individually switchable regions 13, each of the regions being able to be switched between the primary colours. This example may, alternatively, employ a spinning disc filter of the type described with reference to FIG. 5, in place of the switchable strip colour filter 12.
As previously mentioned, spinning disc colour filters would normally have to be spun at great speed to be employed in an autostereoscopic display, but, with the examples of the present invention which employ such filters, this speed is greatly reduced by the employment of only a fraction of one of the coloured apertures in colour modulation at a particular instant. Also, as previously mentioned, the switching time of switchable colour filters is slow, but in the two examples of the present invention which employ such filters, this is overcome by individually switchable strips 13, which can be activated prior to their corresponding aperture 7 being opened in front of them. As each of the strips is only visible for a short period of time, a larger switching time is available for activating them and changing their colour. Different speed of switching colour and aperture can be exploited to give the combined effect on the two at the speed of the fastest, subject to a cycle time of the switching speed of the slowest. The examples of the present invention operate in a similar fashion to the device of FIG. 3, in that the image sequence is run three times on the image source 5, with each of the apertures 7 being activated in turn on the shutter 8 once for each time the sequence is played, the filter 12 being switched between colours in advance of the opening of the aperture 7 so that it has completely changed to the next colour prior to them being made visible to the viewer. | A polychromatic three dimensional display comprises a first (5) and second (8) image sources, the second image source (8) adapted to reduce selectively the field of view of the first image source to provide thereby a time multiplexed three dimensional autostereoscopic image. The display also comprises a switching color filter (12) disposed adjacent to the second image source which comprises a plurality of regions each switchable between different colors to enable color modulation of the generated image. | 7 |
BACKGROUND OF THE INVENTION
[0001] Carbohydrates have the general molecular formula CH 2 O, and thus were once thought to represent “hydrated carbon”. However, the arrangement of atoms in carbohydrates has little to do with water molecules. Starch and cellulose are two common carbohydrates. Both are macromolecules with molecular weights in the hundreds of thousands. Both are polymers; that is, each is built from repeating units, monomers, much as a chain is built from its links.
[0002] Three common sugars share the same molecular formula: C 6 H 12 O 6 . Because of their six carbon atoms, each is a hexose. Glucose is the immediate source of energy for cellular respiration. Galactose is a sugar in milk. Fructose is a sugar found in honey. Although all three share the same molecular formula (C 6 H 12 O 6 ), the arrangement of atoms differs in each case. Substances such as these three, which have identical molecular formulas but different structural formulas, are known as structural isomers. Glucose, galactose, and fructose are “single” sugars or monosaccharides.
[0003] Two monosaccharides can be linked together to form a “double” sugar or disaccharide. Three common disaccharides are sucrose, common table sugar (glucose+fructose); lactose, the major sugar in milk (glucose+galactose); and maltose, the product of starch digestion (glucose+glucose). Although the process of linking the two monomers is complex, the end result in each case is the loss of a hydrogen atom (H) from one of the monosaccharides and a hydroxyl group (OH) from the other. The resulting linkage between the sugars is called a glycosidic bond. The molecular formula of each of these disaccharides is C 12 H 22 O 11 =2 C 6 H 12 O 6 −H2O. All sugars are very soluble in water because of their many hydroxyl groups. Although not as concentrated a fuel as fats, sugars are the most important source of energy for many cells.
BRIEF SUMMARY OF THE INVENTION
[0004] The present invention relates to polysaccharides from microalgae. Representative polysaccharides include those present in the cell wall of microalgae as well as secreted polysaccharides, or exopolysaccharides. In addition to the polysaccharides themselves, such as in an isolated, purified, or semi-purified form, the invention includes a variety of compositions containing one or more microalgal polysaccharides as disclosed herein. The compositions include cosmeceutical compositions which may be used for a variety of indications and uses as described herein. Other compositions include those containing one or more microalgal polysaccharides and a suitable carrier or excipient for injectable administration.
[0005] The invention further relates to methods of producing or preparing microalgal polysaccharides. In some disclosed methods, exogenous sugars are incorporated into the polysaccharides to produce polysaccharides distinct from those present in microalgae that do not incorporate exogenous sugars.
[0006] In another aspect, the invention relates to compositions for topical application. In some embodiments, the composition is that of a cosmeceutical. A cosmeceutical may contain one or more microalgal polysaccharides, or a microalgal cell homogenate, and a topical carrier. In some embodiments, the carrier may be any carrier suitable for topical application, such as, but not limited to, use on human skin or human mucosal tissue. In some embodiments, the composition may contain a purified microalgal polysaccharide, such as an exopolysaccharide, and a topical carrier.
[0007] As a cosmeceutical, the composition may contain a microalgal polysaccharide or homogenate and other component material found in cosmetics. In some embodiments, the component material may be that of a fragrance, a colorant (e.g. black or red iron oxide, titanium dioxide and/or zinc oxide, etc.), a sunblock (e.g. titanium, zinc, etc.), and a mineral or metallic additive.
[0008] In other aspects, the invention includes methods of preparing or producing a microalgal polysaccharide. In some aspects relating to an exopolysaccharide, the invention includes methods that separate the exopolysaccharide from other molecules present in the medium used to culture exopolysaccharide producing microalgae. In some embodiments, separation includes removal of the microalgae from the culture medium containing the exopolysaccharide, after the microalgae has been cultured for a period of time. Of course the methods may be practiced with microalgal polysaccharides other than exopolysaccharides. In other embodiments, the methods include those where the microalgae was cultured in a bioreactor, optionally where a gas is infused into the bioreactor.
[0009] In one embodiment, the invention includes a method of producing an exopolysaccharide, wherein the method comprises culturing microalgae in a bioreactor, wherein gas is infused into the bioreactor; separating the microalgae from culture media, wherein the culture media contains the exopolysaccharide; and separating the exopolysaccharide from other molecules present in the culture media.
[0010] The microalgae of the invention may be that of any species, including those listed in Table 1 herein. In some embodiments, the microalgae is a red algae, such as the red algae Porphyridium , which has two known species ( Porphyridium sp. and Porphyridium cruentum ) that have been observed to secrete large amounts of polysaccharide into their surrounding growth media. In other embodiments, the microalgae is of a genus selected from Rhodella, Chlorella , and Achnanthes . Non-limiting examples of species within a microalgal genus of the invention include Porphyridium sp., Porphyridium cruentum, Porphyridium purpureum, Porphyridium aerugineum, Rhodella maculata, Rhodella reticulata, Chlorella autotrophica, Chlorella stigmatophora, Chlorella capsulata, Achnanthes brevipes and Achnanthes longipes.
[0011] In some embodiments, a polysaccharide preparation method is practiced with culture media containing over 26.7, or over 27, mM sulfate (or total SO 4 2− ). Non-limiting examples include media with more than about 28, more than about 30, more than about 35, more than about 40, more than about 45, more than about 50, more than about 55, more than about 60, more than about 65, more than about 70, more than about 75, more than about 80, more than about 85, more than about 90, more than about 95, or more than about 100 mM sulfate. Sulfate in the media may be provided in one or more of the following forms: Na 2 SO 4 .10H 2 O, MgSO 4 .7H 2 O, MnSO 4 , and CuSO 4 .
[0012] Other embodiments of the method include the separation of an exopolysaccharide from other molecules present in the culture media by tangential flow filtration. Alternatively, the methods may be practiced by separating an exopolysaccharide from other molecules present in the culture media by alcohol precipitation. Non-limiting examples of alcohols to use include ethanol, isopropanol, and methanol.
[0013] In other embodiments, a method may further comprise treating a polysaccharide or exopolysaccharide with a protease to degrade polypeptide (or proteinaceous) material attached to, or found with, the polysaccharide or exopolysaccharide. The methods may optionally comprise separating the polysaccharide or exopolysaccharide from proteins, peptides, and amino acids after protease treatment.
[0014] In other embodiments, a method of formulating a cosmeceutical composition is disclosed. As one non-limiting example, the composition may be prepared by adding separated polysaccharides, or exopolysaccharides, to homogenized microalgal cells before, during, or after homogenization. Both the polysaccharides and the microalgal cells may be from a culture of microalgae cells in suspension and under conditions allowing or permitting cell division. The culture medium containing the polysaccharides is then separated from the microalgal cells followed by 1) separation of the polysaccharides from other molecules in the medium and 2) homogenization of the cells.
[0015] Other compositions of the invention may be formulated by subjecting a culture of microalgal cells and soluble exopolysaccharide to tangential flow filtration until the composition is substantially free of salts. Alternatively, a polysaccharide is prepared after proteolysis of polypeptides present with the polysaccharide. The polysaccharide and any contaminating polypeptides may be that of a culture medium separated from microalgal cells in a culture thereof. In some embodiments, the cells are of the genus Porphyridium.
[0016] In an additional embodiment, a method of cosmetic enhancement is described. In one embodiment, a method may include injecting a polysaccharide produced by microalgae into mammalian skin. Preferably the polysaccharide is sterile and free of protein.
[0017] The details of additional embodiments of the invention are set forth in the accompanying drawings and the description below. Other features and advantages of the invention will be apparent from the drawings and detailed description, and from the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 shows precipitation of 4 liters of Porphyridium cruentum exopolysaccharide using 38.5% isopropanol. (a) supernatant; (b) addition of 38.5% isopropanol; (c) precipitated polysaccharide; (d) separating step.
[0019] FIG. 2 shows growth of Porphyridium sp. and Porphyridium cruentum cells grown in light in the presence of various concentrations of glycerol.
[0020] FIG. 3 shows Porphyridium sp. cells grown in the dark in the presence of various concentrations of glycerol.
[0021] FIG. 4 shows levels of solvent-accessible polysaccharide in Porphyridium sp. homogenates subjected to various amounts of physical disruption from Sonication Experiment 1.
[0022] FIG. 5 shows levels of solvent-accessible polysaccharide in Porphyridium sp. homogenates subjected to various amounts of physical disruption from Sonication Experiment 2.
[0023] FIG. 6 shows protein concentration measurements of autoclaved, protease-treated, and diafiltered exopolysaccharide.
[0024] FIG. 7 shows various amounts and ranges of amounts of compounds found per gram of cells in cells of the genus Porphyridium.
[0025] FIG. 8 shows Porphyridium sp. cultured on agar plates containing various concentrations of zeocin.
DETAILED DESCRIPTION OF THE INVENTION
[0026] U.S. patent application Ser. No. 10/411,910 is hereby incorporated in its entirety for all purposes. U.S. patent application Ser. No. 11/336,426, filed Jan. 19, 2006, entitled “Polysaccharide Compositions and Methods of Producing, Screening, and Formulating Polysaccharide Compositions”, is hereby incorporated in its entirety for all purposes. All other references cited are incorporated in their entirety for all purposes.
[0027] Definitions: The following definitions are intended to convey the intended meaning of terms used throughout the specification and claims, however they are not limiting in the sense that minor or trivial differences fall within their scope.
[0028] “Active in microalgae” means a nucleic acid that is functional in microalgae. For example, a promoter that has been used to drive an antibiotic resistance gene to impart antibiotic resistance to a transgenic microalgae is active in microalgae. Nonlimiting examples of promoters active in microalgae are promoters endogenous to certain algae species and promoters found in plant viruses.
[0029] “ARA” means Arachidonic acid.
[0030] “Axenic” means a culture of an organism that is free from contamination by other living organisms.
[0031] “Bioreactor” means an enclosure or partial enclosure in which cells are cultured in suspension.
[0032] “Carrier suitable for topical administration” means a compound that may be administered, together with one or more compounds of the present invention, and which does not destroy the activity thereof and is nontoxic when administered in concentrations and amounts sufficient to deliver the compound to the skin or a mucosal tissue.
[0033] “Combination Product” means a product that comprises at least two distinct compositions intended for human administration through distinct routes, such as a topical route and an oral route. In some embodiments the same active agent is contained in both the topical and oral components of the combination product.
[0034] “Conditions favorable to cell division” means conditions in which cells divide at least once every 72 hours.
[0035] “DHA” means Docosahexaenoic acid.
[0036] “Endopolysaccharide” means a polysaccharide that is retained intracellularly.
[0037] “EPA” means eicosapentaenoic acid.
[0038] “Exogenous gene” means agene transformed into a wild-type organism. The gene can be heterologous from a different species, or homologous from the same species, in which case the gene occupies a different location in the genome of the organism than the endogenous gene.
[0039] “Exogenously provided” describes a molecule provided to the culture media of a cell culture.
[0040] “Exopolysaccharide” means a polysaccharide that is secreted from a cell into the extracellular environment.
[0041] “Filtrate” means the portion of a tangential flow filtration sample that has passed through the filter.
[0042] “Fixed carbon source” means molecule(s) containing carbon that are present at ambient temperature and pressure in solid or liquid form.
[0043] “Glycopolymer” means a biologically produced molecule comprising at least two monosaccharides. Examples of glycopolymers include glycosylated proteins, polysaccharides, oligosaccharides, and disaccharides.
[0044] “Homogenate” means cell biomass that has been disrupted.
[0045] “Microalgae” means a single-celled organism that is capable of performing photosynthesis. Microalgae include obligate photoautotrophs, which cannot metabolize a fixed carbon source as energy, as well as heterotrophs, which can live solely off of light, solely off of a fixed carbon source, or a combination of the two.
[0046] “Naturally produced” describes a compound that is produced by a wild-type organism.
[0047] “Photobioreactor” means a waterproof container, at least part of which is at least partially transparent, allowing light to pass through, in which one or more microalgae cells are cultured. Photobioreactors may be sealed, as in the instance of a polyethylene bag, or may be open to the environment, as in the instance of a pond.
[0048] “Polysaccharide material” is a composition that contains more than one species of polysaccharide, and optionally contaminants such as proteins, lipids, and nucleic acids, such as, for example, a microalgal cell homogenate.
[0049] “Polysaccharide” means a compound or preparation containing one or more molecules that contain at least two saccharide molecules covalently linked. A “polysaccharide”, “endopolysaccharide” or “exopolysaccharide” can be a preparation of polymer molecules that have similar or identical repeating units but different molecular weights within the population.
[0050] “Port”, in the context of a photobioreactor, means an opening in the photobioreactor that allows influx or efflux of materials such as gases, liquids, and cells. Ports are usually connected to tubing leading to and/or from the photobioreactor.
[0051] “Red microalgae” means unicellular algae that is of the list of classes comprising Bangiophyceae, Florideophyceae, Goniotrichales, or is otherwise a member of the Rhodophyta.
[0052] “Retentate” means the portion of a tangential flow filtration sample that has not passed through the filter.
[0053] “Small molecule” means a molecule having a molecular weight of less than 2000 daltons, in some instances less than 1000 daltons, and in still other instances less than 500 daltons or less. Such molecules include, for example, heterocyclic compounds, carbocyclic compounds, sterols, amino acids, lipids, carotenoids and polyunsaturated fatty acids.
[0054] A molecule is “solvent available” when the molecule is isolated to the point at which it can be dissolved in a solvent, or sufficiently dispersed in suspension in the solvent such that it can be detected in the solution or suspension. For example, a polysaccharide is “solvent available” when it is sufficiently isolated from other materials, such as those with which it is naturally associated, such that the polysaccharide can be dissolved or suspended in an aqueous buffer and detected in solution using a dimethylmethylene blue (DMMB) or phenol:sulfuric acid assay. In the case of a high molecular weight polysaccharide containing hundreds or thousands of monosaccharides, part of the polysaccharide can be “solvent available” when it is on the outermost layer of a cell wall while other parts of the same polysaccharide molecule are not “solvent available” because they are buried within the cell wall. For example, in a culture of microalgae in which polysaccharide is present in the cell wall, there is little “solvent available” polysaccharide since most of the cell wall polysaccharide is sequestered within the cell wall and not available to solvent. However, when the cells are disrupted, e.g., by sonication, the amount of “solvent available” polysaccharide increases. The amount of “solvent accessible” polysaccharide before and after homogenization can be compared by taking two aliquots of equal volume of cells from the same culture, homogenizing one aliquot, and comparing the level of polysaccharide in solvent from the two aliquots using a DMMB assay. The amount of solvent accessible polysaccharide in a homogenate of cells can also be compared with that present in a quantity of cells of the same type in a different culture needed to generate the same amount of homogenate.
[0055] “Substantially free of protein” means compositions that are preferably of high purity and are substantially free of potentially harmful contaminants, including proteins (e.g., at least National Food (NF) grade, generally at least analytical grade, and more typically at least pharmaceutical grade). Compositions are at least 80, at least 90, at least 99 or at least 99.9% w/w pure of undesired contaminants such as proteins are substantially free of protein. To the extent that a given compound must be synthesized prior to use, the resulting product is typically substantially free of any potentially toxic agents, particularly any endotoxins, which may be present during the synthesis or purification process. Compositions are usually made under GMP conditions. Compositions for parenteral administration are usually sterile and substantially isotonic.
I. General
[0056] Polysaccharides form a heterogeneous group of polymers of different length and composition. They are constructed from monosaccharide residues that are linked by glycosidic bonds. Glycosidic linkages may be located between the C 1 (or C 2 ) of one sugar residue and the C 2 , C 3 , C 4 , C 5 or C 6 of the second residue. A branched sugar results if more than two types of linkage are present in single monosaccharide molecule.
[0057] Monosaccharides are simple sugars with multiple hydroxyl groups. Based on the number of carbons (e.g., 3, 4, 5, or 6) a monosaccharide is a triose, tetrose, pentose, or hexose. Pentoses and hexoses can cyclize, as the aldehyde or keto group reacts with a hydroxyl on one of the distal carbons. Examples of monosaccharides are galactose, glucose, and rhamnose.
[0058] Polysaccharides are molecules comprising a plurality of monosaccharides covalently linked to each other through glycosidic bonds. Polysaccharides consisting of a relatively small number of monosaccharide units, such as 10 or less, are sometimes referred to as oligosaccharides. The end of the polysaccharide with an anomeric carbon (C 1 ) that is not involved in a glycosidic bond is called the reducing end. A polysaccharide may consist of one monosaccharide type, known as a homopolymer, or two or more types of monosaccharides, known as a heteropolymer. Examples of homopolysaccharides are cellulose, amylose, inulin, chitin, chitosan, amylopectin, glycogen, and pectin. Amylose is a glucose polymer with α(1→4) glycosidic linkages. Amylopectin is a glucose polymer with α(1→4) linkages and branches formed by α(1→6) linkages. Examples of heteropolysaccharides are glucomannan, galactoglucomannan, xyloglucan, 4-O-methylglucuronoxylan, arabinoxylan, and 4-O-Methylglucuronoarabinoxylan.
[0059] Polysaccharides can be structurally modified both enzymatically and chemically. Examples of modifications include sulfation, phosphorylation, methylation, O-acetylation, fatty acylation, amino N-acetylation, N-sulfation, branching, and carboxyl lactonization.
[0060] Glycosaminoglycans are polysaccharides of repeating disaccharides. Within the disaccharides, the sugars tend to be modified, with acidic groups, amino groups, sulfated hydroxyl and amino groups. Glycosaminoglycans tend to be negatively charged, because of the prevalence of acidic groups. Examples of glycosaminoglycans are heparin, chondroitin, and hyaluronic acid.
[0061] Polysaccharides are produced in eukaryotes mainly in the endoplasmic reticulum (ER) and Golgi apparatus. Polysaccharide biosynthesis enzymes are usually retained in the ER, and amino acid motifs imparting ER retention have been identified (Gene. 2000 Dec. 31; 261(2):321-7). Polysaccharides are also produced by some prokaryotes, such as lactic acid bacteria.
[0062] Polysaccharides that are secreted from cells are known as exopolysaccharides. Many types of cell walls, in plants, algae, and bacteria, are composed of polysaccharides. The cell walls are formed through secretion of polysaccharides. Some species, including algae and bacteria, secrete polysaccharides that are released from the cells. In other words, these molecules are not held in association with the cells as are cell wall polysaccharides. Instead, these molecules are released from the cells. For example, cultures of some species of microalgae secrete exopolysaccharides that are suspended in the culture media.
II. Methods of Producing Polysaccharides
[0063] A. Cell Culture Methods: Microalgae
[0064] Polysaccharides can be produced by culturing microalgae. Examples of microalgae that can be cultured to produce polysaccharides are shown in Table 1. Also listed are references that enable the skilled artisan to culture the microalgae species under conditions sufficient for polysaccharide production. Also listed are strain numbers from various publicly available algae collections, as well as strains published in journals that require public dissemination of reagents as a prerequisite for publication.
[0000]
TABLE 1
Culture and
polysaccharide
Strain Number/
purification method
Monosaccharide
Species
Source
reference
Composition
Culture conditions
Porphyridium
UTEX 1 161
M. A. Guzman-Murillo
Xylose,
Cultures obtained from various sources and were
cruentum
and F. Ascencio., Letters
Glucose,
cultured in F/2 broth prepared with seawater
in Applied Microbiology
Galactose,
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
Glucoronic
distilled water depending on microalgae salt
acid
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Porphyridium
UTEX 161
Fabregas et al., Antiviral
Xylose,
Cultured in 80 ml glass tubes with aeration of
cruentum
Research 44(1999)-67-73
Glucose,
100 ml/min and 10% CO 2 , for 10 s every ten minutes
Galactose and
to maintain pH > 7.6. Maintained at 22° in 12:12
Glucoronic
Light/dark periodicity. Light at 152.3 umol/m2/s.
acid
Salinity 3.5% (nutrient enriched as Fabregas, 1984
modified in 4 mmol Nitrogen/L)
Porphyridium
UTEX 637
Dvir, Brit. J. of Nutrition
Xylose,
Outdoor cultivation for 21 days in artficial sea
sp.
(2000), 84, 469-476.
Glucose and
water in polyethylene sleeves. See Jones (1963)
[Review: S. Geresh
Galactose,
and Cohen & Malis Arad, 1989)
Biosource Technology 38
Methyl
(1991) 195-201]-
hexoses,
Huleihel, 2003, Applied
Mannose,
Spectoscopy, v57, No. 4
Rhamnose
2003
Porphyridium
SAG 2 111.79
Talyshinsky, Marina
xylose,
see Dubinsky et al. Plant Physio. And Biochem.
aerugineum
Cancer Cell Int'l 2002, 2;
glucose,
(192) 30: 409-414. Pursuant to Ramus_1972-->
Review: S. Geresh
galactose,
Axenic culutres are grown in MCYII liquid
Biosource Technology 38
methyl
medium at 25° C. and illuminated with Cool White
(1991) 195-201]1 See
hexoses
fluorescent tubes on a 16:8 hr light dark cycle.
Ramus_1972
Cells kept in suspension by agitation on a
gyrorotary shaker or by a stream of filtered air.
Porphyridium
strain 1380-1a
Schmitt D., Water
unknown
See cited reference
purpurpeum
Research
Volume 35, Issue 3,
March 2001, Pages 779-
785, Bioprocess Biosyst
Eng. 2002 April; 25(1): 35-
42. Epub 2002 Mar. 6
Chaetoceros
USCE 3
M. A. Guzman-Murillo
unknown
See cited reference
sp.
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Chlorella
USCE
M. A. Guzman-Murillo
unknown
See cited reference
autotropica
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Chlorella
UTEX 580
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
autotropica
Research 44(1999)-67-73
100 ml/min and 10% CO2, for 10 s every ten
minutes to maintain pH > 7.6. Maintained at 22° in
12:12 Light/dark periodicity. Light at 152.3
umol/m2/s. Salinity 3.5% (nutrient enriched as
Fabregas, 1984)
Chlorella
UTEX LB2074
M. A. Guzman-Murillo
Un known
Cultures obtained from various sources and were
capsulata
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Chlorella
GGMCC 4
S. Guzman, Phytotherapy
glucose,
Grown in 10 L of membrane filtered (0.24 um)
stigmatophora
Rscrh (2003) 17: 665-670
glucuronic
seawater and sterilized at 120° for 30 min and
acid, xylose,
enriched with Erd Schreiber medium. Cultures
ribose/fucose
maintained at 18 +/− 1° C. under constant 1% CO 2
bubbling.
Dunalliela
DCCBC 5
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
tertiolecta
Research 44(1999)-67-73
100 ml/min and 10% CO2, for 10 s every ten
minutes to maintain pH > 7.6. Maintained at 22° in
12:12 Light/dark periodicity. Light at 152.3
umol/m2/s. Salinity 3.5% (nutrient enriched as
Fabregas, 1984)
Dunalliela
DCCBC
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
bardawil
Research 44(1999)-67-73
100 ml/min and 10% CO2, for 10 s every ten
minutes to maintain pH > 7.6. Maintained at 22° in
12:12 Light/dark periodicity. Light at 152.3
umol/m 2 /s. Salinity 3.5% (nutrient enriched as
Fabregas, 1984)
Isochrysis
HCTMS 6
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
galbana var.
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
tahitiana
in Applied Microbiology
filtered through a 0.45 um millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Isochrysis
UTEX LB 987
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
galbana var.
Research 44(1999)-67-73
100 ml/min and 10% CO2, for 10 s every ten
Tiso
minutes to maintain pH > 7.6. Maintained at 22° in
12:12 Light/dark periodicity. Light at 152.3
umol/m 2 /s. Salinity 3.5% (nutrient enriched as
Fabregas, 1984)
Isochrysis sp.
CCMP 7
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Phaeodactylum
UTEX 642, 646,
M. A M. A. Guzman-
unknown
Cultures obtained from various sources and were
tricornutum
2089
Murillo and F. Ascencio.,
cultured in F/2 broth prepared with seawater
Letters in Applied
filtered through a 0.45 um Millipore filter or
Microbiology 2000, 30,
distilled water depending on microalgae salt
473-478
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Phaeodactylum
GGMCC
S. Guzman, Phytotherapy
glucose,
Grown in 10 L of membrane filtered (0.24 um)
tricornutum
Rscrh (2003) 17: 665-670
glucuronic
seawater and sterilized at 120° for 30 min and
acid, and
enriched with Erd Schreiber medium. Cultures
mannose
maintained at 18 +/− 1° C. under constant 1% CO2
bubbling.
Tetraselmis sp.
CCMP 1634-
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
1640; UTEX
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
2767
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Botrycoccus
UTEX 572 and
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
braunii
2441
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Cholorococcum
UTEX 105
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Hormotilopsis
UTEX 104
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
gelatinosa
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Neochloris
UTEX 1185
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
oleoabundans
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Ochromonas
UTEX L1298
M. A. Guzman-Murillo
unknown
Cultures obtained from various sources and were
Danica
and F. Ascencio., Letters
cultured in F/2 broth prepared with seawater
in Applied Microbiology
filtered through a 0.45 um Millipore filter or
2000, 30, 473-478
distilled water depending on microalgae salt
tolerance. Incubated at 25° C. in flasks and
illuminated with white fluorescent lamps.
Gyrodinium
KG03; KGO9;
Yim, Joung Han et. Al., J.
Homopolysaccharide of
Isolated from seawater collected from red-tide
impudicum
KGJO1
of Microbiol December 2004,
galactose w/2.96%
bloom in Korean coastal water. Maintained in f/2
305-14; Yim, J. H. (2000)
uronic acid
medium at 22° under circadian light at
Ph.D. Dissertations,
100 uE/m2/sec: dark cycle of 14 h: 10 h for 19 days.
University of Kyung Hee,
Selected with neomycin and/or cephalosporin
Seoul
20 ug/ml
Ellipsoidon sp.
See cited
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
references
Research 44(1999)-67-
100 ml/min and 10% CO2, for 10 s every ten
73; Lewin, R. A. Cheng,
minutes to maintain pH > 7.6. Maintained at 22° in
L., 1989. Phycologya 28,
12:12 Light/dark periodicity. Light at 152.3
96-108
umol/m2/s. Salinity 3.5% (nutrient enriched as
Fabregas, 1984)
Rhodella
UTEX 2320
Talyshinsky, Marina
unknown
See Dubinsky O. et al. Composition of Cell wall
reticulata
Cancer Cell Int'l 2002, 2
polysaccharide produced by unicellular red algae
Rhodella reticulata . 1992 Plant Physiology and
biochemistry 30: 409-414
Rhodella
UTEX LB 2506
Evans, L V., et al. J. Cell
Galactose,
Grown in either SWM3 medium or ASP12, MgCl2
maculata
Sci 16, 1-21(1974);
xylose,
supplement. 100 mls in 250 mls volumetric
EVANS, L. V. (1970).
glucuronic
Erlenmeyer flask with gentle shaking and 40001x
Br. phycol. J. 5, 1-13.
acid
Northern Light fluorescent light for 16 hours.
Gymnodinium
Oku-1
Sogawa, K., et al., Life
unknown
See cited reference
sp.
Sciences, Vol. 66, No. 16,
pp. PL 227-231 (2000)
AND Umermura, Ken:
Biochemical
Pharmacology 66 (2003)
481-487
Spirilina
UTEX LB 1926
Kaji, T et. Al., Life Sci
Na-Sp contains
See cited reference
platensis
2002 Mar. 8; 70(16): 1841-
two disaccharide
8 Schaeffer and Krylov
repeats:
(2000) Review-
Aldobiuronic acid
Ectoxicology and
and Acofriose +
Environmental Safety.
other minor
45, 208-227.
saccharides and
sodium ion
Cochlodinuium
Oku-2
Hasui., et. Al., Int. J. Bio.
mannose,
Precultures grown in 500 ml conicals containing
polykrikoides
Macromol. Volume 17
galactose,
300 mls ESM (?) at 21.5° C. for 14 days in
No. 5 1995.
glucose and
continuous light (3500 lux) in growth cabinet) and
uronic acid
then transferred to 5 liter conical flask containing 3
liters of ESM. Grown 50 days and then filtered thru
wortmann GFF filter.
Nostoc
PCC 8 7413,
Sangar, V K Applied
unknown
Growth in nitrogen fixing conditions in BG-11
muscorum
7936, 8113
Micro. (1972) & A. M.
medium in aerated cultures maintained in log phase
Burja et al Tetrahydron
for several months. 250 mL culture media that were
57 (2001) 937-9377;
disposed in a temperature controlled incubator and
Otero A., J Biotechnol.
continuously illuminated with 70 umol photon m − 2
2003 Apr. 24; 102(2): 143-
s − 1 at 30° C.
52
Cyanospira
See cited
A. M. Burja et al.
unknown
See cited reference
capsulata
references
Tetrahydron 57 (2001)
937-9377 & Garozzo, D.,
Carbohydrate Res. 1998
307 113-124; Ascensio,
F., Folia Microbiol
(Praha). 2004; 49(1): 64-
70., Cesaro, A., et al., Int
J Biol Macromol. 1990
April; 12(2): 79-84
Cyanothece sp.
ATCC 51142
Ascensio F., Folia
unknown
Maintained at 27° C. in ASN III medium with
Microbiol (Praha).
light/dark cycle of 16/8 h under fluorescent light of
2004; 49(1): 64-70.
3,000 lux light intensity. In Phillips each of 15
strains were grown photoautotrophically in
enriched seawater medium. When required the
amount of NaNO3 was reduced from 1.5 to 0.35
g/L. Strains axenically grown in an atmosphere of
95% air and 5% CO2 for 8 days under continuous
illumination. with mean photon flux of 30 umol
photon/m2/s for the first 3 days of growth and 80
umol photon/m/s
Chlorella
UTEX 343;
Cheng_2004 Journal of
unknown
See cited reference
pyrenoidosa
UTEX 1806
Medicinal Food 7(2)
146-152
Phaeodactylum
CCAP 1052/1A
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
tricornutum
Research 44(1999)-67-73
100 ml/min and 10% CO2, for 10 s every ten
minutes to maintain pH > 7.6. Maintained at 22° in
12:12 Light/dark periodicity. Light at 152.3
umol/m2/s. Salinity 3.5% (nutrient enriched as
Fabregas, 1984)
Chlorella
USCE
M. A. Guzman-Murillo
unknown
See cited reference
autotropica
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Chlorella sp.
CCM
M. A. Guzman-Murillo
unknown
See cited reference
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Dunalliela
USCE
M. A. Guzman-Murillo
unknown
See cited reference
tertiolecta
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Isochrysis
UTEX LB 987
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
galabana
Research 44(1999)-67-73
100 ml/min and 10% CO 2 , for 10 s every ten minutes
to maintain pH > 7.6. Maintained at 22° in 12:12
Light/dark periodicity. Light at 152.3 umol/m2/s.
Salinity 3.5% (nutrient enriched as Fabregas, 1984)
Tetraselmis
CCAP 66/1A-D
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
tetrathele
Research 44(1999)-67-73
100 ml/min and 10% CO 2 , for 10 s every ten minutes
to maintain pH > 7.6. Maintained at 22° in 12:12
Light/dark periodicity. Light at 152.3 umol/m2/s.
Salinity 3.5% (nutrient enriched as Fabregas, 1984)
Tetraselmis
UTEX LB 2286
M. A. Guzman-Murillo
unknown
See cited reference
suecica
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Tetraselmis
CCAP 66/4
Fabregas et al., Antiviral
unknown
Cultured in 80 ml glass tubes with aeration of
suecica
Research 44(1999)-67-73
100 ml/min and 10% CO 2 , for 10 s every ten minutes
and Otero and Fabregas-
to maintain pH > 7.6. Maintained at 22° in 12:12
Aquaculture 159 (1997)
Light/dark periodicity. Light at 152.3 umol/m2/s.
111-123.
Salinity 3.5% (nutrient enriched as Fabregas, 1984)
Botrycoccus
UTEX 2629
M. A. Guzman-Murillo
unknown
See cited reference
sudeticus
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Chlamydomonas
UTEX 729
Moore and Tisher
unknown
See cited reference
mexicana
Science. 1964 Aug.
7; 145: 586-7.
Dysmorphococcus
UTEX LB 65
M. A. Guzman-Murillo
unknown
See cited reference
globosus
and F. Ascencio., Letters
in Applied Microbiology
2000, 30, 473-478
Rhodella
UTEX LB 2320
S. Geresh et al., J
unknown
See cited reference
reticulata
Biochem. Biophys.
Methods 50 (2002) 179-
187 [Review: S. Geresh
Biosource Technology 38
(1991) 195-201]
Anabena
ATCC 29414
Sangar, V K Appl
In Vegative wall
See cited reference
cylindrica
Microbiol. 1972
where only 18%
November; 24(5): 732-4
is carbohydrate--
Glucose [35%],
mannose [50%],
galactose, xylose,
and fucose. In
heterocyst wall
where 73% is
carbohydrate--
Glucose 73% and
Mannose is 21%
with some
galactose and
xylose
Anabena flos -
A37; J M
Moore, B G [1965] Can J.
Glucose and
See cited reference and APPLIED
aquae
Kingsbury
Microbiol.
mannose
ENVIRONMENTAL MICROBIOLOGY, April
Laboratory,
December; 11(6): 877-85
1978, 718-723)
Cornell
University
Palmella
See cited
Sangar, V K Appl
unknown
See cited reference
mucosa
references
Microbiol. 1972
November; 24(5): 732-4;
Lewin R A., (1956) Can
J Microbiol. 2: 665-672;
Arch Mikrobiol. 1964
Aug. 17; 49: 158-66
Anacystis
PCC 6301
Sangar, V K Appl
Glucose,
See cited reference
nidulans
Microbiol. 1972
galactose,
November; 24(5): 732-4
mannose
Phormidium
See cited
Vicente-Garcia V. et al.,
Galactose,
Cultivated in 2 L BG-11 medium at 28° C. Acetone
94a
reference
Biotechnol Bioeng. 2004
Mannose,
was added to precipitate exopolysaccharide.
Feb. 5; 85(3): 306-10
Galacturonic
acid,
Arabinose,
and Ribose
Anabaenaopsis
1402/1 9
David K A, Fay P. Appl
unknown
See cited reference
circularis
Environ Microbiol. 1977
December; 34(6): 640-6
Aphanocapsa
MN-11
Sudo H., et al., Current
Rhamnose; mannose;
Cultured aerobically for 20 days in seawater-based
halophtia
Micrcobiology Vol. 30
fucose; galactose;
medium, with 8% NaCl, and 40 mg/L NaHPO4.
(1995), pp. 219-222
xylose; glucose
Nitrate changed the Exopolysaccharide content.
In ratio of:
Highest cell density was obtained from culture
15:53:3:3:25
supplemented with 100 mg/l NaNO 3 . Phosphorous
(40 mg/L) could be added to control the biomass
and exopolysaccharide concentration.
Aphanocapsa
See reference
De Philippis R et al., Sci
unknown
Incubated at 20 and 28° C. with artificial light at a
sp
Total Environ. 2005 Nov.
photon flux of 5-20 umol m −2 s −1 .
2;
Cylindrotheca
See reference
De Philippis R et al., Sci
Glucuronic acid,
Stock enriched cultures incubated at 20 and 28° C.
sp
Total Environ. 2005 Nov.
Galacturonic
with artificial light at a photon flux of 5-20 umol
2;
acid, Glucose,
m − 2 s − 1. Exopolysaccharide production done in
Mannose,
glass tubes containing 100 mL culture at 28° C. with
Arabinose,
continuous illumination at photon density of 5-10
Fructose and
uE m − 2 s − 1.
Rhamnose
Navicula sp
See reference
De Philippis R et al., Sci
Glucuronic acid,
Incubated at 20 and 28° C. with artificial light at a
Total Environ. 2005 Nov.
Galacturonic
photon flux of 5-20 umol m − 2 s − 1. EPS production
2;
acid, Glucose,
done in glass tubes containing 100 mL culture at
Mannose,
28° C. with continuous illumination at photon
Arabinose,
density of 5-10 uE m − 2 s − 1.
Fructose and
Rhamnose
Gloeocapsa sp
See reference
De Philippis R et al., Sci
unknown
Incubated at 20 and 28° C. with artifical light at a
Total Environ. 2005 Nov.
photon flux of 5-20 umol m − 2 s − 1.
2;
Leptolyngbya
See reference
De Philippis R et al., Sci
unknown
Incubated at 20 and 28° C. with artificial light at a
sp
Total Environ. 2005 Nov.
photon flux of 5-20 umol m − 2 s − 1.
2;
Symploca sp.
See reference
De Philippis R et al., Sci
unknown
Incubated at 20 and 28° C. with artificial light at a
Total Environ. 2005 Nov.
photon flux of 5-20 umol m − 2 s − 1.
2;
Synechocystis
PCC 6714/6803
Jurgens U J, Weckesser J.
Glucoseamine,
Photoautotrophically grown in BG-11 medium, pH
J Bacteriol. 1986
mannosamine,
7.5 at 25° C. Mass cultures prepared in a 12 liter
November; 168(2): 568-73
galactosamine,
fermentor and gassed by air and carbon dioxide at
mannose and
flow rates of 250 an d2.5 liters/h, with illumination
glucose
from white fluorescent lamps at a constant light
intensity of 5,000 lux.
Stauroneis
See reference
Lind, J L (1997) Planta
unknown
See cited reference
decipiens
203: 213-221
Achnanthes
Indiana
Holdsworth, R H., Cell
unknown
See cited reference
brevipes
University
Biol. 1968 June; 37(3): 831-
Culture
7
Collection
Achnanthes
Strain 330 from
Wang, Y., et al., Plant
unknown
See cited reference
longipes
National Institute
Physiol. 1997
for
April; 113(4): 1071-1080.
Environmental
Studies
[0065] Microalgae are preferably cultured in liquid media for polysaccharide production. Culture condition parameters can be manipulated to optimize total polysaccharide production as well as to alter the structure of polysaccharides produced by microalgae.
[0066] Microalgal culture media usually contains components such as a fixed nitrogen source, trace elements, a buffer for pH maintenance, and phosphate. Other components can include a fixed carbon source such as acetate or glucose, and salts such as sodium chloride, particularly for seawater microalgae. Examples of trace elements include zinc, boron, cobalt, copper, manganese, and molybdenum in, for example, the respective forms of ZnCl 2 , H 3 BO 3 , CoCl 2 .6H 2 O, CuCl 2 .2H 2 O, MnCl 2 .4H 2 O and (NH 4 ) 6 MO 7 O 24 .4H 2 O.
[0067] Some microalgae species can grow by utilizing a fixed carbon source such as glucose or acetate. Such microalgae can be cultured in bioreactors that do not allow light to enter. Alternatively, such microalgae can also be cultured in photobioreactors that contain the fixed carbon source and allow light to strike the cells. Such growth is known as heterotrophic growth. Any strain of microalgae, including those listed in Table 1, can be cultured in the presence of any one or more fixed carbon source including those listed in Tables 2 and 3.
[0000]
TABLE 2
2,3-Butanediol
2-Aminoethanol
2′-Deoxy Adenosine
3-Methyl Glucose
Acetic Acid
Adenosine
Adenosine-5′-Monophosphate
Adonitol
Amygdalin
Arbutin
Bromosuccinic Acid
Cis-Aconitic Acid
Citric Acid
D,L-Carnitine
D,L-Lactic Acid
D,L-α-Glycerol Phosphate
D-Alanine
D-Arabitol
D-Cellobiose
Dextrin
D-Fructose
D-Fructose-6-Phosphate
D-Galactonic Acid Lactone
D-Galactose
D-Galacturonic Acid
D-Gluconic Acid
D-Glucosaminic Acid
D-Glucose-6-Phosphate
D-Glucuronic Acid
D-Lactic Acid Methyl Ester
D-L-α-Glycerol Phosphate
D-Malic Acid
D-Mannitol
D-Mannose
D-Melezitose
D-Melibiose
D-Psicose
D-Raffinose
D-Ribose
D-Saccharic Acid
D-Serine
D-Sorbitol
D-Tagatose
D-Trehalose
D-Xylose
Formic Acid
Gentiobiose
Glucuronamide
Glycerol
Glycogen
Glycyl-LAspartic Acid
Glycyl-LGlutamic Acid
Hydroxy-LProline
i-Erythritol
Inosine
Inulin
Itaconic Acid
Lactamide
Lactulose
L-Alaninamide
L-Alanine
L-Alanylglycine
L-Alanyl-Glycine
L-Arabinose
L-Asparagine
L-Aspartic Acid
L-Fucose
L-Glutamic Acid
L-Histidine
L-Lactic Acid
L-Leucine
L-Malic Acid
L-Ornithine
LPhenylalanine
L-Proline
L-Pyroglutamic Acid
L-Rhamnose
L-Serine
L-Threonine
Malonic Acid
Maltose
Maltotriose
Mannan
m-Inositol
N-Acetyl-DGalactosamine
N-Acetyl-DGlucosamine
N-Acetyl-LGlutamic Acid
N-Acetyl-β-DMannosamine
Palatinose
Phenyethylamine
p-Hydroxy-Phenylacetic Acid
Propionic Acid
Putrescine
Pyruvic Acid
Pyruvic Acid Methyl Ester
Quinic Acid
Salicin
Sebacic Acid
Sedoheptulosan
Stachyose
Succinamic Acid
Succinic Acid
Succinic Acid Mono-Methyl-Ester
Sucrose
Thymidine
Thymidine-5′-Monophosphate
Turanose
Tween 40
Tween 80
Uridine
Uridine-5′-Monophosphate
Urocanic Acid
Water
Xylitol
α-Cyclodextrin
α-D-Glucose
α-D-Glucose-1-Phosphate
α-D-Lactose
α-Hydroxybutyric Acid
α-Keto Butyric Acid
α-Keto Glutaric Acid
α-Keto Valeric Acid
α-Ketoglutaric Acid
α-Ketovaleric Acid
α-Methyl-DGalactoside
α-Methyl-DGlucoside
α-Methyl-DMannoside
β-Cyclodextrin
β-Hydroxybutyric Acid
β-Methyl-DGalactoside
β-Methyl-D-Glucoside
γ-Amino Butyric Acid
γ-Hydroxybutyric Acid
[0000]
TABLE 3
(2-amino-3,4-dihydroxy-5-hydroxymethyl-1-cyclohexyl)glucopyranoside
(3,4-disinapoyl)fructofuranosyl-(6-sinapoyl)glucopyranoside
(3-sinapoyl)fructofuranosyl-(6-sinapoyl)glucopyranoside
1 reference
1,10-di-O-(2-acetamido-2-deoxyglucopyranosyl)-2-azi-1,10-decanediol
1,3-mannosylmannose
1,6-anhydrolactose
1,6-anhydrolactose hexaacetate
1,6-dichlorosucrose
1-chlorosucrose
1-desoxy-1-glycinomaltose
1-O-alpha-2-acetamido-2-deoxygalactopyranosyl-inositol
1-O-methyl-di-N-trifluoroacetyl-beta-chitobioside
1-propyl-4-O-beta galactopyranosyl-alpha galactopyranoside
2-(acetylamino)-4-O-(2-(acetylamino)-2-deoxy-4-O-sulfogalactopyranosyl)-2-deoxyglucose
2-(trimethylsilyl)ethyl lactoside
2,1′,3′,4′,6′-penta-O-acetylsucrose
2,2′-O-(2,2′-diacetamido-2,3,2′,3′-tetradeoxy-6,6′-di-O-(2-tetradecylhexadecanoyl)-
alpha,alpha′-trehalose-3,3′-diyl)bis(N-lactoyl-alanyl-isoglutamine)
2,3,6,2′,3′,4′,6′-hepta-O-acetylcellobiose
2,3′-anhydrosucrose
2,3-di-O-phytanyl-1-O-(mannopyranosyl-(2-sulfate)-(1-2)-glucopyranosyl)-sn-glycerol
2,3-epoxypropyl O-galactopyranosyl(1-6)galactopyranoside
2,3-isoprolylideneerthrofuranosyl 2,3-O-isopropylideneerythrofuranoside
2′,4′-dinitrophenyl 2-deoxy-2-fluoro-beta-xylobioside
2,5-anhydromannitol iduronate
2,6-sialyllactose
2-acetamido-2,4-dideoxy-4-fluoro-3-O-galactopyranosylglucopyranose
2-acetamido-2-deoxy-3-O-(gluco-4-enepyranosyluronic acid)glucose
2-acetamido-2-deoxy-3-O-rhamnopyranosylglucose
2-acetamido-2-deoxy-6-O-beta galactopyranosylgalactopyranose
2-acetamido-2-deoxyglucosylgalactitol
2-acetamido-3-O-(3-acetamido-3,6-dideoxy-beta-glucopyranosyl)-2-deoxy-galactopyranose
2-amino-6-O-(2-amino-2-deoxy-glucopyranosyl)-2-deoxyglucose
2-azido-2-deoxymannopyranosyl-(1,4)-rhamnopyranose
2-deoxy-6-O-(2,3-dideoxy-4,6-O-isopropylidene-2,3-(N-tosylepimino)mannopyranosyl)-4,5-
O-isopropylidene-1,3-di-N-tosylstreptamine
2-deoxymaltose
2-iodobenzyl-1-thiocellobioside
2-N-(4-benzoyl)benzoyl-1,3-bis(mannos-4-yloxy)-2-propylamine
2-nitrophenyl-2-acetamido-2-deoxy-6-O-beta galactopyranosyl-alpha galactopyranoside
2-O-(glucopyranosyluronic acid)xylose
2-O-glucopyranosylribitol-1-phosphate
2-O-glucopyranosylribitol-4′-phosphate
2-O-rhamnopyranosyl-rhamnopyranosyl-3-hydroxyldecanoyl-3-hydroxydecanoate
2-O-talopyranosylmannopyranoside
2-thiokojibiose
2-thiosophorose
3,3′-neotrehalosadiamine
3,6,3′,6′-dianhydro(galactopyranosylgalactopyranoside)
3,6-di-O-methyl-beta-glucopyranosyl-(1-4)-2,3-di-O-methyl-alpha-rhamnopyranose
3-amino-3-deoxyaltropyranosyl-3-amino-3-deoxyaltropyranoside
3-deoxy-3-fluorosucrose
3-deoxy-5-O-rhamnopyranosyl-2-octulopyranosonate
3-deoxyoctulosonic acid-(alpha-2-4)-3-deoxyoctulosonic acid
3-deoxysucrose
3-ketolactose
3-ketosucrose
3-ketotrehalose
3-methyllactose
3-O-(2-acetamido-6-O-(N-acetylneuraminyl)-2-deoxygalactosyl)serine
3-O-(glucopyranosyluronic acid)galactopyranose
3-O-beta-glucuronosylgalactose
3-O-fucopyranosyl-2-acetamido-2-deoxyglucopyranose
3′-O-galactopyranosyl-1-4-O-galactopyranosylcytarabine
3-O-galactosylarabinose
3-O-talopyranosylmannopyranoside
3-trehalosamine
4-(trifluoroacetamido)phenyl-2-acetamido-2-deoxy-4-O-beta-mannopyranosyl-beta-
glucopyranoside
4,4′,6,6′-tetrachloro-4,4′,6,6′-tetradeoxygalactotrehalose
4,6,4′,6′-dianhydro(galactopyranosylgalactopyranoside)
4,6-dideoxysucrose
4,6-O-(1-ethoxy-2-propenylidene)sucrose hexaacetate
4-chloro-4-deoxy-alpha-galactopyranosyl 3,4-anhydro-1,6-dichloro-1,6-dideoxy-beta-lyxo-
hexulofuranoside
4-glucopyranosylmannose
4-methylumbelliferylcellobioside
4-nitrophenyl 2-fucopyranosyl-fucopyranoside
4-nitrophenyl 2-O-alpha-D-galactopyranosyl-alpha-D-mannopyranoside
4-nitrophenyl 2-O-alpha-D-glucopyranosyl-alpha-D-mannopyranoside
4-nitrophenyl 2-O-alpha-D-mannopyranosyl-alpha-D-mannopyranoside
4-nitrophenyl 6-O-alpha-D-mannopyranosyl-alpha-D-mannopyranoside
4-nitrophenyl-2-acetamido-2-deoxy-6-O-beta-D-galactopyranosyl-beta-D-glucopyranoside
4-O-(2-acetamido-2-deoxy-beta-glucopyranosyl)ribitol
4-O-(2-amino-2-deoxy-alpha-glucopyranosyl)-3-deoxy-manno-2-octulosonic acid
4-O-(glucopyranosyluronic acid)xylose
4-O-acetyl-alpha-N-acetylneuraminyl-(2-3)-lactose
4-O-alpha-D-galactopyranosyl-D-galactose
4-O-galactopyranosyl-3,6-anhydrogalactose dimethylacetal
4-O-galactopyranosylxylose
4-O-mannopyranosyl-2-acetamido-2-deoxyglucose
4-thioxylobiose
4-trehalosamine
4-trifluoroacetamidophenyl 2-acetamido-4-O-(2-acetamido-2-deoxyglucopyranosyl)-2-
deoxymannopyranosiduronic acid
5-bromoindoxyl-beta-cellobioside
5′-O-(fructofuranosyl-2-1-fructofuranosyl)pyridoxine
5-O-beta-galactofuranosyl-galactofuranose
6 beta-galactinol
6(2)-thiopanose
6,6′-di-O-corynomycoloyl-alpha-mannopyranosyl-alpha-mannopyranoside
6,6-di-O-maltosyl-beta-cyclodextrin
6,6′-di-O-mycoloyl-alpha-mannopyranosyl-alpha-mannopyranoside
6-chloro-6-deoxysucrose
6-deoxy-6-fluorosucrose
6-deoxy-alpha-gluco-pyranosiduronic acid
6-deoxy-gluco-heptopyranosyl 6-deoxy-gluco-heptopyranoside
6-deoxysucrose
6-O-decanoyl-3,4-di-O-isobutyrylsucrose
6-O-galactopyranosyl-2-acetamido-2-deoxygalactose
6-O-galactopyranosylgalactose
6-O-heptopyranosylglucopyranose
6-thiosucrose
7-O-(2-amino-2-deoxyglucopyranosyl)heptose
8-methoxycarbonyloctyl-3-O-glucopyranosyl-mannopyranoside
8-O-(4-amino-4-deoxyarabinopyranosyl)-3-deoxyoctulosonic acid
allolactose
allosucrose
allyl 6-O-(3-deoxyoct-2-ulopyranosylonic acid)-(1-6)-2-deoxy-2-(3-
hydroxytetradecanamido)glucopyranoside 4-phosphate
alpha-(2-9)-disialic acid
alpha,alpha-trehalose 6,6′-diphosphate
alpha-glucopyranosyl alpha-xylopyranoside
alpha-maltosyl fluoride
aprosulate
benzyl 2-acetamido-2-deoxy-3-O-(2-O-methyl-beta-galactosyl)-beta-glucopyranoside
benzyl 2-acetamido-2-deoxy-3-O-beta fucopyranosyl-alpha-galactopyranoside
benzyl 2-acetamido-6-O-(2-acetamido-2,4-dideoxy-4-fluoroglucopyranosyl)-2-
deoxygalactopyranoside
benzyl gentiobioside
beta-D-galactosyl(1-3)-4-nitrophenyl-N-acetyl-alpha-D-galactosamine
beta-methylmelibiose
calcium sucrose phosphate
camiglibose
cellobial
cellobionic acid
cellobionolactone
Cellobiose
cellobiose octaacetate
cellobiosyl bromide heptaacetate
Celsior
chitobiose
chondrosine
Cristolax
deuterated methyl beta-mannobioside
dextrin maltose
D-glucopyranose, O-D-glucopyranosyl
Dietary Sucrose
difructose anhydride I
difructose anhydride III
difructose anhydride IV
digalacturonic acid
DT 5461
ediol
epilactose
epsilon-N-1-(1-deoxylactulosyl)lysine
feruloyl arabinobiose
floridoside
fructofuranosyl-(2-6)-glucopyranoside
FZ 560
galactosyl-(1-3)galactose
garamine
gentiobiose
geranyl 6-O-alpha-L-arabinopyranosyl-beta-D-glucopyranoside
geranyl 6-O-xylopyranosyl-glucopyranoside
glucosaminyl-1,6-inositol-1,2-cyclic monophosphate
glucosyl (1-4) N-acetylglucosamine
glucuronosyl(1-4)-rhamnose
heptosyl-2-keto-3-deoxyoctonate
inulobiose
Isomaltose
isomaltulose
isoprimeverose
kojibiose
lactobionic acid
lacto-N-biose II
Lactose
lactosylurea
Lactulose
laminaribiose
lepidimoide
leucrose
levanbiose
lucidin 3-O-beta-primveroside
LW 10121
LW 10125
LW 10244
maltal
maltitol
Maltose
maltose hexastearate
maltose-maleimide
maltosylnitromethane heptaacetate
maltosyltriethoxycholesterol
maltotetraose
Malun 25
mannosucrose
mannosyl-(1-4)-N-acetylglucosaminyl-(1-N)-urea
mannosyl(2)-N-acetyl(2)-glucose
melibionic acid
Melibiose
melibiouronic acid
methyl 2-acetamido-2-deoxy-3-O-(alpha-idopyranosyluronic acid)-4-O-sulfo-beta-
galactopyranoside
methyl 2-acetamido-2-deoxy-3-O-(beta-glucopyranosyluronic acid)-4-O-sulfo-beta-
galactopyranoside
methyl 2-acetamido-2-deoxy-3-O-glucopyranosyluronoylglucopyranoside
methyl 2-O-alpha-rhamnopyranosyl-beta-galactopyranoside
methyl 2-O-beta-rhamnopyranosyl-beta-galactopyranoside
methyl 2-O-fucopyranosylfucopyranoside 3 sulfate
methyl 2-O-mannopyranosylmannopyranoside
methyl 2-O-mannopyranosyl-rhamnopyranoside
methyl 3-O-(2-acetamido-2-deoxy-6-thioglucopyranosyl)galactopyranoside
methyl 3-O-galactopyranosylmannopyranoside
methyl 3-O-mannopyranosylmannopyranoside
methyl 3-O-mannopyranosyltalopyranoside
methyl 3-O-talopyranosyltalopyranoside
methyl 4-O-(6-deoxy-manno-heptopyranosyl)galactopyranoside
methyl 6-O-acetyl-3-O-benzoyl-4-O-(2,3,4,6-tetra-O-benzoylgalactopyranosyl)-2-deoxy-2-
phthalimidoglucopyranoside
methyl 6-O-mannopyranosylmannopyranoside
methyl beta-xylobioside
methyl fucopyranosyl(1-4)-2-acetamido-2-deoxyglucopyranoside
methyl laminarabioside
methyl O-(3-deoxy-3-fluorogalactopyranosyl)(1-6)galactopyranoside
methyl-2-acetamido-2-deoxyglucopyranosyl-1-4-glucopyranosiduronic acid
methyl-2-O-fucopyranosylfucopyranoside 4-sulfate
MK 458
N(1)-2-carboxy-4,6-dinitrophenyl-N(6)-lactobionoyl-1,6-hexanediamine
N-(2,4-dinitro-5-fluorophenyl)-1,2-bis(mannos-4′-yloxy)propyl-2-amine
N-(2′-mercaptoethyl)lactamine
N-(2-nitro-4-azophenyl)-1,3-bis(mannos-4′-yloxy)propyl-2-amine
N-(4-azidosalicylamide)-1,2-bis(mannos-4′-yloxy)propyl-2-amine
N,N-diacetylchitobiose
N-acetylchondrosine
N-acetyldermosine
N-acetylgalactosaminyl-(1-4)-galactose
N-acetylgalactosaminyl-(1-4)-glucose
N-acetylgalactosaminyl-1-4-N-acetylglucosamine
N-acetylgalactosaminyl-1-4-N-acetylglucosamine
N-acetylgalactosaminyl-alpha(1-3)galactose
N-acetylglucosamine-N-acetylmuramyl-alanyl-isoglutaminyl-alanyl-glycerol dipalmitoyl
N-acetylglucosaminyl beta(1-6)N-acetylgalactosamine
N-acetylglucosaminyl-1-2-mannopyranose
N-acetylhyalobiuronic acid
N-acetylneuraminoyllactose
N-acetylneuraminoyllactose sulfate ester
N-acetylneuraminyl-(2-3)-galactose
N-acetylneuraminyl-(2-6)-galactose
N-benzyl-4-O-(beta-galactopyranosyl)glucamine-N-carbodithioate
neoagarobiose
N-formylkansosaminyl-(1-3)-2-O-methylrhamnopyranose
O-((Nalpha)-acetylglucosamine 6-sulfate)-(1-3)-idonic acid
O-(4-O-feruloyl-alpha-xylopyranosyl)-(1-6)-glucopyranose
O-(alpha-idopyranosyluronic acid)-(1-3)-2,5-anhydroalditol-4-sulfate
O-(glucuronic acid 2-sulfate)-(1--3)-O-(2,5)-andydrotalitol 6-sulfate
O-(glucuronic acid 2-sulfate)-(1--4)-O-(2,5)-anhydromannitol 6-sulfate
O-alpha-glucopyranosyluronate-(1-2)-galactose
O-beta-galactopyranosyl-(1-4)-O-beta-xylopyranosyl-(1-0)-serine
octyl maltopyranoside
O-demethylpaulomycin A
O-demethylpaulomycin B
O-methyl-di-N-acetyl beta-chitobioside
Palatinit
paldimycin
paulomenol A
paulomenol B
paulomycin A
paulomycin A2
paulomycin B
paulomycin C
paulomycin D
paulomycin E
paulomycin F
phenyl 2-acetamido-2-deoxy-3-O-beta-D-galactopyranosyl-alpha-D-galactopyranoside
phenyl O-(2,3,4,6-tetra-O-acetylgalactopyranosyl)-(1-3)-4,6-di-O-acetyl-2-deoxy-2-
phthalimido-1-thioglucopyranoside
poly-N-4-vinylbenzyllactonamide
pseudo-cellobiose
pseudo-maltose
rhamnopyranosyl-(1-2)-rhamnopyranoside-(1-methyl ether)
rhoifolin
ruberythric acid
S-3105
senfolomycin A
senfolomycin B
solabiose
SS 554
streptobiosamine
Sucralfate
Sucrose
sucrose acetate isobutyrate
sucrose caproate
sucrose distearate
sucrose monolaurate
sucrose monopalmitate
sucrose monostearate
sucrose myristate
sucrose octaacetate
sucrose octabenzoic acid
sucrose octaisobutyrate
sucrose octasulfate
sucrose polyester
sucrose sulfate
swertiamacroside
T-1266
tangshenoside I
tetrahydro-2-((tetrahydro-2-furanyl)oxy)-2H-pyran
thionigerose
Trehalose
trehalose 2-sulfate
trehalose 6,6′-dipalmitate
trehalose-6-phosphate
trehalulose
trehazolin
trichlorosucrose
tunicamine
turanose
U 77802
U 77803
xylobiose
xylose-glucose
xylosucrose
[0068] Microalgae contain photosynthetic machinery capable of metabolizing photons, and transferring energy harvested from photons into fixed chemical energy sources such as monosaccharide. Glucose is a common monosaccharide produced by microalgae by metabolizing light energy and fixing carbon from carbon dioxide. Some microalgae can also grow in the absence of light on a fixed carbon source that is exogenously provided (for example see Plant Physiol. 2005 February; 137(2):460-74). In addition to being a source of chemical energy, monosaccharides such as glucose are also substrate for production of polysaccharides (see Example 14). The invention provides methods of producing polysaccharides with novel monosaccharide compositions. For example, microalgae is cultured in the presence of culture media that contains exogenously provided monosaccharide, such as glucose. The monosaccharide is taken up by the cell by either active or passive transport and incorporated into polysaccharide molecules produced by the cell. This novel method of polysaccharide composition manipulation can be performed with, for example, any microalgae listed in Table 1 using any monosaccharide or disaccharide listed in Tables 2 or 3.
[0069] In some embodiments, the fixed carbon source is one or more selected from glucose, galactose, xylose, mannose, rhamnose, N-acetylglucosamine, glycerol, floridoside, and glucuronic acid. The methods may be practiced cell growth in the presence of at least about 5.0 μM, at least about 10 μM, at least about 15.0 μM, at least about 20.0 μM, at least about 25.0 μM, at least about 30.0 μM, at least about 35.0 μM, at least about 40.0 μM, at least about 45.0 μM, at least about 50.0 μM, at least about 55.0 μM, at least about 60.0 μM, at least about 75.0 μM, at least about 80.0 μM, at least about 85.0 μM, at least about 90.0 μM, at least about 95.0 μM, at least about 100.0 μM, or at least about 150.0 μM, of one or more exogenously provided fixed carbon sources selected from Tables 2 and 3.
[0070] In some embodiments using cells of the genus Porphyridium , the methods include the use of approximately 0.5-0.75% glycerol as a fixed carbon source when the cells are cultured in the presence of light. Alternatively, a range of glycerol, from approximately 4.0% to approximately 9.0% may be used when the Porphyridium cells are cultured in the dark, more preferably from 5.0% to 8.0%, and more preferably 7.0%.
[0071] After culturing the microalgae in the presence of the exogenously provided carbon source, the monosaccharide composition of the polysaccharide can be analyzed as described in Example 5.
[0072] Microalgae culture media can contain a fixed nitrogen source such as KNO 3 . Alternatively, microalgae are placed in culture conditions that do not include a fixed nitrogen source. For example, Porphyridium sp. cells are cultured for a first period of time in the presence of a fixed nitrogen source, and then the cells are cultured in the absence of a fixed nitrogen source (see for example Adda M., Biomass 10:131-140. (1986); Sudo H., et al., Current Microbiology Vol. 30 (1995), pp. 219-222; Marinho-Soriano E., Bioresour Technol. 2005 February; 96(3):379-82; Bioresour. Technol. 42:141-147 (1992)).
[0073] Other culture parameters can also be manipulated, such as the pH of the culture media, the identity and concentration of trace elements such as those listed in Table 3, and other media constituents.
[0074] Microalgae can be grown in the presence of light. The number of photons striking a culture of microalgae cells can be manipulated, as well as other parameters such as the wavelength spectrum and ratio of dark:light hours per day. Microalgae can also be cultured in natural light, as well as simultaneous and/or alternating combinations of natural light and artificial light. For example, microalgae of the genus Chlorella be cultured under natural light during daylight hours and under artificial light during night hours.
[0075] The gas content of a photobioreactor can be manipulated. Part of the volume of a photobioreactor can contain gas rather than liquid. Gas inlets can be used to pump gases into the photobioreactor. Any gas can be pumped into a photobioreactor, including air, air/CO 2 mixtures, noble gases such as argon and others. The rate of entry of gas into a photobioreactor can also be manipulated. Increasing gas flow into a photobioreactor increases the turbidity of a culture of microalgae. Placement of ports conveying gases into a photobioreactor can also affect the turbidity of a culture at a given gas flow rate. Air/CO 2 mixtures can be modulated to generate different polysaccharide compositions by manipulating carbon flux. For example, air:CO 2 mixtures of about 99.75% air:0.25% CO 2 , about 99.5% air:0.5% CO 2 , about 99.0% air:1.00% CO 2 , about 98.0% air:2.0% CO 2 , about 97.0% air:3.0% CO 2 , about 96.0% air:4.0% CO 2 , and about 95.00% air:5.0% CO 2 can be infused into a bioreactor or photobioreactor.
[0076] Microalgae cultures can also be subjected to mixing using devices such as spinning blades and propellers, rocking of a culture, stir bars, and other instruments.
[0077] B. Cell Culture Methods: Photobioreactors
[0078] Microalgae can be grown and maintained in closed photobioreactors made of different types of transparent or semitransparent material. Such material can include Plexiglas® enclosures, glass enclosures, bags bade from substances such as polyethylene, transparent or semitransparent pipes, and other materials. Microalgae can also be grown in open ponds.
[0079] Photobioreactors can have ports allowing entry of gases, solids, semisolids and liquids into the chamber containing the microalgae. Ports are usually attached to tubing or other means of conveying substances. Gas ports, for example, convey gases into the culture. Pumping gases into a photobioreactor can serve to both feed cells CO 2 and other gases and to aerate the culture and therefore generate turbidity. The amount of turbidity of a culture varies as the number and position of gas ports is altered. For example, gas ports can be placed along the bottom of a cylindrical polyethylene bag. Microalgae grow faster when CO 2 is added to air and bubbled into a photobioreactor. For example, a 5% CO 2 :95% air mixture is infused into a photobioreactor containing cells of the genus Porphyridium (see for example Biotechnol Bioeng. 1998 Sep. 20; 59(6):705-13; textbook from office; U.S. Pat. Nos. 5,643,585 and 5,534,417; Lebeau, T., et. al. Appl. Microbiol. Biotechnol (2003) 60:612-623; Muller-Fuega, A., Journal of Biotechnology 103 (2003 153-163; Muller-Fuega, A., Biotechnology and Bioengineering, Vol. 84, No. 5, Dec. 5, 2003; Garcia-Sanchez, J. L., Biotechnology and Bioengineering, Vol. 84, No. 5, Dec. 5, 2003; Garcia-Gonzales, M., Journal of Biotechnology, 115 (2005) 81-90. Molina Grima, E., Biotechnology Advances 20 (2003) 491-515).
[0080] Photobioreactors can be exposed to one or more light sources to provide microalgae with light as an energy source via light directed to a surface of the photobioreactor. Preferably the light source provides an intensity that is sufficient for the cells to grow, but not so intense as to cause oxidative damage or cause a photoinhibitive response. In some instances a light source has a wavelength range that mimics or approximately mimics the range of the sun. In other instances a different wavelength range is used. Photobioreactors can be placed outdoors or in a greenhouse or other facility that allows sunlight to strike the surface. Preferred photon intensities for species of the genus Porphyridium are between 50 and 300 uE m −2 s −1 (see for example Photosynth Res. 2005 June; 84(1-3):21-7).
[0081] Photobioreactor preferably have one or more parts that allow media entry. It is not necessary that only one substance enter or leave a port. For example, a port can be used to flow culture media into the photobioreactor and then later can be used for sampling, gas entry, gas exit, or other purposes. In some instances a photobioreactor is filled with culture media at the beginning of a culture and no more growth media is infused after the culture is inoculated. In other words, the microalgal biomass is cultured in an aqueous medium for a period of time during which the microalgae reproduce and increase in number; however quantities of aqueous culture medium are not flowed through the photobioreactor throughout the time period. Thus in some embodiments, aqueous culture medium is not flowed through the photobioreactor after inoculation.
[0082] In other instances culture media can be flowed though the photobioreactor throughout the time period during which the microalgae reproduce and increase in number. In some instances media is infused into the photobioreactor after inoculation but before the cells reach a desired density. In other words, a turbulent flow regime of gas entry and media entry is not maintained for reproduction of microalgae until a desired increase in number of said microalgae has been achieved, but instead a parameter such as gas entry or media entry is altered before the cells reach a desired density.
[0083] Photobioreactors preferably have one or more ports that allow gas entry. Gas can serve to both provide nutrients such as CO 2 as well as to provide turbulence in the culture media. Turbulence can be achieved by placing a gas entry port below the level of the aqueous culture media so that gas entering the photobioreactor bubbles to the surface of the culture. One or more gas exit ports allow gas to escape, thereby preventing pressure buildup in the photobioreactor. Preferably a gas exit port leads to a “one-way” valve that prevents contaminating microorganisms to enter the photobioreactor. In some instances cells are cultured in a photobioreactor for a period of time during which the microalgae reproduce and increase in number, however a turbulent flow regime with turbulent eddies predominantly throughout the culture media caused by gas entry is not maintained for all of the period of time. In other instances a turbulent flow regime with turbulent eddies predominantly throughout the culture media caused by gas entry can be maintained for all of the period of time during which the microalgae reproduce and increase in number. In some instances a predetermined range of ratios between the scale of the photobioreactor and the scale of eddies is not maintained for the period of time during which the microalgae reproduce and increase in number. In other instances such a range can be maintained.
[0084] Photobioreactors preferably have at least one port that can be used for sampling the culture. Preferably a sampling port can be used repeatedly without altering compromising the axenic nature of the culture. A sampling port can be configured with a valve or other device that allows the flow of sample to be stopped and started. Alternatively a sampling port can allow continuous sampling. Photobioreactors preferably have at least one port that allows inoculation of a culture. Such a port can also be used for other purposes such as media or gas entry.
[0085] Microalgae that produce polysaccharides can be cultured in photobioreactors. Microalgae that produce polysaccharide that is not attached to cells can be cultured for a period of time and then separated from the culture media and secreted polysaccharide by methods such as centrifugation and tangential flow filtration. Preferred organisms for culturing in photobioreactors to produce polysaccharides include Porphyridium sp., Porphyridium cruentum, Porphyridium purpureum, Porphyridium aerugineum, Rhodella maculata, Rhodella reticulata, Chlorella autotrophica, Chlorella stigmatophora, Chlorella capsulata, Achnanthes brevipes and Achnanthes longipes.
[0086] C. Non-Microalgal Polysaccharide Production
[0087] Organisms besides microalgae can be used to produce polysaccharides, such as lactic acid bacteria (see for example Stinglee, F., Molecular Microbiology (1999) 32(6), 1287-1295; Ruas_Madiedo, P., J. Dairy Sci. 88:843-856 (2005); Laws, A., Biotechnology Advances 19 (2001) 597-625; Xanthan gum bacteria: Pollock, T J., J. Ind. Microbiol. Biotechnol., 1997 August; 19(2):92-7.; Becker, A., Appl. Micrbiol. Bio/technol. 1998 August; 50(2):92-7; Garcia-Ochoa, F., Biotechnology Advances 18 (2000) 549-579., seaweed: Talarico, L B., et al., Antiviral Research 66 (2005) 103-110; Dussealt, J., et al., J Biomed Mater Res A., (2005) Novl; Melo, F. R., J Biol Chem 279:20824-35 (2004)).
[0088] D. Ex Vivo Methods
[0089] Microalgae and other organisms can be manipulated to produce polysaccharide molecules that are not naturally produced by methods such as feeding cells with monosaccharides that are not produced by the cells (Nature. 2004 Aug. 19; 430(7002):873-7). For example, species listed in Table I are grown according to the referenced growth protocols, with the additional step of adding to the culture media a fixed carbon source that is not in the culture media as published and referenced in Table 1 and is not produced by the cells in a detectable amount.
[0090] E. In Vitro Methods
[0091] Polysaccharides can be altered by enzymatic and chemical modification. For example, carbohydrate modifying enzymes can be added to a preparation of polysaccharide and allowed to catalyze reactions that alter the structure of the polysaccharide. Chemical methods can be used to, for example, modify the sulfation pattern of a polysaccharide (see for example Carbohydr. Polym. 63:75-80 (2000); Pomin V H., Glycobiology. 2005 December; 15(12):1376-85; Naggi A., Semin Thromb Hemost. 2001 October; 27(5):437-43 Review; Habuchi, O., Glycobiology. 1996 January; 6(1); 51-7; Chen, J., J. Biol. Chem. In press; Geresh., S et al., J. Biochem. Biophys. Methods 50 (2002) 179-187.).
[0092] F. Polysaccharide Purification Methods
[0093] Exopolysaccharides can be purified from microalgal cultures by various methods, including those disclosed herein.
[0094] Precipitation
[0095] For example, polysaccharides can be precipitated by adding compounds such as cetylpyridinium chloride, isopropanol, ethanol, or methanol to an aqueous solution containing a polysaccharide in solution. Pellets of precipitated polysaccharide can be washed and resuspended in water, buffers such as phosphate buffered saline or Tris, or other aqueous solutions (see for example Farias, W. R. L., et al., J. Biol. Chem. (2000) 275; (38)29299-29307; U.S. Pat. No. 6,342,367; U.S. Pat. No. 6,969,705).
[0096] Dialysis
[0097] Polysaccharides can also be dialyzed to remove excess salt and other small molecules (see for example Gloaguen, V., et al., Carbohydr Res. 2004 Jan. 2; 339(1):97-103; Microbiol Immunol. 2000; 44(5):395-400.).
[0098] Tangential Flow Filtration
[0099] Filtration can be used to concentrate polysaccharide and remove salts. For example, tangential flow filtration (TFF), also known as cross-flow filtration, can be used (see for example Millipore Pellicon® device, used with 1000 kD membrane (catalog number P2C01MC01); Geresh, Carb. Polym. 50; 183-189 (2002)). It is preferred that the polysaccharides do not pass through the filter at a significant level. It is also preferred that polysaccharides do not adhere to the filter material. TFF can also be performed using hollow fiber filtration systems.
[0100] Non-limiting examples of tangential flow filtration include use of a filter with a pore size of at least about 0.1 micrometer, at least about 0.12 micrometer, at least about 0.14 micrometer, at least about 0.16 micrometer, at least about 0.18 micrometer, at least about 0.2 micrometer, at least about 0.22 micrometer, or at least about 0.45 micrometer. Preferred pore sizes of TFF allow contaminants to pass through but not polysaccharide molecules.
[0101] Ion Exchange Chromatography
[0102] Anionic polysaccharides can be purified by anion exchange chromatography. (Jacobsson, I., Biochem J. 1979 Apr. 1; 179(1):77-89; Karamanos, N K., Eur J. Biochem. 1992 Mar. 1; 204(2):553-60).
[0103] Protease Treatment
[0104] Polysaccharides can be treated with proteases to degrade contaminating proteins. In some instances the contaminating proteins are attached, either covalently or noncovalently to polysaccharides. In other instances the polysaccharide molecules are in a preparation that also contains proteins. Proteases can be added to polysaccharide preparations containing proteins to degrade proteins (for example, the protease from Streptomyces griseus can be used (SigmaAldrich catalog number P5147). After digestion, the polysaccharide is preferably purified from residual proteins, peptide fragments, and amino acids. This purification can be accomplished, for example, by methods listed above such as dialysis, filtration, and precipitation.
[0105] Heat treatment can also be used to eliminate proteins in polysaccharide preparations (see for example Biotechnol Lett. 2005 January; 27(1): 13-8; FEMS Immunol Med. Microbiol. 2004 Oct. 1; 42(2):155-66; Carbohydr Res. 2000 Sep. 8; 328(2):199-207; J Biomed Mater Res. 1999; 48(2): 111-6.; Carbohydr Res. 1990 Oct. 15; 207(1): 101-20).
[0106] The invention thus includes production of an exopolysaccharide comprising separating the exopolysaccharide from contaminants after proteins attached to the exopolysaccharide have been degraded or destroyed. The proteins may be those attached to the exopolysaccharide during culture of a microalgal cell in media, which is first separated from the cells prior to proteolysis or protease treatment. The cells may be those of the genus Porphyridium as a non-limiting example.
[0107] In one non-limiting example, a method of producing an exopolysaccharide is provided wherein the method comprises culturing cells of the genus Porphyridium ; separating cells from culture media; destroying protein attached to the exopolysaccharide present in the culture media; and separating the exopolysaccharide from contaminants. In some methods, the contaminant(s) are selected from amino acids, peptides, proteases, protein fragments, and salts. In other methods, the contaminant is selected from NaCl, MgSO 4 , MgCl 2 , CaCl 2 , KNO 3 , KH 2 PO 4 , NaHCO 3 , Tris, ZnCl 2 , H 3 BO 3 , CoCl 2 , CuCl 2 , MnCl 2 , (NH 4 ) 6 Mo 7 O 24 , FeCl3 and EDTA.
[0108] Drying Methods
[0109] After purification of methods such as those above, polysaccharides can be dried using methods such as lyophilization and heat drying (see for example Shastry, S., Brazilian Journal of Microbiology (2005) 36:57-62; Matthews K H., Int J. Pharm. 2005 Jan. 31; 289(1-2):51-62. Epub 2004 Dec. 30; Gloaguen, V., et al., Carbohydr Res. 2004 Jan. 2; 339(1):97-103).
[0110] Tray dryers accept moist solid on trays. Hot air (or nitrogen) is circulated to dry. Shelf dryers can also employ reduced pressure or vacuum to dry at room temperature when products are temperature sensitive and are similar to a freeze-drier but less costly to use and can be easily scaled-up.
[0111] Spray dryers are relatively simple in operation, which accept feed in fluid state and convert it into a dried particulate form by spraying the fluid into a hot drying medium.
[0112] Rotary dryers operate by continuously feeding wet material, which is dried by contact with heated air, while being transported along the interior of a rotating cylinder, with the rotating shell acting as the conveying device and stirrer.
[0113] Spin flash dryers are used for drying of wet cake, slurry, or paste which is normally difficult to dry in other dryers. The material is fed by a screw feeder through a variable speed drive into the vertical drying chamber where it is heated by air and at the same time disintegrated by a specially designed disintegrator. The heating of air may be direct or indirect depending upon the application. The dry powder is collected through a cyclone separator/bag filter or with a combination of both.
[0114] Whole Cell Extraction
[0115] Intracellular polysaccharides and cell wall polysaccharides can be purified from whole cell mass (see form example U.S. Pat. No. 4,992,540; U.S. Pat. No. 4,810,646; J Sietsma J H., et al., Gen Microbiol. 1981 July; 125(1):209-12; Fleet G H, Manners D J., J Gen Microbiol. 1976 May; 94(1):180-92).
[0116] G. Microalgae Homogenization Methods
[0117] A pressure disrupter pumps of a slurry through a restricted orifice valve. High pressure (up to 1500 bar) is applied, followed by an instant expansion through an exiting nozzle. Cell disruption is accomplished by three different mechanisms: impingement on the valve, high liquid shear in the orifice, and sudden pressure drop upon discharge, causing an explosion of the cell. The method is applied mainly for the release of intracellular molecules. According to Hetherington et al., cell disruption (and consequently the rate of protein release) is a first-order process, described by the relation: log[Rm/(Rm−R)]=K N P72.9. R is the amount of soluble protein; Rm is the maximum amount of soluble protein K is the temperature dependent rate constant; N is the number of passes through the homogenizer (which represents the residence time). P is the operating pressure.
[0118] In a ball mill, cells are agitated in suspension with small abrasive particles. Cells break because of shear forces, grinding between beads, and collisions with beads. The beads disrupt the cells to release biomolecules. The kinetics of biomolecule release by this method is also a first-order process.
[0119] Another widely applied method is the cell lysis with high frequency sound that is produced electronically and transported through a metallic tip to an appropriately concentrated cellular suspension, ie: sonication. The concept of ultrasonic disruption is based on the creation of cavities in cell suspension.
[0120] Blending (high speed or Waring), the french press, or even centrifugation in case of weak cell walls, also disrupt the cells by using the same concepts.
[0121] Cells can also be ground after drying in devices such as a colloid mill.
[0122] Because the percentage of polysaccharide as a function of the dry weight of a microalgae cell can frequently be in excess of 50%, microalgae cell homogenates can be considered partially pure polysaccharide compositions. Cell disruption aids in increasing the amount of solvent-accessible polysaccharide by breaking apart cell walls that are largely composed of polysaccharide.
[0123] Homogenization as described herein can increase the amount of solvent-available polysaccharide significantly. For example, homogenization can increase the amount of solvent-available polysaccharide by at least a factor of 0.25, at least a factor of 0.5, at least a factor of 1, at least a factor of 2, at least a factor of 3, at least a factor of 4, at least a factor of 5, at least a factor of 8, at least a factor of 10, at least a factor of 15, at least a factor of 20, at least a factor of 25, and at least a factor of 30 or more compared to the amount of solvent-available polysaccharide in an identical or similar quantity of non-homogenized cells of the same type. One way of determining a quantity of cells sufficient to generate a given quantity of homogenate is to measure the amount of a compound in the homogenate and calculate the gram quantity of cells required to generate this amount of the compound using known data for the amount of the compound per gram mass of cells. The quantity of many such compounds per gram of particular microalgae cells are know. For examples, see FIG. 7 . Given a certain quantity of a compound in a composition, the skilled artisan can determine the number of grams of intact cells necessary to generate the observed amount of the compound. The number of grams of microalgae cells present in the composition can then be used to determine if the composition contains at least a certain amount of solvent-available polysaccharide sufficient to indicate whether or not the composition contains homogenized cells, such as for example five times the amount of solvent-available polysaccharide present in a similar or identical quantity of unhomogenized cells.
[0124] H. Analysis Methods
[0125] Assays for detecting polysaccharides can be used to quantitate starting polysaccharide concentration, measure yield during purification, calculate density of secreted polysaccharide in a photobioreactor, measure polysaccharide concentration in a finished product, and other purposes.
[0126] The phenol: sulfuric acid assay detects carbohydrates (see Hellebust, Handbook of Phycological Methods, Cambridge University Press, 1978; and Cuesta G., et al., J Microbiol Methods. 2003 January; 52(1):69-73). The 1,6 dimethylmethylene blue assay detects anionic polysaccharides. (see for example Braz J Med Biol Res. 1999 May; 32(5):545-50; Clin Chem. 1986 November; 32(11):2073-6).
[0127] Polysaccharides can also be analyzed through methods such as HPLC, size exclusion chromatography, and anion exchange chromatography (see for example Prosky L, Asp N, Schweizer T F, DeVries J W & Furda I (1988) Determination of insoluble, soluble and total dietary fiber in food and food products: Interlaboratory study. Journal of the Association of Official Analytical Chemists 71, 1017±1023; Int J Biol Macromol. 2003 November; 33(1-3):9-18)
[0128] Polysaccharides can also be detected using gel electrophoresis (see for example Anal Biochem. 2003 Oct. 15; 321(2):174-82; Anal Biochem. 2002 Jan. 1; 300(1):53-68).
[0129] Monosaccharide analysis of polysaccharides can be performed by combined gas chromatography/mass spectrometry (GC/MS) of the per-O-trimethylsilyl (TMS) derivatives of the monosaccharide methyl glycosides produced from the sample by acidic methanolysis (see Merkle and Poppe (1994) Methods Enzymol. 230:1-15; York, et al. (1985) Methods Enzymol. 118:3-40).
III. Compositions
[0130] A. General
[0131] Compositions of the invention include a microalgal polysaccharide or homogenate as described herein. In embodiments relating to polysaccharides, including exopolysaccharides, the composition may comprise a homogenous or a heterogeneous population of polysaccharide molecules, including sulfated polysaccharides as non-limiting embodiments. Non-limiting examples of homogenous populations include those containing a single type of polysaccharide molecule, such as that with the same structure and molecular weight. Non-limiting examples of heterogeneous populations include those containing more than one type of polysaccharide molecule, such as a mixture of polysaccharides having a molecular weight (MW) within a range or a MW above or below a MW value. For example, the Porphyridium sp. exopolysaccharide is typically produced in a range of sizes from 3-5 million Daltons. Of course a polysaccharide containing composition of the invention may be optionally protease treated, or reduced in the amount of protein, as described above.
[0132] In some embodiments, a composition of the invention may comprise one or more polysaccharides produced by microalgae that have not been recombinantly modified. The microalgae may be those which are naturally occurring or those which have been maintained in culture in the absence of alteration by recombinant DNA techniques or genetic engineering.
[0133] In other embodiments, the polysaccharides are those from modified microalgae, such as, but not limited to, microalgae modified by recombinant techniques. Non-limiting examples of such techniques include introduction and/or expression of an exogenous nucleic acid sequence encoding a gene product; genetic manipulation to decrease or inhibit expression of an endogenous microalgal gene product; and/or genetic manipulation to increase expression of an endogenous microalgal gene product. The invention contemplates recombinant modification of the various microalgae species described herein. In some embodiments, the microalgae is from the genus Porphyridium.
[0134] Polysaccharides provided by the invention that are produced by genetically modified microalgae or microalgae that are provided with an exogenous carbon source can be distinct from those produced by microalgae cultured in minimal growth media under photoautotrophic conditions (ie: in the absence of a fixed carbon source) at least in that they contain a different monosaccharide content relative to polysaccharides from unmodified microalgae or microalgae cultured in minimal growth media under photoautotrophic conditions. Non-limiting examples include polysaccharides having an increased amount of arabinose (Ara), rhamnose (Rha), fucose (Fuc), xylose (Xyl), glucuronic acid (GlcA), galacturonic acid (GalA), mannose (Man), galactose (Gal), glucose (Glc), N-acetyl galactosamine (GalNAc), N-acetyl glucosamine (GlcNAc), and/or N-acetyl neuraminic acid (NANA), per unit mass (or per mole) of polysaccharide, relative to polysaccharides from either non-genetically modified microalgae or microalgae cultured photoautotrophically. An increased amount of a monosaccharide may also be expressed in terms of an increase relative to other monosaccharides rather than relative to the unit mass, or mole, of polysaccharide. In some instances the culture can be in the dark, where the monosaccharide, such as glucose, is used as the sole energy source for the cell. In other instances the culture is in the light, where the cells undergo photosynthesis and therefore produce monosaccharides such as glucose in the chloroplast and transport the monosaccharides into the cytoplasm. Novel polysaccharides produced by non-genetically engineered microalgae can therefore be generated by nutritional manipulation, ie: exogenously providing carbohydrates in the culture media that are taken up through endogenous transport mechanisms. Uptake of the exogenously provided carbohydrates can be induced, for example, by culturing the cells in the dark, thereby forcing the cells to utilize the exogenously provided carbon source. For example, Porphyridium cells cultured in the presence of 7% glycerol in the dark produce a novel polysaccharide because the intracellular carbon flux under these nutritionally manipulated conditions is different from that under photosynthetic conditions. By altering the identity and concentration of monosaccharides in the cytoplasm of the microalgae, through nutritional manipulation, the invention provides novel polysaccharides. Nutritional manipulation can also be performed, for example, by culturing the microalgae in the presence of high amounts of sulfate, as described herein. In some instances nutritional manipulation includes addition of one or more exogenously provided carbon sources as well as one or more other non-carbohydrate culture component, such as 50 mM MgSO 4 .
[0135] In some embodiments, the increase in one or more of the above listed monosaccharides in a polysaccharide may be from below to above detectable levels and/or by at least about 5%, to at least about 2000%, relative to a polysaccharide produced from the same microalgae in the absence of genetic or nutritional manipulation. Therefore an increase in one or more of the above monosaccharides, or other carbohydrates listed in Tables 2 or 3, by at least about 10%, at least about 15%, at least about 20%, at least about 25%, at least about 30%, at least about 35%, at least about 40%, at least about 45%, at least about 50%, at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 100%, at least about 105%, at least about 110%, at least about 150%, at least about 200%, at least about 250%, at least about 300%, at least about 350%, at least about 400%, at least about 450%, at least about 500%, at least about 550%, at least about 600%, at least about 650%, at least about 700%, at least about 750%, at least about 800%, at least about 850%, at least about 900%, at least about 1000%, at least about 1100%, at least about 1200%, at least about 1300%, at least about 1400%, at least about 1500%, at least about 1600%, at least about 1700%, at least about 1800%, or at least about 1900%, or more, may be used in the practice of the invention.
[0136] In cases wherein the polysaccharides from unmodified microalgae do not contain one or more of the above monosaccharides, the presence of the monosaccharide in a microalgal polysaccharide indicates the presence of a polysaccharide distinct from that in unmodified microalgae. Thus using particular strains of Porphyridium sp. and Porphyridium cruentum as non-limiting examples, the invention includes modification of these microalgae to incorporate arabinose and/or fucose, because polysaccharides from two strains of these species do not contain detectable amounts of these monosaccharides (see Example 5 herein). In another non-limiting example, the modification of Porphyridium sp. to produce polysaccharides containing a detectable amount of glucuronic acid, galacturonic acid, or N-acetyl galactosamine, or more than a trace amount of N-acetyl glucosamine, is specifically included in the instant disclosure. In a further non-limiting example, the modification of Porphyridium cruentum to produce polysaccharides containing a detectable amount of rhamnose, mannose, or N-acetyl neuraminic acid, or more than a trace amount of N-acetyl-glucosamine, is also specifically included in the instant disclosure.
[0137] Put more generally, the invention includes a method of producing a polysaccharide comprising culturing a microalgae cell in the presence of at least about 0.01 micromolar of an exogenously provided fixed carbon compound, wherein the compound is incorporated into the polysaccharide produced by the cell. In some embodiments, the compound is selected from Table 2 or 3. The cells may optionally be selected from the species listed in Table 1, and cultured by modification, using the methods disclosed herein, or the culture conditions also lusted in Table 1.
[0138] In some embodiments, the cell is selected from Table 1, such as where the cell is of the genus Porphyridium , as a non-limiting example. In some cases, the cell is selected from Porphyridium sp. and Porphyridium cruentum . Embodiments include those wherein the polysaccharide is enriched for the at least one monosaccharide compared to an endogenous polysaccharide produced by a non-transgenic cell of the same species. The monosaccharide may be selected from Arabinose, Fructose, Galactose, Glucose, Mannose, Xylose, Glucuronic acid, Glucosamine, Galactosamine, Rhamnose and N-acetyl glucosamine.
[0139] These methods of the invention are facilitated by use of non-transgenic cell expressing a sugar transporter, optionally wherein the transporter has a lower K m for glucose than at least one monosaccharide selected from the group consisting of galactose, xylose, glucuronic acid, mannose, and rhamnose. In other embodiments, the transporter has a lower K m for galactose than at least one monosaccharide selected from the group consisting of glucose, xylose, glucuronic acid, mannose, and rhamnose. In additional embodiments, the transporter has a lower K m for xylose than at least one monosaccharide selected from the group consisting of glucose, galactose, glucuronic acid, mannose, and rhamnose. In further embodiments, the transporter has a lower K m for glucuronic acid than at least one monosaccharide selected from the group consisting of glucose, galactose, xylose, mannose, and rhamnose. In yet additional embodiments, the transporter has a lower K m for mannose than at least one monosaccharide selected from the group consisting of glucose, galactose, xylose, glucuronic acid, and rhamnose. In yet further embodiments, the transporter has a lower K m for rhamnose than at least one monosaccharide selected from the group consisting of glucose, galactose, xylose, glucuronic acid, and mannose. Manipulation of the concentration and identity of monosaccharides provided in the culture media, combined with use of transporters that have a different K m for different monosaccharides, provides novel polysaccharides. These general methods can also be used in cells other than microalgae, for example, bacteria that produce polysaccharides.
[0140] In alternative embodiments, the cell is cultured in the presence of at least two monosaccharides, both of which are transporter by the transporter. In some cases, the two monosaccharides are any two selected from glucose, galactose, xylose, glucuronic acid, rhamnose and mannose.
[0141] In some aspects, the invention includes a novel microalgal polysaccharide, such as from microalgae of the genus Porphyridium , comprising detectable amounts of xylose, glucose, and galactose wherein the molar amount of one or more of these three monosaccharides in the polysaccharide is not present in a polysaccharide of Porphyridium that is not genetically or nutritionally modified. An example of a non-nutritionally and non-genetically modified Porphyridium polysaccharide can be found, for example, in Jones R., Journal of Cellular Comparative Physiology 60; 61-64 (1962). In some embodiments, the amount of glucose, in the polysaccharide, is at least about 65% of the molar amount of galactose in the same polysaccharide. In other embodiments, glucose is at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 100%, at least about 105%, at least about 110%, at least about 120%, at least about 130%, at least about 140%, at least about 150%, at least about 200%, at least about 250%, at least about 300%, at least about 350%, at least about 400%, at least about 450%, at least about 500%, or more, of the molar amount of galactose in the polysaccharide. Further embodiments of the invention include those wherein the amount of glucose in a microalgal polysaccharide is equal to, or approximately equal to, the amount of galactose (such that the amount of glucose is about 100% of the amount of galactose). Moreover, the invention includes microalgal polysaccharides wherein the amount of glucose is more than the amount of galactose.
[0142] Alternatively, the amount of glucose, in the polysaccharide, is less than about 65% of the molar amount of galactose in the same polysaccharide. The invention thus provides for polysaccharides wherein the amount of glucose is less than about 60%, less than about 55%, less than about 50%, less than about 45%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5% of the molar amount of galactose in the polysaccharide.
[0143] In other aspects, the invention includes a microalgal polysaccharide, such as from microalgae of the genus Porphyridium , comprising detectable amounts of xylose, glucose, galactose, mannose, and rhamnose, wherein the molar amount of one or more of these five monosaccharides in the polysaccharide is not present in a polysaccharide of non-genetically modified and/or non-nutritionally modified microalgae. In some embodiments, the amount of rhamnose in the polysaccharide is at least about 100% of the molar amount of mannose in the same polysaccharide. In other embodiments, rhamnose is at least about 110%, at least about 120%, at least about 130%, at least about 140%, at least about 150%, at least about 200%, at least about 250%, at least about 300%, at least about 350%, at least about 400%, at least about 450%, or at least about 500%, or more, of the molar amount of mannose in the polysaccharide. Further embodiments of the invention include those wherein the amount of rhamnose in a microalgal polysaccharide is more than the amount of mannose on a molar basis.
[0144] Alternatively, the amount of rhamnose, in the polysaccharide, is less than about 75% of the molar amount of mannose in the same polysaccharide. The invention thus provides for polysaccharides wherein the amount of rhamnose is less than about 70%, less than about 65%, less than about 60%, less than about 55%, less than about 50%, less than about 45%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5% of the molar amount of mannose in the polysaccharide.
[0145] In additional aspects, the invention includes a microalgal polysaccharide, such as from microalgae of the genus Porphyridium , comprising detectable amounts of xylose, glucose, galactose, mannose, and rhamnose, wherein the amount of mannose, in the polysaccharide, is at least about 130% of the molar amount of rhamnose in the same polysaccharide. In other embodiments, mannose is at least about 140%, at least about 150%, at least about 200%, at least about 250%, at least about 300%, at least about 350%, at least about 400%, at least about 450%, or at least about 500%, or more, of the molar amount of rhamnose in the polysaccharide.
[0146] Alternatively, the amount of mannose, in the polysaccharide, is equal to or less than the molar amount of rhamnose in the same polysaccharide. The invention thus provides for polysaccharides wherein the amount of mannose is less than about 95%, less than about 90%, less than about 85%, less than about 80%, less than about 75%, less than about 70%, less than about 65%, less than about 60%, less than about 60%, less than about 55%, less than about 50%, less than about 45%, less than about 40%, less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5% of the molar amount of rhamnose in the polysaccharide.
[0147] In further aspects, the invention includes a microalgal polysaccharide, such as from microalgae of the genus Porphyridium , comprising detectable amounts of xylose, glucose, and galactose, wherein the amount of galactose in the polysaccharide, is at least about 100% of the molar amount of xylose in the same polysaccharide. In other embodiments, rhamnose is at least about 105%, at least about 110%, at least about 120%, at least about 130%, at least about 140%, at least about 150%, at least about 200%, at least about 250%, at least about 300%, at least about 350%, at least about 400%, at least about 450%, or at least about 500%, or more, of the molar amount of mannose in the polysaccharide. Further embodiments of the invention include those wherein the amount of galactose in a microalgal polysaccharide is more than the amount of xylose on a molar basis.
[0148] Alternatively, the amount of galactose, in the polysaccharide, is less than about 55% of the molar amount of xylose in the same polysaccharide. The invention thus provides for polysaccharides wherein the amount of galactose is less than about 50%, less than about 45%, less than about 40%, less than about 35%; less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5% of the molar amount of xylose in the polysaccharide.
[0149] In yet additional aspects, the invention includes a microalgal polysaccharide, such as from microalgae of the genus Porphyridium , comprising detectable amounts of xylose, glucose, glucuronic acid and galactose, wherein the molar amount of one or more of these five monosaccharides in the polysaccharide is not present in a polysaccharide of unmodified microalgae. In some embodiments, the amount of glucuronic acid, in the polysaccharide, is at least about 50% of the molar amount of glucose in the same polysaccharide. In other embodiments, glucuronic acid is at least about 55%, at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, at least about 100%, at least about 105%, at least about 110%, at least about 120%, at least about 130%, at least about 140%, at least about 150%, at least about 200%, at least about 250%, at least about 300%, at least about 350%, at least about 400%, at least about 450%, or at least about 500%, or more, of the molar amount of glucose in the polysaccharide. Further embodiments of the invention include those wherein the amount of glucuronic acid in a microalgal polysaccharide is more than the amount of glucose on a molar basis.
[0150] In other embodiments, the exopolysaccharide, or cell homogenate polysaccharide, comprises glucose and galactose wherein the molar amount of glucose in the exopolysaccharide, or cell homogenate polysaccharide, is at least about 55% of the molar amount of galactose in the exopolysaccharide or polysaccharide. Alternatively, the molar amount of glucose in the exopolysaccharide, or cell homogenate polysaccharide, is at least about 60%, at least about 65%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 100% of the molar amount of galactose in the exopolysaccharide or polysaccharide.
[0151] In yet further aspects, the invention includes a microalgal polysaccharide, such as from microalgae of the genus Porphyridium , comprising detectable amounts of xylose, glucose, glucuronic acid, galactose, at least one monosaccharide selected from arabinose, fucose, N-acetyl galactosamine, and N-acetyl neuraminic acid, or any combination of two or more of these four monosaccharides.
IV. Cosmeceutical Compositions and Topical Application
[0152] A. General
[0153] Compositions, comprising polysaccharides, whole cell extracts, or mixtures of polysaccharides and whole cell extracts, are provided for topical application or non-systemic administration. The polysaccharide may be any one or more of the microalgal polysaccharides disclosed herein, including those produced by a species, or a combination of two or more species, in Table 1. Similarly, a whole cell extract may be that prepared from a microalgal species, or a combination of two or more species, in Table 1. In some embodiments, polysaccharides, such as exopolysaccharides, and cell extracts from microalgae of the genus Porphyridium are used in the practice of the invention. A composition of the invention may comprise from between about 0.001% and about 100%, about 0.01% and about 90%, about 0.1% and about 80%, about 1% and about 70%, about 2% and about 60%, about 4% and about 50%, about 6% and about 40%, about 7% and about 30%, about 8% and about 20%, or about 10% polysaccharide, cell extract, by weight.
[0154] Topical compositions are usually formulated with a carrier, such as in an ointment or a cream, and may optionally include a fragrance. One non-limiting class of topical compositions is that of cosmeceuticals. Other non-limiting examples of topical formulations include gels, solutions, impregnated bandages, liposomes, or biodegradable microcapsules as well as lotions, sprays, aerosols, suspensions, dusting powder, impregnated bandages and dressings, biodegradable polymers, and artificial skin. Another non-limiting example of a topical formulation is that of an ophthalmic preparation. Carriers for topical administration of the compounds of this invention include, but are not limited to, mineral oil, liquid petroleum, white petroleum, propylene glycol, polyoxyethylene polyoxypropylene compound, emulsifying wax and water. Alternatively, the composition can be formulated with a suitable lotion or cream containing the active compound suspended or dissolved in a carrier. Suitable carriers include, but are not limited to, mineral oil, sorbitan monostearate, polysorbate 60, cetyl esters wax, cetearyl alcohol, 2-octyldodecanol, benzyl alcohol and water.
[0155] In some embodiments, the polysaccharides contain fucose moieties. In other embodiments, the polysaccharides are sulfated, such as exopolysaccharides from microalgae of the genus Porphyridium . In some embodiments, the polysaccharides will be those from a Porphyridium species, such as one that has been subject to genetic and/or nutritional manipulation to produce polysaccharides with altered monosaccharide content and/or altered sulfation.
[0156] In additional embodiments, a composition of the invention comprises a microalgal cell homogenate and a topical carrier. In some embodiments, the homogenate may be that of a species listed in Table 1 or may be material produced by a species in the table.
[0157] In further embodiments, a composition comprising purified microalgal polysaccharide and a carrier suitable for topical administration also contains a fusion (or chimeric) protein associated with the polysaccharide. In some embodiments, the fusion protein comprises a first protein, or polypeptide region, with at least about 60% amino acid identity with the protein of SEQ ID NO: 15. In other embodiments, the first protein has at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 98%, or higher, amino acid identity with the sequence of SEQ ID NO:15.
[0158] The fusion protein may comprise a second protein, or polypeptide region, with a homogenous or heterologous sequence. Non-limiting examples of the second protein include an antibody and an enzyme. In optional embodiments, the enzyme is superoxide dismutase, such as that has at least about 60% amino acid identity with the sequence of SEQ ID NO: 12 or SEQ ID NO: 13 as non-limiting examples. In some embodiments, the superoxide dismutase has at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 98%, or higher, amino acid identity with the sequence of SEQ ID NO:12 or 13.
[0159] In other embodiments, the second protein is an antibody. Non-limiting examples of antibodies for use in this aspect of the invention include an antibody that selectively binds to an antigen from a pathogen selected from HIV, Herpes Simplex Virus, gonorrhea, Chlamydia, Human Papillomavirus, and Trichomoniasis. In some embodiments, the antibody is a humanized antibody.
[0160] B. Methods of Formulation
[0161] Polysaccharide compositions for topical application can be formulated by first preparing a purified preparation of polysaccharide. As a non-limiting example, the polysaccharide from aqueous growth media is precipitated with an alcohol, resuspended in a dilute buffer, and mixed with a carrier suitable for application to human skin or mucosal tissue, including the vaginal canal. Alternatively, the polysaccharide can be purified from growth media and concentrated by tangential flow filtration or other filtration methods, and formulated as described above. Intracellular polysaccharides can be also formulated in a similar or identical manner after purification from other cellular components.
[0162] As a non-limiting example, the invention includes a method of formulating a cosmeceutical composition, said method comprising culturing microalgal cells in suspension under conditions to allow cell division; separating the microalgal cells from culture media, wherein the culture media contains exopolysaccharide molecules produced by the microalgal cells; separating the exopolysaccharide molecules from other molecules present in the culture media; homogenizing the microalgal cells; and adding the separated exopolysaccharide molecules to the cells before, during, or after homogenization. In some embodiments, the microalgal cells are from the genus Porphyridium.
[0163] Examples of polysaccharides, both secreted and intracellular, that are suitable for formulation with a carrier for topical application are listed in Table I.
[0164] In further embodiments, polysaccharide is associated with a fusion (or chimeric) protein comprising a first protein (or polypeptide region) with at least about 60% amino acid identity with the protein of SEQ ID NO: 15. In some cases, the first protein has at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 98%, or higher, amino acid identity with the sequence of SEQ ID NO:28.
[0165] The fusion protein may comprise a second protein, or polypeptide region, with a homogenous or heterologous sequence. One non-limiting example of the second protein is a superoxide dismutase enzyme.
[0166] Examples of carriers suitable for formulating polysaccharide are described above. Ratios of homogenate:carrier are typically in the range of about 0.001:1 to about 1:1 (volume:volume), although the invention comprises ratios outside of this range, such as, but not limited to, about 0.01:1 and about 0.1:1.
[0167] Microalgal cellular extracts can also be formulated for topical administration. It is preferable but not necessary that the cells are physically or chemically disrupted as part of the formulation process. For example, cells can be centrifuged from culture, washed with a buffer such as 1.0 mM phosphate buffered saline, pH 7.4, and sonicated. Preferably the cells are sonicated until the cell walls have been substantially disrupted, as can be determined under a microscope. For example, Porphyridium sp. cells can be sonicated using a Misonix sonicator as described in Example 3.
[0168] Cells can also be dried and ground using means such as mortar and pestle, colloid milling, ball milling, or other physical method of breaking cell walls.
[0169] After cell disruption, cell homogenate can be formulated with carrier and fragrance as described above for polysaccharides.
[0170] C. Co-Administered Compositions
[0171] Topical compositions can comprise a portion of a complete composition sold as a single unit. Other portions of the complete compositions can comprise an oral supplement intended for administration as part of a regime for altering skin appearance. Because the top layers of the skin contain dead cells, nutrients delivered via capillaries cannot reach the outer layers of cells. The outer layers of cells must be provided with nutrients though topical administration. However, topical administration is not always an effective method of providing nutrients to deep layers of skin that contain living cells. The compositions provided herein comprise both topical compositions that contain algal polysaccharides and/or cellular extracts as well as oral compositions comprising nutraceutical molecules such as purified polysaccharides, whole cell extracts, carotenoids, polyunsaturated fatty acids, and other molecules that are delivered to the skin via capillaries. The combined effect of the topical and oral administration of these molecules and extracts provides a benefit to skin health that is additive or synergistic compared to the use of only a topical or only an orally delivered product.
[0172] Examples of the topical components of the composition include exopolysaccharide from Porphyridium cruentum, Porphyridium sp., list others. Other components of the topical composition can include polysaccharides and/or cell extracts from species listed in Table I.
[0173] Cellular extracts for topical administration can also include cellular homogenates from microalgae that have been genetically engineered. For example, homogenates of Porphyridium sp. that have been engineered to express an exogenous gene encoding superoxide dismutase can be formulated for topical administration. Other genes that can be expressed include carotenoid biosynthesis enzymes and polyunsaturated fatty acid biosynthesis enzymes.
[0174] Examples of compositions for oral administration include one or more of the following: DHA, EPA, ARA, lineoileic acid, lutein, lycopene, beta carotene, braunixanthin, zeaxanthin, astaxanthin, linoleic acid, alpha carotene, vitamin C and superoxide dismutase. Compositions for oral administration usually include a carrier such as those described above. Oral compositions can be formulated in tablet or capsule form. Oral compositions can also be formulated in an ingestible form such as a food, tea, liquid, etc. Oral compositions can, for example, comprise at least 50 micrograme, at least 100 micrograme, at least 50 milligrams, at least 100 milligrams, at least 500 milligrams, and at least one gram of a small molecule such as a carotenoids or a polyunsaturated fatty acid.
[0175] In another aspect, the invention includes orally administered nutraceutical compositions comprising one or more polysaccharides, or microalgal cell extract or homogenate, of the invention. A nutraceutical composition serves as a nutritional supplement upon consumption. In other embodiments, a nutraceutical may be bioactive and serve to affect, alter, or regulate a bioactivity of an organism.
[0176] A nutraceutical may be in the form of a solid or liquid formulation. In some embodiments, a solid formulation includes a capsule or tablet formulation as described above. In other embodiments, a solid nutraceutical may simply be a dried microalgal extract or homogenate, as well as dried polysaccharides per se. In liquid formulations, the invention includes suspensions, as well as aqueous solutions, of polysaccharides, extracts, or homogenates.
[0177] The methods of the invention include a method of producing a nutraceutical composition. Such a method may comprise drying a microalgal cell homogenate or cell extract. The homogenate may be produced by disruption of microalgae which has been separated from culture media used to propagate (or culture) the microalgae Thus in one non-limiting example, a method of the invention comprises culturing red microalgae; separating the microalgae from culture media; disrupting the microalgae to produce a homogenate; and drying the homogenate. In similar embodiments, a method of the invention may comprise drying one or more polysaccharides produced by the microalgae.
[0178] In some embodiments, a method of the invention comprises drying by tray drying, spin drying, rotary drying, spin flash drying, or lyophilization. In other embodiments, methods of the invention comprise disruption of microalgae by a method selected from pressure disruption, sonication, and ball milling
[0179] In additional embodiments, a method of the invention further comprises formulation of the homogenate, extract, or polysaccharides with a carrier suitable for human consumption. As described herein, the formulation may be that of tableting or encapsulation of the homogenate or extract.
[0180] In further embodiments, the methods comprise the use of microalgal homogenates, extracts, or polysaccharides wherein the cells contain an exogenous nucleic acid sequence, such as in the case of modified cells described herein. The exogenous sequence may encode a gene product capable of being expressed in the cells or be a sequence which increases expression of one or more endogenous microalgal gene product.
[0181] In a preferred embodiment, at the topical composition and the oral composition both contain at least one molecule in common. For example, the topical composition contains homogenate of Porphyridium cells that contain zeaxanthin, and the oral composition contains zeaxanthin. In another embodiment, the topical composition contains homogenate of Porphyridium cells that contain polysaccharide, and the oral composition contains polysaccharide purified from Porphyridium culture media.
[0182] The compositions described herein are packaged for sale as a single unit. For example, a unit for sale comprises a first container holding a composition for topical administration, a second container holding individual doses of a composition for oral administration, and optionally, directions for co-administration of the topical and oral composition.
[0183] Some embodiments of the invention include a combination product comprising 1) a first composition comprising a microalgal extract and a carrier suitable for topical application to skin; and 2) a second composition comprising at least one compound and a carrier suitable for human consumption; wherein the first and second compositions are packaged for sale as a single unit. Thus the invention includes co-packaging of the two compositions, optionally with a instructions and/or a label indicating the identity of the contents and/or their proper use.
[0184] Other combination products are including in the invention. In some embodiments, the first composition may be a topical formulation or non-systemic formulation, optionally a cosmeceutical, as described herein. Preferably, the first composition comprises a carrier suitable for topical application to skin, such as human skin. Non-limiting examples of the second composition include a food composition or nutraceutical as described herein. Preferably, the second composition comprises at least one carrier suitable for human consumption, such as that present in a food product or composition. Combination products of the invention may be packaged separately for subsequent use together by a user or packaged together to facilitate purchase and use by a consumer. Packaging of the first and second compositions may be for sale as a single unit.
[0185] D. Methods of Cosmetic Enhancement
[0186] In a further aspect, the invention includes a polysaccharide composition suitable for injection into skin to improve its appearance. In some embodiments, the injection is made to alleviate or eliminate wrinkles. In other embodiments, the treatment reduces the visible signs of aging and/or wrinkles.
[0187] As known to the skilled person, human skin, as it ages, gradually loses skin components that keep skin pliant and youthful-looking. The skin components include collagen, elastin, and hyaluronic acid, which have been the subject of interest and use to improve the appearance of aging skin.
[0188] The invention includes compositions of microalgal polysaccharides, microalgal cell extracts, and microalgal cell homogenates for use in the same manner as collagen and hyaluronic acid. In some embodiments, the polysaccharides will be those of from a Porphyridium species, such as one that has been subject to genetic and/or nutritional manipulation to produce polysaccharides with altered monosaccharide content and/or altered sulfation. In some embodiments, the polysaccharides are formulated as a fluid, optionally elastic and/or viscous, suitable for injection. The compositions may be used as injectable dermal fillers as one non-limiting example. The injections may be made into skin to fill-out facial lines and wrinkles. In other embodiments, the injections may be used for lip enhancement. These applications of polysaccharides are non-limiting examples of non-pharmacological therapeutic methods of the invention.
[0189] In further embodiments, the microalgal polysaccharides, cell extracts, and cell homogenates of the invention may be co-formulated with collagen and/or hyaluronic acid (such as the Restylane® and Hylaform® products) and injected into facial tissue. Non-limiting examples of such tissue include under the skin in areas of wrinkles and the lips. In a preferred embodiment, the polysaccharide is substantially free of protein. The injections may be repeated as deemed appropriate by the skilled practitioner, such as with a periodicity of about three, about four, about six, about nine, or about twelve months.
[0190] Thus the invention includes a method of cosmetic enhancement comprising injecting a polysaccharide produced by microalgae into mammalian skin. The injection may be of an effective amount to produce a cosmetic improvement, such as decreased wrinkling or decreased appearance of wrinkles as non-limiting examples. Alternatively, the injection may be of an amount which produces relief in combination with a series of additional injections. In some methods, the polysaccharide is produced by a microalgal species, or two or more species, listed in Table 1. In one non-limiting example, the microalgal species is of the genus Porphyridium and the polysaccharide is substantially free of protein.
[0191] The polysaccharide compositions may be in the form of a sterile injectable preparation, for example, as a sterile injectable aqueous or oleaginous suspension. This suspension may be formulated according to techniques known in the art using suitable dispersing or wetting agents (such as, for example, Tween 80) and suspending agents. The sterile injectable preparation may also be a sterile injectable solution or suspension in a non-toxic parenterally-acceptable diluent or solvent, for example, as a solution in 1,3-butanediol. Among the acceptable vehicles and solvents that may be employed are mannitol, water, Ringers solution and isotonic sodium chloride solution. In addition, sterile, fixed oils are conventionally employed as a solvent or suspending medium. For this purpose, any bland fixed oil may be employed including synthetic mono- or diglycerides. Fatty acids, such as oleic acid and its glyceride derivatives are useful in the preparation of injectables, as are natural pharmaceutically-acceptable oils, such as olive oil or castor oil, especially in their polyoxyethylated versions. These oil solutions or suspensions may also contain a long-chain alcohol diluent or dispersant such as Ph. Helv or a similar alcohol.
[0192] Sterile injectable polysaccharide compositions preferably contain less than 1% protein as a function of dry weight of the composition, more preferably less than 0.1% protein, more preferably less than 0.01% protein, less than 0.001% protein, less than 0.0001% protein, more preferably less than 0.00001% protein, more preferably less than 0.000001% protein.
V. Gene Expression in Microalgae
[0193] Genes can be expressed in microalgae by providing, for example, coding sequences in operable linkage with promoters.
[0194] An exemplary vector design for expression of a gene in microalgae contains a first gene in operable linkage with a promoter active in algae, the first gene encoding a protein that imparts resistance to an antibiotic or herbicide. Optionally the first gene is followed by a 3′ untranslated sequence containing a polyadenylation signal. The vector may also contain a second promoter active in algae in operable linkage with a second gene. The second gene can encode any protein, for example an enzyme that produces small molecules or a mammalian growth hormone that can be advantageously present in a nutraceutical.
[0195] It is preferable to use codon-optimized cDNAs: for methods of recoding genes for expression in microalgae, see for example US patent application 20040209256.
[0196] It has been shown that many promoters in expression vectors are active in algae, including both promoters that are endogenous to the algae being transformed algae as well as promoters that are not endogenous to the algae being transformed (ie: promoters from other algae, promoters from plants, and promoters from plant viruses or algae viruses). Example of methods for transforming microalgae, in addition to those demonstrated in the Examples section below, including methods comprising the use of exogenous and/or endogenous promoters that are active in microalgae, and antibiotic resistance genes functional in microalgae, have been described. See for example; Curr Microbiol. 1997 December; 35(6):356-62 ( Chlorella vulgaris ); Mar Biotechnol (NY). 2002 January; 4(1):63-73 ( Chlorella ellipsoidea ); Mol Gen Genet. 1996 Oct. 16; 252(5):572-9 ( Phaeodactylum tricornutum ); Plant Mol. Biol. 1996 April; 31(1):1-12 ( Volvox carteri ); Proc Natl Acad Sci USA. 1994 Nov. 22; 91(24):11562-6 ( Volvox carteri ); Falciatore A, Casotti R, Leblanc C, Abrescia C, Bowler C, PMID: 10383998, 1999 May; 1(3):239-251 (Laboratory of Molecular Plant Biology, Stazione Zoologica, VIIIa Comunale, 1-80121 Naples, Italy) ( Phaeodactylum tricornutum and Thalassiosira weissflogii ); Plant Physiol. 2002 May; 129(1):7-12. ( Porphyridium sp.); Proc Natl Acad Sci USA. 2003 Jan. 21; 100(2):438-42. ( Chlamydomonas reinhardtii ); Proc Natl Acad Sci USA. 1990 February; 87(3):1228-32. ( Chlamydomonas reinhardtii ); Nucleic Acids Res. 1992 Jun. 25; 20(12):2959-65; Mar Biotechnol (NY). 2002 January; 4(1):63-73 ( Chlorella ); Biochem Mol Biol Int. 1995 August; 36(5):1025-35 ( Chlamydomonas reinhardtii ); J. Microbiol. 2005 August; 43(4):361-5 (Dunaliella); Yi Chuan Xue Bao. 2005 April; 32(4):424-33 ( Dunaliella ); Mar Biotechnol (NY). 1999 May; 1(3):239-251. ( Thalassiosira and Phaedactylum ); Koksharova, Appl Microbiol Biotechnol 2002 February; 58(2): 123-37 (various species); Mol Genet Genomics. 2004 February; 271(1):50-9 ( Thermosynechococcus elongates ); J. Bacteriol. (2000), 182, 211-215; FEMS Microbiol Lett. 2003 Apr. 25; 221(2):155-9; Plant Physiol. 1994 June; 105(2):635-41; Plant Mol. Biol. 1995 December; 29(5):897-907 (Synechococcus PCC 7942); Mar Pollut Bull. 2002; 45(1-12):163-7 (Anabaena PCC 7120); Proc Natl Acad Sci USA. 1984 March; 81(5):1561-5 (Anabaena (various strains)); Proc Natl Acad Sci USA. 2001 Mar. 27; 98(7):4243-8 (Synechocystis); Wirth, Mol Gen Genet. 1989 March; 216(1):175-7 (various species); Mol Microbiol, 2002 June; 44(6):1517-31 and Plasmid, 1993 September; 30(2):90-105 ( Fremyella diplosiphon ); Hall et al. (1993) Gene 124: 75-81 ( Chlamydomonas reinhardtii ); Gruber et al. (1991). Current Micro. 22: 15-20; Jarvis et al. (1991) Current Genet. 19: 317-322 (Chlorella); for additional promoters see also Table 1 from U.S. Pat. No. 6,027,900).
[0197] Suitable promoters may be used to express a nucleic acid sequence in microalgae. In some embodiments, the sequence is that of an exogenous gene or nucleic acid. In some embodiments the exogenous gene can encode a superoxide dismutase (SOD) or an SOD fusion. In cases of an exogenous nucleic acid coding sequence, the codon usage may be optionally optimized in whole or in part to facilitate expression in microalgae.
[0198] In other embodiments, the invention provides for the expression of a protein sequence found to be tightly associated with microalgal polysaccharides. One non-limiting example is the protein of SEQ ID NO: 15, which has been shown to be tightly associated with, but not covalently bound to, the polysaccharide from Porphyridium sp. (see J. Phycol. 40: 568-580 (2004)). When Porphyridium culture media is subjected to tangential flow filtration using a filter containing a pore size well in excess of the molecular weight of the protein of SEQ ID NO: 15, the polysaccharide in the retentate contains detectable amounts of the protein, indicating its tight association with the polysaccharide. The calculated molecular weight of the protein is approximately 58 kD, however with glycosylation the protein is approximately 66 kD.
[0199] Such a protein may be expressed directly such that it will be present with the polysaccharides of the invention or expressed as part of a fusion or chimeric protein as described herein. As a fusion protein, the portion that is tightly associated with a microalgal polysaccharide effectively links the other portion(s) to the polysaccharide. A fusion protein may comprise a second protein or polypeptide, with a homogenous or heterologous sequence. A homogenous sequence would result in a dimer or multimer of the protein while a heterologous sequence can introduce a new functionality, including that of a bioactive protein or polypeptide.
[0200] Non-limiting examples of the second protein include an enzyme. In optional embodiments, the enzyme is superoxide dismutase, such as that has at least about 60% amino acid identity with the sequence of SEQ ID NO: 12 or SEQ ID NO: 13 as non-limiting examples. In some embodiments, the superoxide dismutase has at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, at least about 95%, or at least about 98%, or higher, amino acid identity with the sequence of SEQ ID NO: 12 or 13. In other embodiments, the enzyme is a phytase (such as GenBank accession number CAB91845 and U.S. Pat. Nos. 6,855,365 and 6,110,719).
[0201] One advantage to a fusion is that the bioactivity of the polysaccharide and the bioactivity from the protein can be combined in a product without increasing the manufacturing cost over only purifying the polysaccharide. As a non-limiting example, the potent antioxidant properties of a Porphyridium polysaccharide can be combined with the potent antioxidant properties of superoxide dismutase in a fusion, however the polysaccharide:superoxide dismutase combination can be isolated to a high level of purity using tangential flow filtration. In another non-limiting example, the potent antiviral properties of a Porphyridium polysaccharide can be added to the potent neutralizing activity of recombinant antibodies fused to the protein (SEQ ID NO: 15) that tightly associates with the polysaccharide.
[0202] In other embodiments, the invention includes genetic expression methods comprising the use of an expression vector. In one method, a microalgal cell, such as a Porphyridium cell, is transformed with a dual expression vector under conditions wherein vector mediated gene expression occurs. The expression vector may comprise a resistance cassette comprising a gene encoding a protein that confers resistance to an antibiotic such as zeocin, operably linked to a promoter active in microalgae. The vector may also comprise a second expression cassette comprising a second protein to a promoter active in microalgae. The two cassettes are physically linked in the vector. The transformed cells may be optionally selected based upon the ability to grow in the presence of the antibiotic or other selectable marker under conditions wherein cells lacking the resistance cassette would not grow, such as in the dark. The resistance cassette, as well as the expression cassette, may be taken in whole or in part from another vector molecule.
[0203] In one non-limiting example, a method of expressing an exogenous gene in a cell of the genus Porphyridium is provided. The method may comprise operably linking a gene encoding a protein that confers resistance to the antibiotic zeocin to a promoter active in microalgae to form a resistance cassette; operably linking a gene encoding a second protein to a promoter active in microalgae to form a second expression cassette, wherein the resistance cassette and second expression cassette are physically connected to form a dual expression vector; transforming the cell with the dual expression vector; and selecting for the ability to survive in the presence of at least 2.5 ug/ml zeocin, preferably at least 3.0 ug/ml zeocin, and more preferably at least 3.5 ug/ml zeocin, more preferably at least 5.0 ug/ml zeocin.
[0204] In additional aspects, the expression of a protein that produces small molecules in microalgae is included and described. Some genes that can be expressed using the methods provided herein encode enzymes that produce nutraceutical small molecules such as lutein, zeaxanthin, and DHA. Preferably the genes encoding the proteins are synthetic and are created using preferred codons on the microalgae in which the gene is to be expressed. For example, enzyme capable of turning EPA into DHA are cloned into the microalgae Porphyridium sp. by recoding genes to adapt to Porphyridium sp. preferred codons. For examples of such enzymes see Nat. Biotechnol. 2005 August; 23(8): 1013-7. For examples of enzymes in the carotenoid pathway see SEQ ID NOs: 18 and 19. The advantage to expressing such genes is that the nutraceutical value of the cells increases without increasing the manufacturing cost of producing the cells.
[0205] For sequence comparison to determine percent nucleotide or amino acid identity, typically one sequence acts as a reference sequence, to which test sequences are compared. When using a sequence comparison algorithm, test and reference sequences are input into a computer, subsequence coordinates are designated, if necessary, and sequence algorithm program parameters are designated. The sequence comparison algorithm then calculates the percent sequence identity for the test sequence(s) relative to the reference sequence, based on the designated program parameters.
[0206] Optimal alignment of sequences for comparison can be conducted, e.g., by the local homology algorithm of Smith & Waterman, Adv. Appl. Math. 2:482 (1981), by the homology alignment algorithm of Needleman & Wunsch, J. Mol. Biol. 48:443 (1970), by the search for similarity method of Pearson & Lipman, Proc. Nat'l. Acad. Sci. USA 85:2444 (1988), by computerized implementations of these algorithms (GAP, BESTFIT, FASTA, and TFASTA in the Wisconsin Genetics Software Package, Genetics Computer Group, 575 Science Dr., Madison, Wis.), or by visual inspection (see generally Ausubel et al., supra).
[0207] Another example of algorithm that is suitable for determining percent sequence identity and sequence similarity is the BLAST algorithm, which is described in Altschul et al., J. Mol. Biol. 215:403-410 (1990). Software for performing BLAST analyses is publicly available through the National Center for Biotechnology Information (http://www.ncbi.nlm.nih.gov/). This algorithm involves first identifying high scoring sequence pairs (HSPs) by identifying short words of length W in the query sequence, which either match or satisfy some positive-valued threshold score T when aligned with a word of the same length in a database sequence. T is referred to as the neighborhood word score threshold (Altschul et al., supra.). These initial neighborhood word hits act as seeds for initiating searches to find longer HSPs containing them. The word hits are then extended in both directions along each sequence for as far as the cumulative alignment score can be increased. Cumulative scores are calculated using, for nucleotide sequences, the parameters M (reward score for a pair of matching residues; always >0) and N (penalty score for mismatching residues; always <0). For amino acid sequences, a scoring matrix is used to calculate the cumulative score. Extension of the word hits in each direction are halted when: the cumulative alignment score falls off by the quantity X from its maximum achieved value; the cumulative score goes to zero or below, due to the accumulation of one or more negative-scoring residue alignments; or the end of either sequence is reached. For identifying whether a nucleic acid or polypeptide is within the scope of the invention, the default parameters of the BLAST programs are suitable. The BLASTN program (for nucleotide sequences) uses as defaults a word length (W) of 11, an expectation (E) of 10, M=5, N=−4, and a comparison of both strands. For amino acid sequences, the BLASTP program uses as defaults a word length (W) of 3, an expectation (E) of 10, and the BLOSUM62 scoring matrix. The TBLATN program (using protein sequence for nucleotide sequence) uses as defaults a word length (W) of 3, an expectation (E) of 10, and a BLOSUM 62 scoring matrix. (see Henikoff & Henikoff, Proc. Natl. Acad. Sci. USA 89:10915 (1989)).
[0208] In addition to calculating percent sequence identity, the BLAST algorithm also performs a statistical analysis of the similarity between two sequences (see, e.g., Karlin & Altschul, Proc. Nat'l. Acad. Sci. USA 90:5873-5787 (1993)). One measure of similarity provided by the BLAST algorithm is the smallest sum probability (P(N)), which provides an indication of the probability by which a match between two nucleotide or amino acid sequences would occur by chance. For example, a nucleic acid is considered similar to a reference sequence if the smallest sum probability in a comparison of the test nucleic acid to the reference nucleic acid is less than about 0.1, more preferably less than about 0.01, and most preferably less than about 0.001.
[0209] It should be apparent to one skilled in the art that various embodiments and modifications may be made to the invention disclosed in this application without departing from the scope and spirit of the invention. All publications mentioned herein are cited for the purpose of describing and disclosing reagents, methodologies and concepts that may be used in connection with the present invention. Nothing herein is to be construed as an admission that these references are prior art in relation to the inventions described herein.
EXAMPLES
Example 1
Growth of Porphyridium cruentum and Porphyridium sp.
[0210] Porphyridium sp. (strain UTEX 637) and Porphyridium cruentum (strain UTEX 161) were inoculated into autoclaved 2 liter Erlenmeyer flasks containing an artificial seawater media:
[0000] 1495 ASW medium recipe from the American Type Culture Collection (components are per 1 liter of media)
[0000] NaCl 27.0 g MgSO 4 •7H 2 O 6.6 g MgCl 2 •6H 2 O 5.6 g CaCl 2 •2H 2 O 1.5 g KNO 3 1.0 g KH 2 PO 4 0.07 g NaHCO 3 0.04 g 1.0 M Tris-HCl buffer, pH 7.6 20.0 ml Trace Metal Solution (see below) 1.0 ml Chelated Iron Solution (see below) 1.0 ml Distilled water bring to 1.0 L Trace Metal Solution: ZnCl 2 4.0 mg H 3 BO 3 60.0 mg CoCl 2 •6H 2 O 1.5 mg CuCl2•2H 2 O 4.0 mg MnCl 2 •4H 2 O 40.0 mg (NH 4 ) 6 Mo 7 O 24 •4H 2 O 37.0 mg Distilled water 100.0 ml Chelated Iron Solution: FeCl 3 •4H 2 O 240.0 mg 0.05 M EDTA, pH 7.6 100.0 ml
Media was autoclaved for at least 15 minutes at 121° C.
[0211] Inoculated cultures in 2 liter flasks were maintained at room temperature on stir plates. Stir bars were placed in the flasks before autoclaving. A mixture of 5% CO 2 and air was bubbled into the flasks. Gas was filter sterilized before entry. The flasks were under 24 hour illumination from above by standard fluorescent lights (approximately 150 uE/m −1 /s −1 ). Cells were grown for approximately 12 days, at which point the cultures contained approximately of 4×10 6 cells/mL.
Example 2
[0212] Dense Porphyridium sp. and Porphyridium cruentum cultures were centrifuged at 4000 rcf. The supernatant was subjected to tangential flow filtration in a Millipore Pellicon 2 device through a 1000 kD regenerated cellulose membrane (filter catalog number P2C01MC01). Approximately 4.1 liters of Porphyridium cruentum and 15 liters of Porphyridium sp. supernatants were concentrated to a volume of approximately 200 ml in separate experiments. The concentrated exopolysaccharide solutions were then diafiltered with 10 liters of 1 mM Tris (pH 7.5). The retentate was then flushed with 1 mM Tris (pH 7.5), and the total recovered polysaccharide was lyophilized to completion. Yield calculations were performed by the dimethylmethylene blue (DMMB) assay. The lyophilized polysaccharide was resuspended in deionized water and protein was measured by the bicinchoninic acid (BCA) method. Total dry product measured after lyophilization was 3.28 g for Porphyridium sp. and 2.0 g for Porphyridium cruentum . Total protein calculated as a percentage of total dry product was 12.6% for Porphyridium sp. and 15.0% for Porphyridium cruentum.
Example 3
[0213] A measured mass (approximately 125 grams) of freshly harvested Porphyridium sp. cells, resuspended in a minimum amount of dH 2 O sufficient to allow the cells to flow as a liquid, was placed in a container. The cells were subjected to increasing amounts of sonication over time at a predetermined sonication level. Samples were drawn at predetermined time intervals, suspended in measured volume of dH 2 O and diluted appropriately to allow visual observation under a microscope and measurement of polysaccharide concentration of the cell suspension using the DMMB assay. A plot was made of the total amount of time for which the biomass was sonicated and the polysaccharide concentration of the biomass suspension. Two experiments were conducted with different time intervals and total time the sample was subjected to sonication. The first data set from sonication experiment 1 was obtained by subjecting the sample to sonication for a total time period of 60 minutes in 5 minute increments. The second data set from sonication experiment 2 was obtained by subjecting the sample to sonication for a total time period of 6 minutes in 1-minute increments. The data, observations and experimental details are described below. Standard curves were generated using TFF-purified, lyophilized, weighed, resuspended Porphyridium sp. exopolysaccharide.
[0214] General Parameters of Sonication Experiments 1 and 2
[0215] Cells were collected and volume of the culture was measured. The biomass was separated from the culture solution by centrifugation. The centrifuge used was a Form a Scientific Centra-GP8R refrigerated centrifuge. The parameters used for centrifugation were 4200 rpm, 8 minutes, rotor# 218. Following centrifugation, the biomass was washed with dH 2 O. The supernatant from the washings was discarded and the pelleted cell biomass was collected for the experiment.
[0216] A sample of 100 μL of the biomass suspension was collected at time point 0 (0TP) and suspended in 900 μL dH 2 O. The suspension was further diluted ten-fold and used for visual observation and DMMB assay. The time point 0 sample represents the solvent-available polysaccharide concentration in the cell suspension before the cells were subjected to sonication. This was the baseline polysaccharide value for the experiments.
[0217] The following sonication parameters were set: power level=8, 20 seconds ON/20 seconds OFF (Misonix 3000 Sonicator with flat probe tip). The container with the biomass was placed in an ice bath to prevent overheating and the ice was replenished as necessary. The sample was prepared as follows for visual observation and DMMB assay: 100 μL of the biomass sample+900 μL dH 2 O was labeled as dilution 1. 100 μL of (i) dilution 1+900 μL dH 2 O for cell observation and DMMB assay.
[0218] Sonication Experiment 1
[0219] In the first experiment the sample was sonicated for a total time period of 60 minutes, in 5-minute increments (20 seconds ON/20 seconds OFF). The data is presented in Tables 4, 5 and 6. The plots of the absorbance results are presented in FIG. 4 .
[0000]
TABLE 4
SONICATION RECORD - EXPERIMENT 1
Time
point
Ser#
(min)
Observations
1
0
Healthy red cells
2
5
Red color disappeared, small greenish circular particles
3
10
Small particle, smaller than 5 minute TP
4
15
Small particle, smaller than 10 minute TP. Same
observation as 10 minute time
5
20
Similar to 15 minute TP. Small particles; empty circular
shells in the field of vision
6
25
Similar to 20 minute TP
7
30
Similar to 25 minute TP, particles less numerous
8
35
Similar to 30 minute TP
9
40
Similar to 35 minute TP
10
45
Similar to 40 minute TP
11
50
Very few shells, mostly fine particles
12
55
Similar to 50 minute TP.
13
60
Fine particles, hardly any shells
TP = time point.
[0000]
TABLE 5
STANDARD CURVE RECORD - SONICATION EXPERIMENT 1
Absorbance (AU)
Concentration (μg)
0
Blank, 0
0.02
0.25
0.03
0.5
0.05
0.75
0.07
1.0
0.09
1.25
[0000]
TABLE 6
Record of Sample Absorbance versus Time Points - Sonication
Experiment 1
SAMPLE
Solvent-Available
TIME POINT
Polysaccharide
(MIN)
(μg)
0
0.23
5
1.95
10
2.16
15
2.03
20
1.86
25
1.97
30
1.87
35
2.35
40
1.47
45
2.12
50
1.84
55
2.1
60
2.09
[0220] The plot of polysaccharide concentration versus sonication time points is displayed above and in FIG. 4 . Solvent-available polysaccharide concentration of the biomass (cell) suspension reaches a maximum value after 5 minutes of sonication. Additional sonication in 5-minute increments did not result in increased solvent-available polysaccharide concentration.
[0221] Homogenization by sonication of the biomass resulted in an approximately 10-fold increase in solvent-available polysaccharide concentration of the biomass suspension, indicating that homogenization significantly enhances the amount of polysaccharide available to the solvent. These results demonstrate that physically disrupted compositions of Porphyridium for oral or other administration provide novel and unexpected levels or polysaccharide bioavailability compared to compositions of intact cells. Visual observation of the samples also indicates rupture of the cell wall and thus release of insoluble cell wall-bound polysaccharides from the cells into the solution that is measured as the increased polysaccharide concentration in the biomass suspension.
Sonication Experiment 2
[0222] In the second experiment the sample was sonicated for a total time period of 6 minutes in 1-minute increments. The data is presented in Tables 7, 8 and 9. The plots of the absorbance results are presented in FIG. 5 .
[0000]
TABLE 7
SONICATION EXPERIMENT 2
Time
point
Ser#
(min)
Observations
1
0
Healthy red-brown cells appear circular
2
1
Circular particles scattered in the field of vision with few
healthy cells. Red color has mostly disappeared from cell
bodies.
3
2
Observation similar to time point 2 minute.
4
3
Very few healthy cells present. Red color has disappeared
and the concentration of particles closer in size to whole
cells has decreased dramatically.
5
4
Whole cells are completely absent. The particles are
smaller and fewer in number.
6
5
Observation similar to time point 5 minute.
7
6
Whole cells are completely absent. Large particles are
completely absent.
[0000]
TABLE 8
STANDARD CURVE RECORD - SONICATION EXPERIMENT 2
Absorbance (AU)
Concentration (μg)
−0.001
Blank, 0
0.017
0.25
0.031
0.5
0.049
0.75
0.0645
1.0
0.079
1.25
[0000]
TABLE 9
Record of Sample Absorbance versus Time Points - Sonication
Experiment 2
SAMPLE
Solvent-Available
TIME POINT
Polysaccharide
(MIN)
(μg)
0
0.063
1
0.6
2
1.04
3
1.41
4
1.59
5
1.74
6
1.78
[0223] The value of the solvent-available polysaccharide increases gradually up to the 5 minute time point as shown in Table 9 and FIG. 5 .
Example 4
[0224] Porphyridium sp. culture was centrifuged at 4000 rcf and supernatant was collected. The supernatant was divided into six 30 ml aliquots. Three aliquots were autoclaved for 15 min at 121° C. After cooling to room temperature, one aliquot was mixed with methanol (58.3% vol/vol), one was mixed with ethanol (47.5% vol/vol) and one was mixed with isopropanol (50% vol/vol). The same concentrations of these alcohols were added to the three supernatant aliquots that were not autoclaved. Polysaccharide precipitates from all six samples were collected immediately by centrifugation at 4000 rcf at 20° C. for 10 min and pellets were washed in 20% of their respective alcohols. Pellets were then dried by lyophilization and resuspended in 15 ml deionized water by placement in a 60° C. water bath. Polysaccharide pellets from non-autoclaved samples were partially soluble or insoluble. Polysaccharide pellets from autoclaved ethanol and methanol precipitation were partially soluble. The polysaccharide pellet obtained from isopropanol precipitation of the autoclaved supernatant was completely soluble in water.
Example 5
[0225] Approximately 10 milligrams of purified polysaccharide from Porphyridium sp. and Porphyridium cruentum (described in Example 3) were subjected to monosaccharide analysis.
[0226] Monosaccharide analysis was performed by combined gas chromatography/mass spectrometry (GC/MS) of the per-O-trimethylsilyl (TMS) derivatives of the monosaccharide methyl glycosides produced from the sample by acidic methanolysis.
[0227] Methyl glycosides prepared from 500 μg of the dry sample provided by the client by methanolysis in 1 M HCl in methanol at 80° C. (18-22 hours), followed by re-N-acetylation with pyridine and acetic anhydride in methanol (for detection of amino sugars). The samples were then per-O-trimethylsilylated by treatment with Tri-Sil (Pierce) at 80° C. (30 mins). These procedures were carried out as previously described described in Merkle and Poppe (1994) Methods Enzymol. 230:1-15; York, et al. (1985) Methods Enzymol. 118:3-40. GC/MS analysis of the TMS methyl glycosides was performed on an HP 5890 GC interfaced to a 5970 MSD, using a Supelco DB-1 fused silica capillary column (30 m 0.25 mm ID).
[0000] Monosaccharide compositions were determined as follows:
[0000]
TABLE 10
Porphyridium sp. monosaccharide analysis
Glycosyl residue
Mass (μg)
Mole %
Arabinose (Ara)
n.d.
n.d.
Rhamnose (Rha)
2.7
1.6
Fucose (Fuc)
n.d.
n.d.
Xylose (Xyl)
70.2
44.2
Glucuronic acid (GlcA)
n.d.
n.d.
Galacturonic acid (GalA)
n.d.
n.d.
Mannose (Man)
3.5
1.8
Galactose (Gal)
65.4
34.2
Glucose (Glc)
34.7
18.2
N-acetyl galactosamine (GalNAc)
n.d.
n.d.
N-acetyl glucosamine (GlcNAc)
trace
trace
Σ
=
176.5
[0000]
TABLE 11
Porphyridium cruentum monosaccharide analysis
Glycosyl residue
Mass (μg)
Mole %
Arabinose (Ara)
n.d.
n.d.
Rhamnose (Rha)
n.d.
n.d.
Fucose (Fuc)
n.d.
n.d.
Xylose (Xyl)
148.8
53.2
Glucuronic Acid (GlcA)
14.8
4.1
Mannose (Man)
n.d.
n.d.
Galactose (Gal)
88.3
26.3
Glucose (Glc)
55.0
16.4
N-acetyl glucosamine (GlcNAc)
trace
trace
N-acetyl neuraminic acid (NANA)
n.d.
n.d.
Σ
=
292.1
Mole % values are expressed as mole percent of total carbohydrate in the sample.
n.d. = none detected.
Example 6
[0228] Porphyridium sp. was grown as described. 2 liters of centrifuged Porphyridium sp. culture supernatant were autoclaved at 121° C. for 20 minutes and then treated with 50% isopropanol to precipitate polysaccharides. Prior to autoclaving the 2 liters of supernatant contained 90.38 mg polysaccharide. The pellet was washed with 20% isopropanol and dried by lyophilization. The dried material was resuspended in deionized water. The resuspended polysaccharide solution was dialyzed to completion against deionized water in a Spectra/Por cellulose ester dialysis membrane (25,000 MWCO). 4.24% of the solid content in the solution was proteins as measured by the BCA assay.
Example 7
[0229] Porphyridium sp. was grown as described. 1 liters of centrifuged Porphyridium sp. culture supernatant was autoclaved at 121° C. for 15 minutes and then treated with 10% protease (Sigma catalog number P-5147; protease treatment amount relative to protein content of the supernatant as determined by BCA assay). The protease reaction proceeded for 4 days at 37° C. The solution was then subjected to tangential flow filtration in a Millipore Pellicono cassette system using a 0.1 micrometer regenerated cellulose membrane. The retentate was diafiltered to completion with deionized water. No protein was detected in the diafiltered retentate by the BCA assay. See FIG. 6 .
[0230] Optionally, the retentate can be autoclaved to achieve sterility if the filtration system is not sterile. Optionally the sterile retentate can be mixed with pharmaceutically acceptable carrier(s) and filled in vials for injection.
[0231] Optionally, the protein free polysaccharide can be fragmented by, for example, sonication to reduce viscosity for parenteral injection as, for example, an antiviral compound. Preferably the sterile polysaccharide is not fragmented when prepared for injection as a joint lubricant.
Example 8
[0232] Cultures of Porphyridium sp. (UTEX 637) and Porphyridium cruentum (strain UTEX 161) were grown, to a density of 4×10 6 cells/mL, as described in Example 1. For each strain, about 2×10 6 cells/mL cells per well (˜500 uL) were transferred to 11 wells of a 24 well microtiter plate. These wells contained ATCC 1495 media supplemented with varying concentration of glycerol as follows: 0%, 0.1%, 0.25%, 0.5%, 0.75%, 1%, 2%, 3%, 5%, 7% and 10%. Duplicate microtiter plates were shaken (a) under continuous illumination of approximately 2400 lux as measured by a VWR Traceable light meter (cat #21800-014), and (b) in the absence of light. After 5 days, the effect of increasing concentrations of glycerol on the growth rate of these two species of Porphyridium in the light was monitored using a hemocytometer. The results are given in FIG. 2 and indicate that in light, 0.25 to 0.75 percent glycerol supports the highest growth rate, with an apparent optimum concentration of 0.5%.
[0233] Cells in the dark were observed after about 3 weeks of growth. The results are given in FIG. 3 and indicate that in complete darkness, 5.0 to 7.0% glycerol supports the highest growth rate, with an apparent optimum concentration of 7.0%.
Example 9
Cosmeceutical Compositions
[0234] Porphyridium sp. (UTEX 637) was grown to a density of approximately 4×10 6 cells/mL, as described in Example 1. Approximately 50 grams of wet pelleted, and washed cells were completely homogenized using approximately 20 minutes of sonication as described. The homogenized biomass was mixed with carriers including, water, butylene glycol, mineral oil, petrolatum, glycerin, cetyl alcohol, propylene glycol dicaprylate/dicaprate, PEG-40 stearate, C11-13 isoparaffin, glyceryl stearate, tri (PPG-3 myristyl ether) citrate, emulsifying wax, dimethicone, DMDM hydantoin, methylparaben, carbomer 940, ethylparaben, propylparaben, titanium dioxide, disodium EDTA, sodium hydroxide, butylparaben, and xanthan gum. The mixture was then further homogenized to form a composition suitable for topical administration. The composition was applied to human skin daily for a period of one week.
Example 10
[0235] Approximately 4500 cells (300 ul of 1.5×10 5 cells per ml) of Porphyridium sp. and Porphyridium cruentum cultures in liquid ATCC 1495 ASW media were plated onto ATCC 1495 ASW agar plates (1.5% agar). The plates contained varying amounts of zeocin, sulfometuron, hygromycin and spectinomycin. The plates were put under constant artificial fluorescent light of approximately 480 lux. After 14 days, plates were checked for growth. Results were as follows:
[0000]
Conc. (ug/ml)
Growth
Zeocin
0.0
++++
2.5
+
5.0
−
7.0
−
Hygromycin
0.0
++++
5.0
++++
10.0
++++
50.0
++++
Specinomycin
0.0
++++
100.0
++++
250.0
++++
750.0
++++
[0236] After the initial results above were obtained, a titration of zeocin was performed to more accurately determine growth levels of Porphyridium in the presence of zeocin. Porphyridium sp. cells were plated as described above. Results are shown in FIG. 8 .
Example 11
Nutritional Manipulation to Generate Novel Polysaccharides
[0237] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing glucose, are cultured in ATCC 1495 media in the light in the presence of 1.0% glucose for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
[0238] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing xylose, are cultured in ATCC 1495 media in the light in the presence of 1.0% xylose for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
[0239] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing galactose, are cultured in ATCC 1495 media in the light in the presence of 1.0% galactose for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
[0240] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing glucuronic acid, are cultured in ATCC 1495 media in the light in the presence of 1.0% glucuronic acid for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
[0241] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing glucose, are cultured in ATCC 1495 media in the dark in the presence of 1.0% glucose for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
[0242] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing xylose, are cultured in ATCC 1495 media in the dark in the presence of 1.0% xylose for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
[0243] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing galactose, are cultured in ATCC 1495 media in the dark in the presence of 1.0% galactose for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
[0244] Cells expressing an endogenous monosaccharide transporter, containing a monosaccharide transporter and capable of importing glucuronic acid, are cultured in ATCC 1495 media in the dark in the presence of 1.0% glucuronic acid for approximately 12 days. Exopolysaccharide is purified as described in Example 2. Monosaccharide analysis is performed as described in Example 5.
Example 12
[0245] 128 mg of intact lyophilized Porphyridium sp. cells were ground with a mortar/pestle. The sample placed in the mortar pestle was ground for 5 minutes. 9.0 mg of the sample of the ground cells was placed in a micro centrifuge tube and suspended in 1000 μL of dH2O. The sample was vortexed to suspend the cells. 3.
[0246] A second sample of 9.0 mg of intact, lyophilized Porphyridium sp. cells was placed in a micro centrifuge tube and suspended in 1000 μL of dH2O. The sample was vortexed to suspend the cells.
[0247] The suspensions of both cells were diluted 1:10 and polysaccharide concentration of the diluted samples was measured by DMMB assay. Upon grinding, the suspension of ground cells resulted in an approximately 10-fold increase in the solvent-accessible polysaccharide as measured by DMMB assay over the same quantity of intact cells.
[0000]
TABLE 10
Read 1
Read 2
Avg. Abs
Conc.
Sample Description
(AU)
(AU)
(AU)
(μg/mL)
Blank
0
−0.004
−0.002
0
50 ng/μL Std., 10 μL; 0.5 μg
0.03
0.028
0.029
NA
100 ng/μL Std., 10 μL; 1.0 μg
0.056
0.055
0.0555
NA
Whole cell suspension
0.009
0.004
0.0065
0.0102
Ground cell suspension
0.091
0.072
0.0815
0.128
[0248] Reduction in the particle size of the lyophilized biomass by homogenization in a mortar/pestle results in better suspension and increase in the solvent-accessible polysaccharide concentration of the cell suspension.
[0249] All references cited herein, including patents, patent applications, and publications, are hereby incorporated by reference in their entireties, whether previously specifically incorporated or not.
[0250] Having now fully described this invention, it will be appreciated by those skilled in the art that the same can be performed within a wide range of equivalent parameters, concentrations, and conditions without departing from the spirit and scope of the invention and without undue experimentation.
[0251] While this invention has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth. | Provided herein are oral skin care supplements and nutraceutical compositions and methods of use for improving the health and appearance of skin. Also provided are nutraceutical compositions that, when orally consumed will provide nourishment and deliver essential skin health nutrition to the skin. These nutraceutical compositions include omega 3 rich oils, vitamins, lutein, marine collagen and elastin. Also provided is a unique microalgae oral delivery system targeting the health and appearance of skin. | 0 |
FIELD OF THE INVENTION
This invention relates generally to underwater vehicles such as torpedoes and also has applicability to underwater or partially submerged structural components of water vehicles generally.
BACKGROUND OF THE INVENTION
Underwater vehicles, such as torpedoes, are generally of longitudinally elongated configuration and can present storage problems because of the length, particularly if prior to deployment they are stored in the limited confines of e.g. a submarine or even a surface ship. At the same time, it is important to configure such underwater vehicles in a fashion that promotes efficient travel through the water, a design consideration often at odds with longitudinal dimensional considerations for such an underwater vehicle.
In the prior art related to airborne missiles (as opposed to underwater vehicles), there are some examples of arrangements intended to reconfigure or augment the configuration of a missile at or after launch. For example, in U.S. Pat. No. 4,244,294, "Stowable Nozzle Plug and Method for Air Breathing Missile," a missile with an air breathing gas turbine engine is configured with a translating exhaust plug nozzle intended to minimize longitudinal length of the engine section. Specifically, a translatable exhaust nozzle plug is stowed totally within the outer confines of a missile housing and a booster rocket is attached, holding it in place. Upon release of the booster rocket, a spring shifts the translatable portion of the exhaust nozzle plug, such that it extends outside the missile housing. Alternatively, start up of the turbine engine with generation of exhaust gases is referred to as a means for extending the nozzle plug (via the pressure from the exhaust gases) as is a lanyard attached to the booster which ends up being jettisoned, with the lanyard mechanically pulling out or extending the nozzle plug.
In another prior patent related to rocket engines, U.S. Pat. No. 4,525,999, "Actuator for Deploying Flexible Bodies," there is disclosed a rocket motor nozzle extension which is flexible and in a folded position and which has a telescoping actuator assembly attached to it. A gas generator is provided which forces gas into the telescoping actuator which, in turn, extends the telescoping sections which lock in an extended position. The gas in the telescoping sections is vented.
OBJECTS AND SUMMARY OF THE INVENTION
It is an object of the present invention to provide a method and system for altering the configuration of an underwater vehicle between a more compact longitudinal configuration for storage, to a more elongated and streamlined configuration at or after launch, to facilitate more efficient in the water or under the water travel of the vehicle.
Briefly, in accordance with one embodiment of the invention, an underwater vehicle has a generally longitudinally extending housing terminating in at least one blunt end. Adjacent to and inboard of the blunt end of the longitudinally extended housing there is provided a compartment, and disposed in the compartment there is provided a folded, flexible bladder secured to a portion of the housing adjacent the blunt end. At or after launch of the underwater vehicle, or selectively at any other time in which it is desired to do so, an inboard mounted water pump which communicates with the interior of the bladder is operated to pressurize the bladder with regard to the surrounding ambient water, causing the bladder to unfold and be extended outboard of the housing blunt end, thus streamlining the underwater vehicle.
Other objects, advantages and details and alternative embodiments of the present invention will be apparent from the following detailed description taken in conjunction with the accompanying drawings, with the scope of the invention being reflected in the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevation of an underwater vehicle, partially in section and partially diagrammatic, illustrating storage of a folded bladder adjacent to a blunt end of the underwater vehicle.
FIG. 2 is a side elevation similar to FIG. 1, which shows the bladder in an extended or inflated position.
FIG. 3 is a side elevation similar to FIG. 1 illustrating an embodiment of the invention in which, stored in the compartment along with the folded bladder, there is also provided storage of a hydrophone and/or cable spool arrangement for trailing behind the underwater vehicle after launch.
FIG. 4 is a side elevation similar to FIG. 2, but showing the bladder of the arrangement of FIG. 3 in an inflated or filled or pressurized condition.
FIG. 5 is a side elevation of one component of an offshore floating structure, showing application of the selectively reconfigurable underwater pontoon portion of the structure.
FIG. 6 is a side elevation of the arrangement of FIG. 5, showing deployment of the inflatable bladders on both ends of the pontoon arrangement of FIG. 5, for streamlining the pontoon of FIG. 5 for travel through the water.
DETAILED DESCRIPTION
Turning now to FIG. 1, there is shown in a longitudinal cross-section, partly in diagrammatic form, an example of one embodiment of the invention. In FIG. 1 an underwater vehicle generally indicated by reference numeral 10 has a generally longitudinally extending underwater rigid housing 11. The generally longitudinally extending rigid housing 11 has a blunt end 12, which in accordance with the principles of this invention can be the forward or aft section of the underwater vehicle 10, referring to forward and aft by reference to the intended travel direction of the underwater vehicle 10 through the water. Assume for the moment that what is illustrated in FIG. 1 is the aft end of an underwater vehicle, such as a torpedo. A compartment 13 is provided within the housing 11 situated adjacent to the blunt end 12 of the underwater vehicle 10. Disposed within the compartment 13 is a flexible bladder 14 which, as shown in FIG. 1, is folded upon itself such that it fits in a folded condition within the compartment 13. A rigid or semi-rigid nose portion 16 may be provided at the outboard end of the flexible bladder 14 to close and seal the flexible bladder.
As shown in FIG. 1, the flexible bladder 14 is suitably affixed to a wall 17 which can be part of the interior configuration of the rigid housing 11, and defining the compartment 13. As shown in FIG. 1, a clamping ring 18 sandwiches the open end of flexible bladder 13 to an e.g. circular clamping mandrel 19 affixed to the wall 17.
In FIG. 1 the blunt end of the underwater vehicle 10 is illustrated as being closed and/or sealed by a cover 21, which can be suitably secured to the blunt end to dose the otherwise open end of compartment 13. As illustrated in FIG. 1, the cover 21 can be held on the blunt end 12 through a springing action of the cover acting on the rigid housing wall. Alternatively, a cover can be provided which is releasably held in any of the many other fashions known in the art, such as by remotely actuated releasable clamps or bolts, physical means such as a lanyard, etc.
FIG. 1 illustrates an inlet 22 extending through the wall 17 into the closed volume bounded by the folded flexible bladder 14. Inlet 22 is connected via a suitable conduit 23 to a pump 24. The pump 24 is selectively actuated to pump ambient water from around the underwater vehicle 10 through conduit 23 and inlet 22 into the interior closed volume of flexible bladder 14. Alternatively, if pump 24 runs continuously, such as might be the case in a water jet propelled vehicle or torpedo, then pump 24 can have selectively actuatable valve means for communicating water under pressure through conduit 23 and inlet 22 into the interior of the folded flexible bladder 14.
Referring now to FIG. 2, there is shown the arrangement of FIG. 1 in which, after deployment or launch of the underwater vehicle 10 for travel through the water, the cover plate 21 has been jettisoned and the inflatable bladder 14 has been inflated, filled or pressurized with water. The bladder is reinforced with fiber so that it maintains a predetermined hydrodynamic shape. As illustrated in FIG. 2, the bladder 14 in its pressurized or inflated condition is generally of a streamlined shape narrowing down to a small diameter, and its end can be closed by the rigid plug 16 which can be made of hard rubber or the like. The inflatable bladder 14 is filled, deployed or pressurized through pump 24 being actuated to pump through conduit 23 and through inlet 22 water into the interior of the bladder 14. The resulting arrangement as shown in FIG. 2 presents a streamlined profile at the end of the underwater vehicle 10 (as opposed to the blunt end) which makes for efficient travel of the underwater vehicle through the water.
In one preferred embodiment of the invention, the inflatable bladder concept of this invention is applied to an underwater torpedo which has jet pump water propulsion as opposed to the prior propulsion techniques of open propellers or shrouded propellers. Such a jet pump configuration readily lends itself to application of this invention, inasmuch as deployment of the inflatable bladder to streamline the blunt end of the torpedo does not run afoul of or interfere with propellers or the like. In the case of this one preferred embodiment, the pump 24 can be the jet propulsion pump for the torpedo or underwater vehicle 10. This leads to several advantages, in that the pump 24 or at least the water coursing through the pump and being exited as a means of propulsion is in communication with the ambient water surrounding the torpedo or underwater vehicle. A relative pressure of only 1-3 PSI within the interior of the inflatable bladder 14 as compared to the ambient water surrounding it has been found to be quite ample for maintaining the inflatable bladder 10 in an inflated or pressurized condition as shown in FIG. 2. In the case of a torpedo or underwater vehicle 10 wherein the pump 24 is a jet propulsion pump for the torpedo or vehicle, automatic pressure equalization takes place for depths traversed by the underwater vehicle between the interior of the inflatable bladder 14 in its inflated condition as shown in FIG. 2, and the surrounding ambient water. That is, since the water being pumped out of pump 24 to propel the vehicle is in communication with the ambient water, the pressure differential between the ambient or surrounding water and the interior of the filled or pressurized inflatable bladder 14 stays relatively constant, regardless of the water depth. This is an especially important consideration for torpedoes or underwater vehicles which operate over a wide range of water depths.
Alternatively, of course, the pump 24 need not be a propulsion pump for the vehicle and can be operated to selectively inflate the bladder 14 at whatever time is desired at or after launch, through radio controls or the like sending signals to the pump 24 for actuating it and/or opening a valve to fill the interior of the bladder 14 with water. In accordance with one embodiment of the invention, the inflatable bladder 14 was constructed of neoprene infiltrated nylon fabric, the same material used for evacuation slides on airplanes. Many other suitable materials exist, however, and the bladder could be made of Kevlar, for example. The purpose of the reinforcing materials is to maintain the bladder in a desired shape after inflation.
Turning now to FIGS. 3 and 4, one particular embodiment of the invention is shown as applied to an underwater torpedo useful for towing a hydrophone array or the like, or where a spool of e.g. fiber optic cable which is connected to a mother ship or vehicle from which the torpedo is launched is utilized with the cable being deployed as the torpedo travels through the water. Like reference numerals are used in FIGS. 3 and 4 respectively as in FIGS. 1 and 2 to refer to common elements carried over from FIGS. 1 and 2 into FIGS. 3 and 4.
As before, the longitudinally extending rigid housing 11 has a compartment 13 adjacent a blunt end of the housing within which a folded flexible bladder 14 is disposed. At of the folded, flexible bladder 14 there is provided a hydrophone and cable spool assembly 31, shown only in diagrammatic form in FIG. 3. A cable for connecting the hydrophone and cable spool assembly 31 to suitable electronics assemblies 32 carried within the longitudinal housing 11 is provided and is identified by reference numeral 33 in FIG. 3. The cable 33 is held and suitably secured in a waterproof fashion by the rigid blunt end 16 of the flexible bladder and passes through in a waterproof fashion the inner wall 17 for connection to the electronics 32. Instead of a hydrophone and cable array, the assembly 31 can of course be a spool of fiber optic or other cable for deployment as the torpedo travels through the water while maintaining connection with a mother ship or other vehicle from which the torpedo was launched.
Referring to FIG. 4, there is shown the arrangement of FIG. 3 after the flexible folded bladder 14 has been inflated or pressurized by water to place it in an unfolded, extended condition as shown in FIG. 4, streamlining the blunt end of housing 11. As illustrated in FIG. 4, the cable 33 is deployed behind the extended bladder 14 for towing a hydrophone 34 or the like.
The arrangement of FIGS. 3 and 4 works particularly well in the case of torpedoes or other underwater vehicles which are propelled by a jet pump, because such a jet pump propelled vehicle has no external propeller or the like which would interfere with the extension of bladder 14 to achieve streamlining or interfere with deployment of the hydrophone and cable spool arrangement 31. Also, and as mentioned before in connection with FIGS. 1 and 2, for arrangements wherein the pump 24 supplying water to inflate the bladder 14 is the jet propulsion pump, because it is in communication with the ambient water surrounding the longitudinally extending rigid hull 11 and bladder 14, automatic pressure compensation occurs with regard to transit of the underwater vehicle through varying depths of water. It has been found that a pressure differential of only 1-3 PSI between the interior water inflating bladder 14 and the ambient water surrounding the under-water vehicle functions quite well in maintaining the flexible bladder 14 in an inflated or pressurized condition.
It has been found in experiments that extending an inflatable bladder in the fashion discussed above in connection with FIGS. 1-4 to streamline a blunt end of an underwater vehicle such as a torpedo, results in a 30% reduction of drag over the same underwater vehicle with only the blunt end.
Turning now to a consideration of FIGS. 5 and 6, there is diagrammatically illustrated another application for the principles of the invention in which a blunt end or ends of an underwater or in-the-water portion of a water vehicle is provided with a selectively deployable tapered bladder for streamlining the blunt end of the underwater or in-the-water portion for efficient transit through the water with reduced drag. It is known to assemble structures such as offshore drilling platforms and the like by transporting portions of the structure through the water to their destination. Generally, various subassemblies of such an offshore platform are separately transported through the water and then bolted or otherwise affixed together at the destination to form an overall composite structure. Because of the manner in which these various sections are assembled, it is obviously desirable to have whatever the underwater or partially in-water structure of pontoons or the like not extend past the perimeter or edge of the sections to be joined, as well as being generally planar or flat for purposes of being joined together, such that usually there is provided blunt ends to pontoons or the like supporting the various sections. While this facilitates bolting the sections together when they have been transported through the water to their destination, it results in an inefficient underwater or in-the-water design of the pontoons.
FIGS. 5 and 6 show application of the principles of this invention to pontoons, either underwater or in-the-water pontoons, for supporting and transporting sections of an offshore assembly. In the drawings, the section of the offshore assembly or the like is diagrammatically illustrated by reference numeral 36 shown as connected by struts 37 to a pontoon assembly 38. The section 36 can of course in certain cases be quite large, displacing 10,000 tons or more. The pontoon assembly 38 has suitable end sections or the like indicated by reference numerals 39 which are provided adjacent blunt ends of the generally longitudinally extending cylindrical rigid housing 41. Compartments 42 and 43 are provided adjacent the blunt ends of the pontoon assembly 38. Flexible bladders 45 and 46 are respectively disposed in the compartments 42 and 43 and are shown in FIG. 5 in the non-deployed or folded condition, and are suitably fastened through fixing means 51 (indicated only diagrammatically) in a water sealed relationship to one of the walls of the compartments 42 and 43. Water inlets 47 and 48 are provided extending within the interior volume of the bladders 45 and 46 provided in the compartments 42 and 43. The inlets 47 and 48 communicate with a pump 49. The pump 49 is adapted to be utilized to pump ambient surrounding water through the inlets 47 and 48 to expand and inflate the bladders 45 and 46. When this occurs, the general configuration of the underwater or in the water pontoon assembly 38 is as shown in FIG. 6. It has been found that differential pressures as low as 1-3 PSI between the ambient surrounding water and the water utilized to inflate bladders 45 and 46 works very satisfactorily. The pump 49 can be a selectively actuated auxiliary pump run by onboard electrical power, or can be part of the pump circuit for a jet pump propulsion unit which is used for transporting the sections for structures intended to be assembled in the water. Of course, the type of structures of which the present invention is applicable for moving sections include not only all drilling platforms and the like which end up being rigidly affixed to the bottom of the ocean, but also to floating assemblies of any and all kinds. After transiting the sections to their intended location through configuring the in the water or underwater portion of the structure as shown in FIG. 6, then the inflatable or pressurized bladders 45 and 46 may be depressurized and stored or folded back within their respective compartments in the pontoon structure 38.
While certain preferred and exemplary embodiments of the present invention have been discussed in connection with the included drawings, it should be clear that it is believed the concept and the principles of the present invention has wide application. | An underwater vehicle has a generally longitudinally extending housing terminating in at least one blunt end. Adjacent to and inboard of the blunt end of the longitudinally extended housing there is provided a compartment, and disposed in the compartment there is provided a folded, flexible bladder secured to a portion of the housing adjacent the blunt end and having a tapering configuration when pressurized or inflated. At or after launch of the underwater vehicle, or selectively at any other time in which it is desired to do so, an inboard mounted water pump which communicates with the interior of the bladder is operated to pressurize the bladder with regard to the surrounding ambient water, causing the tapered bladder to unfold and be extended outboard of the housing blunt end, thus streamlining the underwater vehicle. | 1 |
CROSS-REFERENCE TO A RELATED APPLICATION
[0001] This application is a continuation-in-part of patent application Ser. No. 10/890,579 filed on Jul. 14, 2004.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a method for continuous coloring textiles, as well as to the device for performing the method.
[0003] Methods and devices of this type are known in the art, for example for indigo coloring of textiles, in which a coloring substance which is not soluble in water is converted by means of alkali or reduction agent into a water-soluble form which has affinity to threads. In this manner the coloring substance can color the threads of the textiles, which is also called pad dying. After a subsequent oxidation, the coloring substance obtains indigo blue color. Also, other copper coloring substances such as indanthrene and sulphur coloring substances can be used. The textiles in this application include textile webs or threads.
[0004] German patent document DE 43 14 402 A1 discloses a method of indigo coloring of threads, in which the threads are pad dyed with a coloring substances many times and oxidized in a subsequent oxidation line. Between the pad dying and the oxidation the threads are damped. By this the reaction times for the pad dying and the oxidation can be shortened.
[0005] German patent document DE 43 42 313 A1 discloses a device for application of indigo coloring substance, in which a thread assembly is guided via an inlet squeezing mechanism into a coloring substance emersion bath and further via an outlet squeezing mechanism of a retention line for extraction of the coloring substance. A wet retention line is arranged between the coloring substance emersion bath and the inlet squeezing mechanism, which is encapsulated against air entry and is held with low oxygen or oxygen free. Thereby a reduction of the chemicals consumption is provided.
[0006] The disadvantage of the known methods and devices is that on the threads of the textiles a great quantity of oxygen adheres, for example on the outer surface or dissolved in the liquid, and therefore is introduced into the trough with the coloring substance. Thereby an undesirable oxidation of the coloring substance occurs, and of the auxiliary substances such as reduction agents and alkali in the trough. This leads to a high consumption of the chemicals with corresponding costs.
SUMMARY OF THE INVENTION
[0007] Accordingly, it is an object of the present invention to provide a method for coloring of textiles, in which they are pad dyed many times with coloring substances and subsequently in an oxidation line are oxidized, wherein the method and the device are improved so that considerable quantities of chemicals can be saved and simultaneously a uniform coloring result can be provided.
[0008] In keeping with these objects and with others which will become apparent hereinafter, one feature of the present invention resides, briefly stated, in a method of coloring of continuous textiles, comprising pad dying of the textiles many times in at least one trough; subsequently oxidizing the textiles in an oxidation line; then washing and drying the textiles, which includes expelling of oxygen from the textiles immediately before each pad dying, wherein a reintroduction of oxygen in the textiles is prevented before each oxidation.
[0009] Since oxygen is expelled from the textiles directly before each pad dying, a further penetration of oxygen into the textiles before the oxidation is prevented, and therefore it is excluded that undesired oxygen reaches the coloring bath.
[0010] Oxygen in a coloring bath causes an oxidation of a coloring substance, so that it no longer has affinity to threads or in other words it is water-insoluble and can no more be used efficiently for coloring. Furthermore, the oxygen acts so that auxiliary substances such as reduction agents and alkali are consumed and/or converted into an inefficient form.
[0011] Therefore, in the known methods more coloring and auxiliary substances must be dosed into the coloring bath than it is required by the threads themselves.
[0012] The inventive method eliminates these disadvantages, and it prevents oxidation of coloring substances and auxiliary substances, without being used for the coloring process. When compared with known methods, a saving of 30-40% of the total consumption of chemicals with corresponding cost reduction is possible. Furthermore, coloring results are obtained.
[0013] The expelling of the oxygen by emersion in a liquid and subsequent squeezing in accordance with another feature of the present invention guarantees its complete removal. The use of washing water guides chemicals, which are lost in known methods with the waste water, back into the covering process, so that they can be again utilized. The washing water is oxygen-free, it has the required pH value, and therefore it suits the best for the expelling of oxygen from textiles.
[0014] The oxygen-free atmosphere between the expelling of the oxygen and the subsequent oxidation area prevents that the textiles, before or after wetting with a coloring substance, again take oxygen and introduce it then into the coloring bath. The maintaining of the once produced oxygen-free atmosphere is possible with very low expenses, since in operation it is practically not influenced by the passing textiles.
[0015] In accordance with another feature of the present invention a nitrogen atmosphere is utilized for the inventive method. Nitrogen is inert and price favorable.
[0016] In accordance with another feature of the present invention, a device for coloring of textiles is proposed, which includes a plurality of coloring troughs each connected with a supply of a coloring substance; a second squeezing mechanism connected after each of said coloring troughs; a plurality of oxidation lines each arranged behind the second squeezing mechanism; a washing trough; a dryer; means for expelling oxygen from the textiles arranged immediately before each of said coloring troughs; further means which prevent a contact of the textiles with oxygen between each means for expelling and the second squeezing mechanism.
[0017] The novel features which are considered as characteristic for the present invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] The single FIGURE of the drawings is a view showing a diagram of a part of a device for coloring of threads in accordance with the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] A device for coloring textiles in accordance with the present invention has a plurality of wetting stages 1 . An oxidation line 2 and a washing device 3 follows each wetting stage 1 . Furthermore, the device in accordance with the present invention has not shown means for supplying threads 4 , in which the threads are wound for example in a bobbin by spools and supplied to coloring, and means for drying of the colored threads 4 .
[0020] Each wetting stage 1 includes means for expelling oxygen 5 from the threads 4 , a coloring substance trough 6 , and a second squeezing mechanism 7 .
[0021] The means for expelling 5 contain a trough 8 with at least one first deviating roll 9 , and a first squeezing mechanism 10 arranged at an outlet of the threads 4 from the trough 8 . An overflow conduit 11 is attached to the trough 8 and is connected with a drain.
[0022] At a short distance in the running direction of the threads 4 behind the first squeezing mechanism 10 , the coloring trough 6 is provided with a plurality of second deviating rolls 12 . The threads 4 are guided over the second deviating rolls 12 so that they run a sufficiently along the line in the coloring trough 6 . The second squeezing mechanism 7 is arranged in the outlet region of the coloring troughs 6 above a coloring substance float level, so that the squeezed out bath float flows back into the coloring trough 6 .
[0023] A region starting before the outlet of the threads 4 from the float of the trough 8 and ending behind the inlet of the threads in the second squeezing mechanism 7 is protected by further means from the surrounding atmosphere. For this purpose, a hood 13 is arranged so that it is immersed with its part into the float of the trough 8 and is substantially air tightly closed from the trough 8 , the coloring substance trough 6 and the second squeezing mechanism 7 . The hood 13 is connected through a not show conduit with a nitrogen source.
[0024] After the squeezing mechanism 7 , the threads 4 pass through the oxidation line 2 . In this line they perform several deviations.
[0025] Several combinations of the wetting stage 1 and the oxidation line 2 can be arranged, one after the other, as shown for example by the interruption by the threads 4 .
[0026] A washing device 3 is arranged after the last oxidation line 2 . It includes a washing trough 14 as well as a sequence of third deviating rolls 15 and third squeezing mechanisms 16 . The washing trough 14 is connected by a conduit 17 with branches with each of the troughs 8 . Depending on space peculiarities, a pump 18 is arranged in the conduit 17 .
[0027] Finally, a not shown dryer is arranged after the washing device 3 .
[0028] In operation the threads 4 are pulled from the bobbin and guided as a thread assembly to coloring. For the coloring, one of the coloring processes described herein above is performed.
[0029] The threads 4 which can take the oxygen from the air are first immersed in the trough 8 which is filled with washing water from the washing trough 14 . The washing water has a favorable pH value of approximately 11 or higher and contains residuals of coloring substance and auxiliary substances such as alkali and reduction agent. With these properties of the washer water, the oxygen is removed from the threads 4 substantially or completely, and the threads take a part of the coloring substance. In this way substantially less coloring substance and auxiliary substances must be dosed in the coloring trough 6 .
[0030] After the immersion, the threads 4 are pressed in the first squeezing mechanism 10 , so that excessive liquid is squeezed out and flows back into the trough 8 .
[0031] In the coloring trough 8 the threads are deviated over the second deviating rolls 11 so that they have a sufficient contact time for material exchange with the coloring float. In the coloring float the required quantities of water, coloring substance and auxiliary substances are dosed. Shortly before leaving the coloring float the threads 4 are again pressed in the second squeezing mechanism 7 . For this purpose the squeezing pressures in the first and in the second squeezing mechanism 10 , 7 are identical, so that the threads 4 in the inlet of the color trough 6 have the same moisture as in its outlet, and an dilution of the coloring float is prevented.
[0032] The whole region between the first and the second squeezing mechanism 7 , 10 is provided under the hood 13 with an inert atmosphere. For this purpose during the starting phase of the device for coloring, the air under the hood 13 is replaced with nitrogen, which is supplied for example from a pressure gas container through the associated conduit. During the normal operation no or only an occasional post-dosing of nitrogen is required.
[0033] From the outlet of the second squeezing mechanism 7 , the threads are supplied directly into the oxidation line, where the coloring substance is reacted with the air oxygen in the desired known manner.
[0034] Depending on the requirements, several of the above mentioned device components-(wetting stage 1 and oxidation line 2 ) are connected in a sequence one behind the other, and the threads pass through several coloring steps one after the other.
[0035] After the last coloring step, the threads are washed in the washing trough 14 . For this purpose they are immersed many times one after the other alternatingly in the washing trough 14 , and squeezed in the third squeezing mechanism 13 . Therefore excessive coloring substance and auxiliary substances are removed from the threads 4 .
[0036] Finally, the threads 4 are dried and again processed, for example wound.
[0037] Instead of the threads 4 , also other textiles, such as for example a web, can be treated in accordance with the present invention.
[0038] It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of methods and constructions differing from the types described above.
[0039] While the invention has been illustrated and described as embodied in method of and device for covering of textiles, it is not intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
[0040] Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention. | Coloring of continuous textiles includes pad dying the textiles many times in at least one trough; subsequently oxidizing the textiles in an oxidation line; then washing and drying the textiles; and expelling oxygen from the textiles immediately before each pad dying, wherein a reintroduction of oxygen in the textiles is prevented before each green painting. | 3 |
BACKGROUND OF THE INVENTION
This invention is concerned with compositions useful in the molding and curing of automobile tire carcasses and similar hollow rubber articles and is directed particularly at compositions useful to prevent adhesion of the interior of the tire carcass to the pressure bag used in conjunction with the mold.
In the manufacture of automobile tires, uncured rubber is compounded with a variety of agents built into a carcass with desired reinforcing fabric, synthetic fibers, fiber glass roving or metal strands in various configurations. The raw carcass is then cured in a mold; the inside of the raw carcass must be coated with a release film to prevent adhesion of the carcass to the pressure bag during the curing operation, conducted at fairly high temperatures with the carcass under pressure. During the curing operation, an air bag is placed inside the carcass and is inflated to apply the desired pressure to force the carcass into intimate contact with the mold which corresponds to the tread to be imparted to the finished tire. It is necessary that a film of some material be placed between the interior of the raw carcass and the air bag to prevent adhesion of the carcass interior to the air bag. This has been done in the past by spraying the inside surface of the tire carcass with a release coating comprising a dispersion of mica in a silicone containing formulation. Because of the raw materials used, these coatings are expensive and they have two major disadvantages. The first and most objectionable problem with these release coatings which contain silicone is that, where the carcass needs some repair after curing, it is extremely difficult to apply more compound over the interior surface and get adequate adhesion. It is necessary to first completely dissolve away the release coating-- time-consuming, expensive operation. The second problem is that the pressure bags accumulate deposits which build up, so that they must be cleaned after a certain number of molding cycles. This invention aims to overcome both the repair and build-up problems connected with silicone release coatings, while at the same time providing good release at substantial cost savings.
STATEMENT OF THE INVENTION
We obtain these results by the use of a sprayable mold release coating consisting essentially of an aqueous dispersion of about 40% to about 50% (based on entire coating weight) of mica in a nominal particle size range of about 160- 325 standard U.S. mesh sieve, about 4% to about 10% of an aklyl acid phosphate in which the aklyl group contains at least 8 to about 18 carbon atoms, about 2% to 10% of a volatile hydrocarbon, preferably about 5% to 10% of a nonaromatic petroleum distillate, and sufficient surfactant to keep the composition homogeneous, the entire composition being at a pH of about 4.5 to 5.0.
DETAILED DESCRIPTION OF THE INVENTION
In the molding of tires, the inside of the uncured carcass is coated with a release agent to prevent adhesion, during curing, of the inside of the carcass to the air bag, which is inflated to keep the carcass under pressure in contact with the tire mold during the curing cycle. It is desirable that the coating be capable of rapid spray application to ensure a uniform effective film of release agent over the entire inner surface of the carcass, wherever it comes into contact with the air bag.
The mold release coating of this invention is essentially an aqueous dispersion of mica, an alkyl acid phosphate and volatile hydrocarbon containing the correct proportions of the various ingredients to ensure that the coating forms a film over the carcass interior which is sufficiently uniform to ensure complete coating of the carcass and provide a film thick enough to prevent spot adhesion, which will occur if the uncured rubber in the carcass is in contact with the cured rubber of the air bag during the cure.
To obtain this desired result, it is necessary that the composition comprises an aqueous dispersion containing from about 40% to about 50% of ground mica. If less than about 40% is used, the film applied in a standard spraying operation is too thin. Obviously, a thicker film could be obtained by spraying more slowly or by spraying a second coat-- either alternative involves costs both in time and the probability of extra cost due to excessive film build-up. Above about 50% of mica, the physical characteristics of the dispersion become undesirable for spray application.
The mica should be in a particle size range of 160 to 325 standard U.S. mesh sieve. Too many coarse particles cause film discontinuities; if the mica is too fine, application difficulties ensue.
The mica is preferably dispersed in water containing some surfactant to aid in the dispersion. Generally speaking, anionic and nonionic surfactants can be used to aid in the dispersion. However, they are not essential elements in the composition, being used primarily to reduce the cost of the dispersion process. The mica dispersion may be further improved by adding small amounts of water-dispersible high polymers to the dispersion-- example, cellulose derivatives such as methylcellulose, hydroxypropyl methylcellulose, carboxy methylcellulose, hydroxyethyl cellulose, starches, natural gums and the like. These materials, like surfactants, are used in minor quantities to get desirable viscosity control at minimum costs.
A second essential ingredient of the composition is an alkyl acid phosphate, in which the alkyl group contains at least 8 carbon atoms. The compounds may be monoesters, diesters or combinations thereof, and are available commercially, using all the commercial alcohols. Such esters with alkyl groups containing up to 18 carbon atoms are available, and all of them are useful which contain 8 or more carbon atoms.
As with the mica, there are critical limits on the amounts of alkyl acid phosphate. At least about 2% is necessary to get satisfactory release; amounts in excess of 10% are undesirable, both from cost considerations and for getting optimum uniformity of results.
The third ingredient of the composition is a volatile hydrocarbon, whose function seems to be to wet out the unvulcanized rubber in the tire carcass and thus ensure proper distribution and adhesion of the film. With aromatic hydrocarbons, as little as 2% is effective. However, since aromatic hydrocarbons are undesirable because of their pollutant effect and their potential toxicity, we preferably use liquid volatile non-aromatic petroleum distillates in a range of 5% to 10% of the weight of the entire composition. Liquids as highly volatile as the hexanes and octanes may be used, or as difficultly volatile as the kerosenes; they are all readily evaporated by the heat of the tire molding operation. Cleanest results are obtained with the various naphthas used in the paint industry, in the 300°-400° F. boiling range. Since the composition is aqueous, a surfactant is desirable to ensure proper blending of the hydrocarbon with the system. Surfactants which produce an oil-in-water emulsion should be used.
The compositions of this invention are preferably produced by dispersing the mica in water, separately dissolving the alkyl acid phosphate and surfactant in the hydrocarbon, and blending the two by adding the phosphate-surfactant-hydrocarbon solution to the mica dispersion, adjusting the pH and body of the composition with aqueous ammonia, amines, or other soluble alkalis such as caustic soda, to a final pH of about 4.5 to 5.0 and to desired spraying viscosity. This is generally about 2000 to 4000 centipoises at ambient spraying temperatures, most preferably 3000 to 3500 centipoises. The pH control is essential. At high pH, the composition tends to stratify, so that it requires stirring during use; at low pH, the composition becomes too thin for adequate film building under desirable spraying conditions.
Conventional antifoaming agents may be added to the composition to eliminate the necessity for deaerating the composition after dispersion and mixing operations. They are not essential ingredients, being useful to minimize production expense.
The following typical example of the invention is given by way of illustration and not by way of limitation:
__________________________________________________________________________A. Mica Dispersion Ingredients Parts by Weight__________________________________________________________________________1. Water 3652. R & H Tamol 850 (Sodium salt of a carboxylated polyelectrolyte - 30% aqueous solution) 53. R & H Triton CF-10 (Alkylaryl polyether - 100% active nonionic, 60% by weight ethylene oxide, HLB of 14) 54. Ultra Adhesives Dee Fo 97-2 (Antifoam agent- typical product is a blend of emulsified mineral oils, silica derivatives and esters. Does not contain silicone compounds or derivatives 25. Mica - water ground 325 mesh 440 Mixed well with above to obtain a uniform dispersion.B. Dispersion Ingredients Parts by Weight__________________________________________________________________________1. Engelhard Attagel 40 (Attapulgite clay) 52. Union Carbide Cellosize QP-100M-H (Hydroxyethyl cellulose) 1.253. Water 43.75 Mixed so as to obtain a uniform dispersion.C Dispersion Ingredients Parts by Weight__________________________________________________________________________1. Witco PS-400 (Mixed mono-dialkyl (C.sub.8 -C.sub.10) acid phosphate, about half mono and half diester) 402. Olin B-150 (Nonylphenoxy polyethanol, 100% active nonionic, 44% by weight ethylene oxide, HLB of 8.8 7.53. Antifoam agent (same as A.4 above) 2.04. Petroleum naphtha or mineral spirits (boiling range 320-360° F.) 70 Mixed well so as to obtain an uniform dispersion.__________________________________________________________________________
Dispersion B was added to the Mica Dispersion A while mixing; this mixture was added to Dispersion C while stirring well. The pH of the finished material was adjusted to between 4.5 and 5.0 with 28% aqueous ammonia; this required 12.0 parts by weight. The product had a viscosity of about 3000 centipoises at 20° C. It gave excellent results when used to coat the interior of raw tire carcasses prior to molding and curing. On our extensive test run, in a tire plant, uniform coating was obtained, the cured tires separated from the air bag without sticking. Injured carcasses could be repaired without removal of the coating. The air bags and tire molds came out of the operation clean, with no accumulation of coating, so they could be re-used immediately.
As indicated above, this example can be modified extensively so long as the essential ingredients and proportions of properly sized mica, alkyl acid phosphates with 8 to 18 carbon atom alkyls, and volatile hydrocarbon are used, and the proper pH is attained, all as defined in the claims. | A composition is described for coating the inside surfaces of tire carcasses and other hollow rubber articles prior to curing so as to prevent adhesion between the carcass and the pressure bag during the cure stage, comprising a sprayable film formed from an aqueous dispersion containing about 40 to 50% of finely ground mica, a small amount of volatile hydrocarbon, about 4 to 10% of an alkyl acid phosphate and sufficient surfactant to keep the composition from separating. | 1 |
The present invention relates to a shoe closure system and a method for tying a lace tied shoe wherein a movable clutch is securely captivated on a shoe lace.
BACKGROUND OF THE INVENTION
Laced shoes are very comfortable to wear because the user can tighten the laces to suit his preference and to compensate for stretching of the upper, swollen feet and so forth. One problem with laced shoes, however, is that they often become untied during use requiring the wearer to stop what he is doing and retie his shoes. This is especially a problem for young children who usually cannot tie their own shoes until they are about six or seven years old but who insist on doing things themselves and sometimes break the counter by stepping in and out without untying the bow.
Velcro closures address the problems associated with laced shoes but give the shoe an undistinguished appearance that lacks the decorative aspect or grown-up look of a lace. In addition, the ripping sound of opening the closure is distracting and irresistibly fascinating to children.
A number of difference devices have been proposed for clamping on bows to keep them from untying. These devices, however, do not eliminate the need for tying a bow. Other devices function as clutches to take the place of a bow. These latter devices, while obviating the need for tying a bow, are easily slid off the free ends of the lace and are therefore hazardous for young children. The shoe tying system described in U.S. Pat. No. 4,458,373 to Maslow partially confronts the latter objection by tying the free ends of the laces to the front of the shoe. For the Maslow system to work, however, the laces must be left long giving the shoes a sloppy appearance and the knot can be untied and the cord-lock slid off.
In view of the above, there is a need for a shoe closure system and method for tying which does away with the need to tie a bow and which does not slip off the lace. It is therefore an object of the present invention to provide such a system and method. Other objects and features will be in part apparent and in part pointed out hereinafter.
The invention accordingly comprises the constructions and methods hereinafter described, the scope of the invention being indicated in the following claims.
SUMMARY OF THE INVENTION
A shoe closure system and a method for tying a lace tied shoe wherein a movable clutch is threaded on the ends of a lace and held captive by a stop means securely attached thereto. In a preferred embodiment the ends of the lace are joined together and the stop means releasably stuck to the shoe or to the lace adjacent the front of the shoe.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings, in which several of various possible embodiments of the invention is illustrated, corresponding reference characters refer to corresponding parts throughout the several view of the drawings and in which:
FIG. 1 is a top and side perspective view of a pair of shoes having a shoe closure system in accordance with the present invention;
FIG. 2 is a top view of the right shoe partly broken away as shown in FIG. 1 with the free ends of the lace released;
FIG. 3 is an enlarged top view of the right shoe as shown in FIG. 2 with the shoe closure system released;
FIG. 4 is a side view of a cord-lock;
FIG. 5 is a sectional view taken along line 5--5 in FIG. 4; and,
FIG. 6 is an alternative stop means for the clutch shown in section on a shoe.
DETAILED DESCRIPTION OF THE INVENTION
Referring to the drawings more particularly by reference character, reference numeral 10 refers to a shoe closure system in accordance with the present invention including a movable clutch 12 held captive on a lace 14 by a stop means 16 located adjacent the free ends of the lace.
As shown in FIGS. 1-3, a lace tied shoe 18 has an upper 20 attached to a sole 22 and forming a collar 24 about the foot of a wearer. The vamp of upper 20 is split at 26 with at least one lace hole 28 provided on each side thereof, more typically, however, provided in series with an equal number of holes on each side. Lace 14 is inserted through an opposing pair of lace holes 28 starting at the bottom of split 26 closest the front of the shoe and laced in a conventional manner through the series of lace holes that are provided. At the top of the split, the free ends of lace 14 extend through terminal lace holes 28 on each side of split 26 and then pass through and are retained by clutch 12 (e.g. clutches if a separate clutch is provided on each lace) which tightens upper 20 over the instep of the wearer.
The free ends of lace 14 are attached to stop means 16 which retain movable clutch 12 on the lace. Separate stop means can be provided on the free ends of each lace but it is preferred that the ends of lace 14 be joined by the stop. For safety and convenience, it is important that stop means 16 not be easily removable from lace 14 thus excluding the expedient of a simple knot but a shielded knot 30, as shown in FIG. 6, e.g. recessed in a bead 32 threaded on the free ends of lace 14 and preferably fused or coated such that it does not untie, may be used on shoes for all but the youngest of children. It is preferred, however, that the free ends of lace 14 be sewed, glued or otherwise securely attached to stop means 16 and that stop means 16 be releasably stuck to shoe 18 or to lace 14 adjacent the front of the shoe such that the free ends of the lace are dressed neatly against the laced portion of the lace as shown in FIG. 1. This preferred embodiment also keeps stop means 16 from bouncing at the ends of lace 14 when shoes 18 are worn.
Suitable means for releasably sticking stop means 16 to the shoe or the bottom of the lace release by pulling on the free ends of the lace adjacent the stop. As shown in FIG. 2, this can be accomplished in a variety of ways such as by attaching a magnet 34 to the underside of stop means 16 which is releasably attracted to a metal 36 fixedly attached to shoe 18 or to lace 14 adjacent the front of the shoe. Other releasable sticking means include Velcro, snaps, hooks and the like as will occur to those skilled in the art.
As shown in the drawings, clutch 12 is a cord-lock having a piston 38 inserted into a cylindrical base 40 which is closed at one end and open at the other. While clutch 12 is illustrated as a cord-lock, it can take the form of other movable means capable of grasping the free ends of lace 14 tightly such as a spring clamp or the like. With continuing reference to the drawings, cylinder 40 is filled with a coiled spring 42 which is compressed when the piston is pressed into the cylinder. The piston is provided with an opening 44 which, when the piston is pressed down into the cylinder compressing spring 42, matches an opening 46 near the open end of cylinder 40. When opening 44 is aligned with opening 46, the free ends of lace 14 may be inserted through the openings. When piston 38 is then released, spring 42 exerts upward pressure and clamps lace 14 in holes 44 and 46 preventing further movement of clutch 12 on lace 14.
Spring 42 is sized for close fit within cylinder 40 and the forward end of piston 38 is of reduced diameter 48 for close fit within the terminal coil of spring 42 to prevent piston 38 from being separated from cylinder 40 under normal circumstances. On the other hand, piston 38 can be released from spring 42 by pulling on it with sufficient force and exchanged for another piston 38 which may be formed of some other color or otherwise decorated to mix and match cylinder bases and pistons as desired when system 10 is disassembled.
In use, lace 14 which for children's shoes generally is too short to be tied into a bow is laced into lace tied shoe 18 through lace holes 28. The free ends of lace 14 are then threaded through movable clutch 12 and stop means 16 are securely attached so that the clutch is captivated on the lace and is movable between collar 24 of the shoe and the stop means. In a preferred embodiment stop means 16 is releasably stuck to the shoe or lace to keep the stop means from bouncing when the wearer takes a step.
In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results attained. As various changes could be made in the above constructions and methods without departing from the scope of the invention, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. | A shoe closure system and method for a lace tied shoe which eliminates the need for tying a bow and which does not slip off the lace. The lace is secured by a movable clutch which is captivated on a lace by a stop securely attached to the free ends of the lace and preferably releasably stuck to the shoe or to the lace adjacent the front of the shoe. | 0 |
BACKGROUND AND SUMMARY OF THE INVENTION
This invention relates to the treatment of wellbore casing, tubing, drillstring, etc. to remove pipe dope. Pipe dope is a pipe thread sealant. The primary function of thread compounds is to provide sealability, galling resistance, and uniform frictional characteristics while lubricating the thread pattern of drill pipe during make up.
The current API MODIFIED pipe dope was introduced in 1955. The API MODIFIED contains lead, zinc, graphite and copper. Other metals such as aluminum flake, brass, bronze, nickel, talc, silica, calcium carbonate and clays have been used in other compounds. The heavy metals, up to 25 percent of the volume provide the sealability with their particle size being in the range of 45 microns.
The API 8 round connections are tapered with the primary sealing mechanism being achieved by making up the threads until plastic deformation of the threads occurs. The thread compound must create a film strong enough to maintain a barrier and seal between the two contacting surfaces. If the integrity of the thread compound film was broken down, the bearing stresses and heat created at the point of contact would cause the connection to weld together. The joint would eventually break down due to the tearing of the weld during additional rotation.
Unfortunately these thread compounds will effectively seal off pore throats in the formation, gravel pack or even whole perforations. By design, these compounds are resistant to temperature and chemical degradation and are difficult to remove from tubing, and nearly impossible to remove from the confines of a pore throat.
The extent of the problem can be illustrated by a typical scenario involving the completion of a 10,000 foot well with 27/8-inch, 6.4 pound tubing. The tubing string would have 322 connections, assuming 31 foot joint length. If an average of two teaspoons of dope per connection were extruded into the string, approximately one quart of dope would end up in the tubing. Considering that the dope is water insoluble and if it were to collect in the bottom of the work string, a total of four feet of tubing could be filled. In addition most completions require several pipe trips involving the re-doping of many of the connections.
A common misconception is that pipe dope is removed or is soluble in acid or caustic when a pickle job is conducted. Acid or caustic however has almost no effect on the pipe dope.
In the past the pipe dope has been removed by using various solvents such as xylene, toluene and even low flash point terpenes. Because of increasing safety and environmental concerns these chemicals are unattractive.
A new composition for cleaning pipe dope from a well system has been developed. The composition includes a terpene hydrocarbon with a flash point of greater than 140° F. mixed with either an oil soluble aliphatic hydrocarbon, an ester with a flash point of greater than 140° F., or mixtures of both oil soluble aliphatic hydrocarbons and esters. The oil soluble aliphatic hydrocarbon component may be a mixture of different oil soluble aliphatic hydrocarbons and, likewise, the ester component may be a mixture of esters. The preferred terpenes are biodegradable monoterperens more preferably alpha-pinene derivatives. The preferred oil soluble aliphatic hydrocarbons have a viscosity of less than 10 cps @ 75° F. Preferred esters are acetic acid esters of C 6 -C 8 branched alcohols. The preferred oil soluble aliphatic hydrocarbons are petroleum napthas. In the preferred mixture the terpene hydrocarbon is from about 90% to about 50% by weight of the composition and the oil soluble aliphatic hydrocarbon, ester, or mixture of both is about 10% to about 50% by weight of the composition.
A process has been developed to use the composition mixed with a brine solution such as seawater to remove the pipe dope. Although the composition can be pumped in the well without dilution, it has been found that a dilute solution offers excellent cleaning capability with about 5 to 20 minutes of contact with the area to cleaned with 10 minutes of contact time preferred. The same pump that is used on a rig to pump the cement can be utilized to pump a combination brine and pipe dope cleaning composition. Since the same pumping system is used and the contact time for a dilute solution is only 10 minutes, a significant savings in rig time utilization is achieved.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 shows the chemical structures of d-Limonene, alpha-pinene and some derivatives of alpha-pinene in IUPAC format.
DETAILED DESCRIPTION OF THE INVENTION
The composition is a blend of high flash point (greater than 140° F.) terpene hydrocarbon with oil soluble aliphatic hydrocarbons or esters with a flash point greater than 140° F. used in the removal of pipe dope. The composition can be pumped neat or in conjunction with seawater. The material is not soluble in seawater but when pumped in turbulent flow the solvent is broken into small droplets. The small droplets are more effective in removing the pipe dope and as a result higher pump rates can be used. The higher pump rate reduces rig operation time by several hours.
Pickling of the string can be conducted in several ways. A pump rate of 1 bbl/min has long been established in the industry. The purpose of the pipe dope pickling is to remove the dope. A subsequent treatment (acid pickling) is performed following or in conjunction with the pipe dope pickling to remove scale, rust or other contaminants by use of 5 to 15% HCl. The solvent removes the dope that may be covering the scale to improve the efficiency of the acid treatment.
A typical treatment is as follows. Pump a pill consisting of 4 drums (5 barrels) of the pipe dope cleaning composition down the tubing at 1 bbl/min. The preferred composition is about 70% alpha-pinene derivatives, Glidsol 180 manufactured by Glidco and 30% of the preferred aliphatic hydrocarbon, petroleum naptha. When the pill reaches the bottom of the tubing, but before turning the corner, reverse the flow and pump the material out of the string or tubing. This provides a total contact time of 10 minutes. The pump sequence can have a pill of acid, normally 5 to 15% HCl following directly behind the solvent. The HCl is in an aqueous solution of water, seawater, filtered brine or other available aqueous solutions.
If the tubing had a volume of 180 bbls, 6 hours would be required to pickle the string. If one pumps at 2 bbl/min (50% dilution of pipe dope cleaning composition in seawater) the time would be cut in half. For a Gulf of Mexico operation at $24,000.00/day current rig cost, the savings would be $3,000.00 and in a North Sea operation with a daily current rig rate of $60,000.00/day the savings would be $7,500.00.
EXAMPLE 1
Pipe dope is difficult to remove from steel. A test is conducted to see how quickly API MODIFIED COMPLEX pipe dope can be removed from steel. A 400 ml beaker is filled with roughly 250 ml of the fluid to be evaluated. A magnetic stir bar is used to put the fluid in turbulent flow. A steel coupon with approximately 1 inch by 2 inch area covered with about 3/32 inch layer of pipe dope is lowered into the fluid and the cleaning efficiency is measured with respect to time. The solvent tested shows a flash point measured by the Pensky Martin Closed Cup method (PMCC) in the following Table 1 and as noted in other tables herein.
TABLE 1______________________________________SOLVENT/ OIL AND PERCENT CLEANINGFlash point WATER EFFICIENCY @(PMCC, °F.) SOLUBLE 5 min. 10 min. 15 min.______________________________________Product A Y/N 57 90 97Terpene Y/N 86 97 100HydrocarbonGlidsol 180/142d-Limonene A/120 YIN 77 93 100d-Limonene B/122 Y/N 93 1002-ethyl hexyl Y/N 71 85 97acetate/160Seawater N/Y 0 0 05% HCl in N/Y 0 0 0seawater______________________________________
The results summarized in Table 1 show the following. The high flash terpene hydrocarbon exceeds the performance of an existing high flash point material Product A which is a blend of d-Limonene and high flash point paraffin oil which suppresses the flash point but lowers the solvent action. The high flash point terpene is comparable to two low flash point d-Limonene materials. Seawater and HCl are ineffective in removing pipe dope.
Glidsol 180 is produced by Glidco and is a product of alpha-pinene derivatives. D-Limonene as shown in FIG. 1 is from citrus oil and has been used as a cleaner for various oil field applications. The structure of d-Limonene is known as the terpene hydrocarbon dipentene. Also shown in FIG. 1 is alpha-pinene which can be obtained from the sulfate liquor by product of the Kraft paper process. The alpha-pinene can be chemically modified to form the alpha-pinene derivative structures also shown in FIG. 1 that are similar to d-Limonene. The alpha-pinene derivatives shown on FIG. 1 are exemplary and many other structures are known to those skilled in the art. These structures have similar cleaning abilities, but have been discovered to have distinct advantages in drilling applications in pipe dope removal and wellbore clean up. The flash point of these derivatives is greater than 140° F. making them safe to transport and handle. The flash point of dipentene (d-Limonene) is below 140° F. The use of the alpha-pinene derivatives in combination the oil soluble aliphatic hydrocarbons and esters of the present invention has produced unusual results in cleaning pipe dope.
EXAMPLE 2
The following Table 2 is a sampling of various types of solvents and the ability to clean pipe dope using the methodology of Example 1.
TABLE 2______________________________________ Flash Percent Cleaning Point Oil H.sub.2 O Efficiency °F. Solu- Solu- 10 15Solvent Class (PMCC) bility bility 5 min min min______________________________________EXXSOL AHC 221 Y N 37 68 91D-110SHELLSOL AHC 142 Y N 77 97 100142 HTISOPAR M PAHC 177 Y N 12 30 46EXXATE E 151 Y N 78 97 100700PINE TE 200 Y N 26 55 77ESTEREASTMAN GE 212 Y Y 28 44 72DBDOW DPMA GE 186 Y N.sub.SM 6 9 15DOW EB GE 150 Y Y 3 6 11______________________________________ AHC Alphatic Hydrocarbon PAHC Paraffinc Aliphatic Hydrocarbon E Esters TE Terpene Ester GE Gylcol Ether EXXSOL D110 Petroleum Naptha, Exxon Chemical SHELLSOL 142 HT Petroleum Naptha, Shell Oil ISOPAR M Isoparaffinic Hydrocarbon, Exxon Chemical EXXATE 700 Acetic Acid Ester of C.sub.6 -C.sub.8 branched alcohols also known as Oxoheptyl alcohol, Exxon Chemical EASTMAN DB Diethylene Glycol Monobutyl ether, Eastman Chemical DOW DPMA Dipropyl Gylcol Monomethyl Ether Acetate, Dow Chemical DOW EB Ethylene Gycol NButyl Ether, Dow Chemical
EXAMPLE 3
A test on blends of an aliphatic hydrotreated hydrocarbon in removing API MODIFIED COMPLEX. The test procedure was the same as that in Example 1. The terpene hydrocarbon was Glidsol 180.
TABLE 3______________________________________SOLVENT/ PERCENT CLEANING(X/Y + RATIO BY EFFICIENCY @WEIGHT) 5 min. 10 min. 15 min.______________________________________SHELLSOL 142 HT 77 97 100Terpene 86 97 100Hydrocarbon (TH)TH/AH 90/10 80 93 100TH/AH 80/20 88 100TH/AH 70/30 91 100TH/AH 60/40 77 97 100TH/AH 50/50 70 95 100______________________________________
These data show that maximum efficiency was achieved at a ratio between 80/20 and 60/40 terpene/aliphatic hydrocarbon. In commercial operations a preferred blend is 70/30 terpene/aliphatic hydrocarbon.
EXAMPLE 4
A test was conducted on a 70/30% by weight, TH/AH blend mixed with seawater in removing API MODIFIED COMPLEX pipe dope at 75° F. The rest of the test procedure was the same as that in Example 1.
TABLE 4______________________________________ PERCENT CLEANING EFFICIENCY @SOLVENT 2.5 min. 5 min. 10 min. 15 min.______________________________________20% in seawater 48 87 97 10040% in seawater 67 90 10060% in seawater 70 94 10080% in seawater 72 97 100100% TH/AH 84 90 100______________________________________
EXAMPLE 5
A test was conducted on a 70%/30% by weight TH/AH blend mixed with seawater in removing API MODIFIED COMPLEX pipe dope at 110° F. The rest of test procedure was the same as that in Example 1.
TABLE 5______________________________________ PERCENT CLEANING EFFICIENCY @SOLVENT 1 min. 2.5 min. 5 min. 10 min.______________________________________20% in seawater 38 75 10040% in seawater 47 88 10060% in seawater 61 91 10080% in seawater 58 94 100100% TH/AH 47 81 100______________________________________
The data in Examples 4 and 5 show the improved cleaning of the seawater blends over the neat solvent procedure. The drop of in performance between 60 and 100% solvent indicates the improved performance of droplets in turbulent flow.
EXAMPLE 6
A test was conducted to determine the effectiveness of Exxon D-110 a petroleum naptha aliphatic hydrocarbon with the preferred terpene, Glidsol 180. The test procedure was the same as Example 1.
TABLE 6______________________________________ PERCENT CLEANINGSOLVENT 5 min. 10 min. 15 min.______________________________________Glidsol 180 (TH) 86 97 100EXXON D-110 (AH) 38 69 91TH/AH by weight %90/10 93 10080/20 94 10070/30 87 97 100______________________________________
EXAMPLE 7
A test was conducted on an ester and the preferred terpene hydrocarbon Glidsol 180. The test procedure was the same as Example 1. The ester is Exxate 700 which is an acetic acid ester of C 6 -C 8 branched alcohols.
TABLE 7______________________________________ PERCENT CLEANINGSOLVENT 5 min. 10 min. 15 min.______________________________________Glidsol 180 (TH) 86 97 100EXXATE 700 (E) 78 97 100TH/E by weight %90/10 94 10080/20 93 10070/30 91 100______________________________________
The results with the ester are slightly better than the SHELLSOL HT, however the cost of the ester is significantly more. Also, 2-ethylhexylacetate can be used.
It is apparent that there has been described herein a chemical composition and process for effectively removing pipe dope from a well drilling system. Various changes and alterations may be made in the practice of the chemical composition and process by those skilled in the art without departing from the spirit of this invention. It is intended that such changes be included within the scope of the appended claims. The present description is intended to be illustrative and not limit the present invention. | An improved chemical composition and process for cleaning pipe dope from wellbores has been established. The chemical composition is of an aliphatic hydrocarbon and/or esters with a biodegradable water insoluble monoterpene preferably having a flash point (PMCC) greater than 140° F. the mixture then used neat, or in a dispersion of seawater, being used to remove pipe dope from tubing, casing and the like. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims benefit from U.S. Provisional Patent Application No. 61/431,949, entitled “COLOR SPOON,” filed on Jan. 12, 2011, which is hereby incorporated by reference in its entirety.
FIELD
[0002] This application relates to a method of allowing customers to personally view cosmetic materials they located on the internet without leaving their homes and more particularly to a colored spoon.
BACKGROUND
[0003] In earlier days, consumers would go to a shopping mall or to a store and browse products they were looking to purchase. In the case of nail polish, they would often look at samples of the nail polish to ensure that it was the color they desired. The ability to look at the color of the nail polish with their own eyes, with the nail polish being used in a similar manner to how the consumer would use such a product, was invaluable to a consumer before making such a purchase. This left most consumers happy with the color of nail polish they purchased.
[0004] Today, more and more purchases, including nail polish, are occurring over the internet. This is because of the greater convenience purchasing products over the internet provides. However, one drawback of purchasing products over the internet, and especially nail polish, is that it can often be very difficult to clearly see what a product looks like. This is especially true with shades of colors, as the limited resolution of computer screens often blur and distort the actual shade of the color. This has often lead online consumers of nail polish to purchase colors thinking that they are getting the exact color they see on the screen, and then being disappointed by the actual color they receive when the product arrives. This has led to many unhappy customers who are receiving products they do not desire. The large amounts of unsatisfied customers lead to many returns, loss of future customers, loss profits and increased costs to the seller.
[0005] In addition, when viewing colors on a computer screen, a consumer is only viewing the color in a two-dimensional view, in a manner that is not similar to how that color will be used by the consumer. This also has led to many unhappy consumers who are disappointed by the color they receive when they finally view it in a three dimensions and use the product in a manner it was intended to be used.
[0006] The present invention provides a design that overcomes these challenges, including providing a method of allowing customers to personally view cosmetic samples of colors they located on the internet without having to leave their homes.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] Embodiments of the present disclosure are described herein with reference to the drawings wherein:
[0008] FIG. 1 illustrates a screen shot of how the color segments are displayed;
[0009] FIG. 2 illustrates a top view of the color spoon; and
[0010] FIG. 3 illustrates a top view of the color plate.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0011] Reference will now be made in detail to embodiments of the invention, examples of which are illustrated in the accompanying drawings. It is to be understood that other embodiments may be utilized and structural and functional changes may be made without departing from the respective scope of the invention.
[0012] The following is a method of relaying to consumers information about the color of goods sold. In particular nail polish, lip gloss, make-up, or any other cosmetic good. In general, the method comprises a consumer entering a website and viewing a webpage with all colors listed. The consumer then selects a color it desires and submits that information into the webpage. The consumer then enters in their personal information. The company then sends samples of the selected products and colors to the consumer. The samples may be obtained for a small price and that price may be used as a credit for a future purchase. The samples sent to the consumer may be color spoons 10 with end portions 12 that are colored with the selected color. This enables a consumer, without leaving their home, to view colors of nail polishes in person before they purchase them. This also enables a customer, without leaving their home, to not only inspect the actual color of a cosmetic material, but to also inspect the relation of the cosmetic material to a customer's skin tone.
[0013] A consumer may enter a website, such as, but not limited to, zoya.com. In one embodiment, the consumer may then proceed to a display by selecting an option group such as, but not limited to, nail polish, lip gloss or color spoons. After selecting an option group the consumer is then lead to a webpage 14 that shows multiple colors available in a display of color segments for the selected option group. In another embodiment, a consumer may select an option group such as, but not limited to, a product type, product name, seasonal collection, or color finder which then the colors of the cosmetics are shown in color segments on the webpage which then leads the consumer to a webpage 14 that shows multiple colors available in a display of color segments 26 for the selected option group.
[0014] FIG. 1 shows one embodiment of how the color segments 26 may be displayed. The color segments 26 may be arranged in a variety of ways such as, but not limited to, color family, color shades, name, or number color. As shown in FIG. 1 , the color segments 26 are aligned vertically in one column. However, the color segments 26 may be arranged in many fashions such as vertically in two or more columns or horizontally in one or more rows.
[0015] In one embodiment, the color segments 26 are arranged so that they are placed adjacently in order of color shades that are most similar. In one embodiment, a consumer may select a color from a color chart by clicking on a desired color link 16 , typing in a desired color, or by any other means known for selection from a website. In one embodiment an “ADD TO BAG” 18 icon may be placed adjacent to each color segment 26 . A consumer may then select that icon to indicate that is the color of the color spoon 12 they are interested in purchasing.
[0016] In one embodiment the consumer may then enter how many products he wishes to purchase. A quantity box 20 where the consumer may enter in the quantity of products he wishes to purchase may be labeled “Qty”, as shown in FIG. 1 , but may also be labeled in any other manner. The number that may be entered into the quantity box 20 may be one or more. The number may be selected from a drop down box listing increasing numbers or may also be typed into the quantity box 20 .
[0017] At some point, either before selecting the color or after selecting the color, a consumer may enter personal information into the website including, but not limited to, a mailing address, payment information, a login ID and corresponding password, email address, personal preferences, or any other information commonly entered into websites during purchases. Color spoons 10 or color plates 24 containing the color shades selected by the consumer are then shipped to the consumer's mailing address for the consumer to sample. In one embodiment the color spoons 10 or color plates 24 are shipped to the consumer at no cost of the consumer. However, in other embodiments the consumer may be charged partially or fully for shipping.
[0018] In one embodiment the consumer may be charged for each color spoon 10 . In another embodiment the amount the consumer is charged for each color spoon 10 may be applied to any future purchase made on the website. This information may be stored on the website and may be saved to each consumer's personal login information. The information may also be stored in any other fashion known.
[0019] A color spoon 10 may be comprised of a plastic material or any other similar material. In one embodiment a color spoon 10 is substantially clear and may enable visible light to pass through.
[0020] The single color spoon 10 may contain a handle 22 and an end portion 12 that is shaped substantially similar to a human finger nail. In one embodiment, the handle 22 may be narrower than the color spoon end portion 12 , as shown in FIG. 2 . The color spoon end portion 12 is shaped in a concave shape at the non-colored side. The non-concave area of the color spoon end portion may be coated with a particular shade of nail polish or any other cosmetic material. In one embodiment, a color spoon end portion 12 is coated with the actual color of a cosmetic material, not a color match.
[0021] The concave side may be placed over the consumer's fingernail to enable a consumer to see how a particular shade of nail polish would look on their fingernails. This enables a consumer to see if they like a particular shade of nail polish by enabling them to see the color directly, and over their fingernail, instead of through a computer screen. In addition, the shape of the color spoon end portion 12 enables a consumer to place a fingernail-like colored material over their own fingernail to sample the nail polish as close as they can without putting the nail polish on their own nails.
[0022] In one embodiment color spoon end portions 12 may be provided in color spoons 10 as shown in FIG. 2 or may be attached to a plate to form a color plate 24 as shown in FIG. 3 . A color plate 24 may be comprised of plastic or any other similar material that may be used to make the color spoons. A color plate 24 may contain two or more color spoon end portions 12 on the perimeter of the plate. In one embodiment, the color plate 24 is of a rectangular shape with the color spoon end portions 12 being placed on opposite sides of the rectangular plate. In one embodiment, it is common for the color spoon end portions 12 to be placed on the longer end of the rectangular shaped color plate, although the color spoon end portions 12 could be placed at any location on the perimeter of the color plate 24 .
[0023] The present invention provides a design that overcomes the many challenges associated with ordering cosmetics, in particular nail polish, on the internet which will lead to increased customer satisfaction. | This application relates to a method of allowing customers to personally view cosmetic materials they located on the internet without leaving their homes and more particularly to a colored spoon. | 0 |
BACKGROUND
[0001] Nanoscale technologies, similar to other technologies, face challenges in high power consumption and signal delay due to global interconnects, but due to their scope, addressing these challenges opens new areas of research. One research area is through silicon via (TSV) based 3D integrated chip (IC) technology, where each layer or stratum is fabricated separately and subsequently vertically integrated. With 3D ICs, the fabrication of disparate strata and the final system integration may be completed in separate manufacturing facilities, allowing for greater efficiency and the possibility of modular layers. The packaging manufacturer performing the final bonding, thus, may not necessarily need each layer's technology-dependent parameters such as voltage levels and frequency of operation to assemble the 3D IC. This transparency-to-technology information allows for off-the-shelf integration where dies from different foundries are bonded together by the packaging manufacturer to form a heterogeneous 3D IC.
[0002] A semiconductor device scaling has exacerbated fundamental problems with CMOS technology like parametric variation and device aging. The most significant ill effect of these problems is seen through power supply voltage variation. Conventional microprocessor designs compensate for the worst case power supply voltage variation by introducing voltage guard bands which leads to a significant overhead on the total power consumption of the IC. In-situ aging sensors are deployed on microprocessors to automate the effects of circuit aging. However, a run-time aging detection and correction technique which can be used in tandem with on-chip voltage regulators is missing.
SUMMARY OF THE INVENTION
[0003] A circuit that detects the power supply voltage requirement of each voltage domain in an IC includes 1) a ring oscillator in each voltage domain, and 2) a power module. Two different circuit implementations of the power module may provide a precise reference voltage to on-chip voltage regulators (LDO or DC-DC switching buck converter). The power module supports DVFS and can provide the desired power supply voltage for advanced CMOS technology nodes (45 nm and beyond) in less than 100 ns. The voltage detection circuit clamps the voltage to the desired level to address power supply voltage variations due to PVT and ageing. The proposed technique has minimal power and area overhead to compensate for the power supply voltage variation, thus reducing power supply voltage margins which yields higher power saving.
[0004] The proposed circuit technique has another application for 3-D heterogeneous ICs. The 3-D IC may include RF, analog, micro/nano-electromechanical systems (MEMS/NEMS) as well as emerging technologies such as nano-FET and graphene-based device planes. The design and fabrication of these disparate device planes may take place at separate facilities. Unless technology specific information on each device plane is provided, the packaging facility carrying out the final 3-D integration of the device planes is unaware of the power supply voltage requirements of the different ICs. The proposed circuit detects the power supply voltage needs of each voltage domain on different device plans of the 3-D IC. This facilitates true plug-and-play integration for 3-D heterogeneous ICs.
BRIEF DESCRIPTION OF THE DRAWINGS
[0005] FIG. 1 shows the placement of components on the device and power planes.
[0006] FIG. 2 shows a current starved RO with an output switching inverter.
[0007] FIG. 3 shows the simulation results for detecting and clamping the power supply voltage for a voltage domain in a 22 nm device plane.
[0008] FIGS. 4( a ), 4( b ), and 4( c ) are graphs that show the ring oscillator frequency variation with threshold voltage VTH, channel length, and MOSFET low-field mobility.
[0009] FIG. 5 shows the circuit implementation of a Frequency to Voltage Converter (FVC).
[0010] FIG. 6 shows a Voltage Controlled Current Source (VCVS) comprising a voltage comparator and a current source that charges a capacitor C.
[0011] FIG. 7 shows the transient response of the 22 nm ring oscillator (Fout_22 nm), the FVC output voltage (Vfvc), and the control voltage generated by the VCVS block (Vctrl_22 nm).
[0012] FIG. 8 shows a block diagram of the various components of the 3-D IC supply voltage detection and clamping circuit.
[0013] FIGS. 9( a )-9( c ) show various circuit details described herein.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Introduction
[0014] The plug-and-play approach described above may be driven in several ways. First, organizations may develop, and the industry adopts, guidelines to standardize the interface circuit properties (location and electrical characteristics of IO ports and ESD protection) for each device plane. Second, the 3D IC stack's global power and clock-generation circuits must be met for each stratum.
[0015] The power supply voltage detection and power delivery circuit described herein provides the global power generation and distribution through a power delivery system that senses the power supply voltage needed by each voltage domain (VDD_DP) in each device plane at run time. A dedicated power plane detects each domain's power supply voltage requirement, and delivers power to all voltage domains in the 3D stack accordingly. The power plane generates a range of voltages (ideally from 0.5 V to 5 V) to meet the power supply voltage requirements of the various technology nodes. Further, device planes may have significantly varying power budgets, requiring single or multiple power planes interspersed between device planes, depending upon the 3D IC stack configuration.
[0016] The design described herein provides power to a heterogeneous device configuration that may include CMOS, MEMS, or RFICs operating on disparate substrates not limited to Silicon or III-V technologies (GaAs, GaN, InP, etc.).
[0017] II. Run Time Voltage Detection and Power Delivery
[0018] Each voltage domain within each device plane includes a ring oscillator capable of generating an output frequency F out of 1 GHz when a control voltage equal to the power supply voltage V DD _ DP of the domain is applied. A 1 GHz frequency is an arbitrarily chosen value for the proposed circuit and may be adjusted based on set standards, and reflects one value that serves as a common frequency of operation for all ring oscillators placed on different device planes in a given 3-D IC stack. As proposed, the only required overhead for each voltage domain is the ring oscillator. The remaining components of the voltage sense circuit are part of the power module placed on the dedicated power plane.
[0019] FIG. 1 shows the placement of the components on the device and power planes. The 3-D stack 100 includes device planes 110 , 120 containing multiple voltage domains 112 , 114 and 122 , 124 served by a power plane 130 with multiple power modules 132 , 134 . Each power module 132 , 134 includes a voltage-controlled voltage source (VCVS) 136 controlled by voltage generated from a frequency to voltage converter (FVC) 138 . A ring oscillator 116 placed in each voltage domain provides a controlling frequency to the FVC 138 .
[0020] The Fout generated by the ring oscillator 116 propagates through TSVs 150 to the power plane 130 . The FVC 138 generates a voltage Vfvc inversely proportional to Fout. Vfvc is equal to 690 mV when an input frequency of 1 GHz is applied to the FVC 138 . The ring oscillator frequency 116 increases until 1 GHz is reached, which is determined by comparing the FVC 138 output voltage to a reference voltage source Vref set to 690 mV. The VCVS 136 supplies the control voltage to the ring oscillator 116 . The VCVS 136 is controlled by a voltage comparator that compares the Vfvc with Vref. Dedicated power modules 132 , 134 comprising the FVC 138 and the VCVS 136 facilitate point of load power delivery that: 1) reduces noises due to a reduction of the parasitic impedance of the power distribution network as the voltage source is closer to the load circuit, 2) supplies different voltages to heterogeneous circuits, and 3) provides finer granularity for voltage control.
[0021] The circuit structure and operation of components included in the voltage sense and power delivery circuit are described below. Circuits may be designed with 45 nm and 22 nm PTM models for, respectively, the power plane and device plane, but circuits designed and fabricated in any technology node are plausible.
[0022] A. Ring Oscillator Circuit for Individual Voltage Domains
[0023] Ring oscillators (RO) may be used as voltage controlled oscillators (VCO) in high performance integrated circuits as the fundamental block for frequency synthesizers, clock recovery circuits, and clock distribution networks. The application of ring oscillators is not limited to VCOs, as ROs may be used for on-chip thermal sensors and test structures to measure process variability. The RO's flexibility may be attributed to a simple CMOS implementation with no passive components, which reduces the occupied silicon area. The output frequency may be stable in the presence of process, voltage, and temperature variation (PVT) and the applied control voltage.
[0024] Several ring oscillator circuit topologies may provide a steady frequency reference for the detection of the targeted VDD_DP of a given voltage domain. The selected ring oscillator circuit topology should provide a large frequency range when the applied control voltage varies from VDD_DP/2 to VDD_DP and a minimum variation in frequency due to sensitivity to PVT. A current starved RO with an output switching inverter (shown in FIG. 2 ) provides frequency stability in terms of temperature variation (less than 2%), a low phase noise of 0.06 radians, and frequency sensitivity to power supply variation of less than 10%.
[0025] The current-starved topology with an output switching inverter is a building block to implement the ring oscillator. The control voltage Vctrl 202 is applied to both the control transistor M 1 204 and VDD_DP as shown in FIG. 2 . The RO circuit 200 may be implemented using a 22 nm high-performance (HP) PTM model with a VDD_DP of 0.8 V. An output frequency of 1 GHz is achieved with three current starved inverting stages ( 210 , 212 , 214 ) each with transistor W/L ratios ranging between 8 to 10. None of the transistors are minimum-sized to reduce the impact of line-edge roughness and random dopant fluctuations that cause significant variation in the VTH in the subnanometer technology nodes.
[0026] The VTH, low-field mobility, and effective channel length are three parameters impacted by lithographic variation, stress, and doping concentration in strained silicon technology. The impact of process variation on the output frequency of the ring oscillator is evaluated with Monte Carlo analysis. A typical corner is simulated for statistical variation of VTH, channel length, and mobility considering both process variation and device mismatch. The ring oscillator frequency variation with VTH , channel length, and MOSFET low-field mobility is shown, respectively, in FIGS. 4( a ), 4( b ), and 4( c ) .
[0027] The corresponding ratio of the variance to the mean for VTH, the effective channel length, and the low-field mobility as a percentage are, respectively, 11.9%, 5.64%, and 6.12%. The ring oscillator therefore exhibits moderate deviation in output frequency with process variation. The power module on the power plane that detects the ring oscillator frequency is designed to compensate for deviation from the 1 GHz target frequency due to PVT variation to ensure reliable detection and setting of the power supply voltage.
[0028] B. Frequency to Voltage Converter Circuit
[0029] The output from the ring oscillator 116 on the device planes 110 , 120 is connected to an FVC circuit 138 placed on the dedicated power plane 130 . The connection between the ring oscillator 116 and the FVC 138 is through TSVs 150 . With careful floor planning and the development of 3-D IC interface circuit standards, the vertical alignment of the ring oscillators 116 and the FVC circuits 138 on the respective device and power planes ensures minimum electrical degradation of the frequency signal in terms of induced jitter and propagation delay. The FVC 138 operates based on charge redistribution between two switching capacitors. The generated output voltage is linearly related to the input frequency and does not require filtering to remove AC ripples, which is a common limitation with other FVC implementations using low pass filtering techniques or digital counters. The circuit implementation is area efficient, as a limited number of components are required. The FVC circuit 138 is implemented using a 45 nm low-performance (LP) PTM model with the power supply voltage VDD_PP set to 1 V.
[0030] FIG. 5 shows a circuit implementation of the FVC 138 with transistors M 1 -M 5 . The current source may be set to 20 μA. The capacitors C 1 550 and C 2 552 may be each 10 fF and implemented as MOSCAPS to reduce the occupied silicon area. The voltage across the capacitors 550 , 552 is inversely proportional to the frequency of the input signal and corresponds to a voltage of 690 mV when the input frequency is 1 GHz.
[0031] C. Voltage-Controlled Voltage Source Implementation
[0032] As shown in FIG. 6 , the control voltage (Vctrl) and power supply voltage (VDD_DP) of the RO in the device plane are provided by a voltage controlled voltage source (VCVS 136 ) that is part of the power module in the power plane 130 . The VCVS 136 includes a voltage comparator and a current source that charges a capacitor C. The charging of the capacitor through the current source is controlled by the output of the voltage comparator. The VCVS 136 is implemented using the 45 nm thick oxide PTM model available through the NCSU 45 nm PDK. The current source is designed to generate stable output voltages up to 3 V, which is sufficient to serve analog and IO devices implemented in subnanometer technologies. It is possible to generate output voltages up to 5 V by selecting an older technology node (greater than 65 nm) to implement the current source on the dedicated power plane 130 . By supplying voltages from 0.5 V to 5 V, a wide range of disparate technologies are integrated to form a 3-D system.
[0033] The ring oscillator 116 generates distinct frequencies when the input control voltage lies between VDD_DP/2 and VDD_DP. The FVC 138 responds to these frequencies by generating an output voltage inversely proportional to the input frequencies. The varying output voltage from the FVC 138 is constantly compared to Vref. When Vfvc is equal to or less than Vref, the comparator output becomes active low and stops the charging of the capacitor C through the current source, as shown in FIG. 6 .
[0034] III. Simulation Results
[0035] The three circuit blocks, which include the 22 nm three stage current starved output switching ring oscillator circuit on the device plane (power supply voltage VDD_DP of 0.8 V), the 45 nm FVC circuit (power supply voltage VDD_PP of 1 V), and the 45 nm VCVS, are simulated together. The simulation also includes the impedance of the TSVs. The connectivity of the circuit blocks is shown in FIG. 6 and the transient response is shown in FIG. 7 . Assuming a vertical alignment between the power module on the power plane and the ring oscillator on the device plane, the interconnect length is negligible and is not considered in the simulation.
[0036] The control voltage from the VCVS and the output signal of the ring oscillator propagate through TSVs. The impact of the TSVs is incorporated by using an equivalent RC pi-model. The values of the DC resistance (505.8 mΩ), 1 GHz resistance (570.72 mΩ), and capacitance (8.7 fF) of a single
[0037] TSV are computed from closed form expressions. The pi-model represents a Tungsten filled TSV with a length of 16 μm, diameter of 1.5 μm, and dielectric thickness of 0.25 μm. Each RC pi-model shown in FIG. 6 represents two TSVs in parallel.
[0038] FIG. 7 shows the transient response of the 22 nm ring oscillator (Fout_22 nm), the FVC output voltage (Vfvc), and the control voltage generated by the VCVS block (Vctrl_22 nm). The ring oscillator is the only load element served by the power module for the transient simulation. The VCVS transient simulation therefore excludes the impact of load transients and resistive losses due to the power delivery network and additional load circuits. The desired power supply voltage of 0.8 V is reached in less than 80 ns. The proposed voltage detection and power delivery circuit is further tested to provide the power supply voltage to a 45 nm device plane. A three-stage current starved ring oscillator is designed using a 45 nm LP PTM model (VDD_DP of 1 V). The VCVS is able to reliably generate a control voltage of 1 V (Vctrl_45 nm) in less than 100 ns, as shown in FIG. 7( c ) .
[0039] IV. Universal Power Plane
[0040] Through silicon via (TSV) based 3D integrated circuits (IC) permit the integration of heterogeneous technologies with CMOS. The integrated system may include RF, analog, micro-nano-electromechanical systems (MEMS/NEMS) as well as emerging technologies such as nano-FET and graphene-based device planes. The design and fabrication of these disparate device planes may take place at separate facilities. Unless technology specific information on each device plane is provided, the packaging facility carrying out the final 3D integration of the device planes may be unaware of the power supply voltage requirements of the different ICs.
[0041] A universal power plane comprises circuits capable of detecting the power supply voltage requirement of each device plane in the 3-D IC stack. The universal power plane may have multiple on-chip voltage regulators serving the power needs of each voltage domain in each device plane of the 3D stack. This arrangement facilitates point-of-load power delivery through the use of TSVs. The shorter path between the power source and load leads to both lower IR drop and parasitic impedance of the power distribution network. Each dedicated voltage regulator for a given voltage domain facilitates dynamic voltage and frequency scaling (DVFS). 3D IC interface guidelines would help to successfully implement this circuit, and would include specifications for the location of ports for power, clock, and signal delivery for each device plane of the 3D IC stack.
[0042] V. Alternate Power Supply Detection and Clamping Circuit
[0043] FIG. 8 shows a block diagram of the various components of a 3-D IC supply voltage detection and clamping circuit 800 . Each voltage domain in the device plane 810 comprises a ring oscillator 816 with a current-starved output switching stage. The ring oscillator 816 operates at a frequency of 1 GHz when the applied control voltage equals the power supply voltage of the given domain. The oscillation frequency of 1 GHz is selected and achievable with minimum current starved inverter stages in a deep sub-micron CMOS technology as well as in GaAs based RF circuits. The power module 830 that serves a voltage domain consists of a clock divider 860 , frequency detector 870 , voltage ramp generator 880 , voltage peak detector 890 , and a voltage regulator 850 .
[0044] The ring oscillator 816 output frequency may be down-converted by a factor of 40 by the clock divider 860 comprising a divide-by-8 cascaded together with a divide-by-5 circuit block. The frequency comparator compares the output of the clock divider 860 with a 25 MHz clock source (off-chip crystal oscillator) 865 . The frequency comparator 900 may be implemented using four D-FFs 910 as shown in FIG. 9( a ) . The frequency comparator may be preferable over a phase frequency detector (PFD) as the PFD generates UP and DOWN signals (due to D-FF clock-to-Qdelay) even when the inputs are phase locked. In addition, the voltage detection circuit does not require that the down converted ring oscillator frequency is matched in phase with the 25 MHz reference signal.
[0045] A voltage ramp generator circuit (RGC) 920 includes a constant current source charging a capacitor C 1 and a switch S 1 that controls the duration of the ramp voltage, as shown in FIG. 9( b ) . The UP and inverted DOWN signal are logically ANDed together (UPDOWN) to generate the control signal for S 1 . When the 3-D IC is first powered on, the ramp generator provides an initial voltage to the ring oscillator, and the UP signal from the frequency detector is high as the down converted frequency from the ring oscillator is less than 25 MHz. The frequency increases as the ramp generator output voltage increases. When the ring oscillator reaches the 1 GHz frequency, the UP signal may be de-asserted and any further increase in frequency asserts the DOWN signal. The switch S 1 is in the open state, preventing any further increase of charge (and therefore voltage) on C 1 . The voltage VRGC on C 1 corresponds to the power supply voltage of the voltage domain (VDD_VI) in which the ring oscillator is placed. The discharging of the capacitor C 1 through the load circuit causes the ring oscillator frequency to drop below 1 GHz, which re-asserts the UP signal and places Si in the closed state. The UP signal continues to periodically toggle ensuring that the voltage VRGC is maintained at the desired level.
[0046] The variations in VRGC due to discharging of the capacitor C 1 are filtered using a voltage peak detector circuit 930 (shown in FIG. 9( c ) . The peak detector circuit consists of a PMOS M 1 that controls the current charging the capacitor C 2 . A voltage comparator compares the output voltage VRef across the capacitor C 2 with VRGC. The output voltage from the comparator biases M 1 . VRef follows the positive transition of VRGC and at steady state equals the maximum value of VRGC. The peak detector circuit therefore provides a steady voltage reference with less than 1% ripple voltage variation from the targeted power supply voltage of the device plane (VDD_VI). VRef is used as the reference voltage for the voltage regulator serving the load circuit in the device plane. On-chip voltage regulator topologies like the LDO and buck converter are suitable for integration with the proposed voltage detection and clamping circuit. The stable reference voltage provided by the proposed circuit ensures superior line regulation offered by the voltage regulator.
[0047] VI. Simulated Circuit Results
[0048] Two device planes may be simulated using the 45 nm low-performance (LP) (VDD_VI of 1 V) and 22 nm high-performance (HP) (VDD_VI of 0.8 V) PTM models [6]. The designed ring oscillators for each device plane include three inverter stages in a current starved output-switching configuration. The design is robust against threshold voltage variation, channel length variation, and low-field mobility variation.
[0049] The components of the power module may be implemented with the 45 nm PTM models. The divide-by-40 clock divider and frequency detector circuits are simulated using the 45 nm LP PTM model (VDD_PP of 1 V). The voltage ramp generator and peak detector circuits are implemented using the 45 nm thick oxide (VDD_Ramp of 3 V) PTM model. A DC-DC level shifter is used to convert the UP and DOWN signals from a VDD_PP of 1 V to a VDD_Ramp of 3 V. The slope of the voltage ramp signal is deliberately kept low (0 V to 3 V in 2 μs) to ensure stable operation. The minimum voltage detected reliably by the power module is 0.7 V. The maximum voltage provided by the ramp generator is 2.5 V. SPICE circuit simulations indicate a maximum variation of 1% in the reference voltage VRef provided to the on-chip voltage regulator for VDD_VI of less than 1 V. This is comparable to the stability of reference voltages used by off-chip buck converters, where approximately 1% variation is currently achieved.
[0050] The simulation results for detecting and clamping the power supply voltage for a voltage domain in a 22 nm device plane are shown in FIG. 3 . VRef reaches VDD_VI of 0.8 V in 370 ns. The detection and clamping circuits on the 45 nm device plane require 420 ns for VRef to reach the target voltage VDD_VI of 1 V. The proposed circuit therefore offers a fast transition to the desired power supply voltage level at startup and is suitable for integration with on-chip voltage regulators.
[0051] VII. Other Applications
[0052] Other applications of the circuits described herein may be as a way to maintain consistent voltage over time to overcome degradation. The power supply power detection and power delivery unit could, through its detection ability, detect any degradation and maintain consistent voltage through the circuit.
[0053] The power supply detection and power delivery unit may auto compensate for the drift in power supply voltage with time due to the aging of devices in each voltage domain served by a ring oscillator.
[0054] Further, the units may be fabricated in a 2-D or 3-D IC. The units may provide run-time aging or process, voltage, and temperature (PVT) variation detection and correction used in conjunction with on-chip voltage regulators.
[0055] The power supply detection and power delivery unit may be part of a power conditioning circuit of a battery charged portable electronic device and the power delivery unit is integrated into a portable charger. The run-time voltage detection mechanism eliminates the need to down convert the voltage from 5V as obtained through standard USB based battery chargers.
[0056] VIII. Conclusions
[0057] A mechanism to detect the power supply voltage of a given voltage domain in a 3-D IC is implemented by placing a ring oscillator in each domain located on disparate device planes. The chosen circuit topology for the ring oscillator exhibits acceptable response to deviations due to PVT variations in a 22 nm technology. A u/p ratio (as a percentage) of 11.9%, 5.64%, and 6.12% is determined for, respectively, threshold voltage variation, channel length variation, and low-field mobility. The power requirement of each voltage domain is served by a single power plane that includes multiple point of load power modules, with each module consisting of a voltage controlled voltage source regulated by a frequency to voltage converter. The power supply voltage detection and delivery mechanism is demonstrated by simulating the device plane and power plane in two different technology nodes. The targeted power supply voltage for both the 22 nm and 45 nm device planes is detected and set in less than 100 ns, as shown through simulation.
[0058] A circuit to detect and reliably set the power supply voltage of a given voltage domain in a 3-D IC is also described. All components except for a ring oscillator are part of the power module located in a separate and dedicated 45 nm power plane. Multiple power modules serve as point of load voltage delivery circuits to the different device planes. Correct power supply voltage detection and clamping is demonstrated through circuit simulation for two device planes, one in 22 nm and the other in 45 nm technologies. The power module is capable of setting the power supply voltage of a device plane ranging from 0.7 V to 2.5 V. The precise voltage generated from the power module acts as a reference voltage for an on-chip LDO or buck converter. The reference voltage is within 1% of the targeted power supply voltage, as indicated by simulated results.
[0059] The power regulation described herein has been made in reference to ICs and in particular IC manufacture with layers produced separately. Other uses of the device described herein, however, are possible, including the use of the device as a universal power converter that could be used to allow for power differences between electric devices and power delivery systems.
[0060] While the invention has been described with reference to the embodiments above, a person of ordinary skill in the art would understand that various changes or modifications may be made thereto without departing from the scope of the claims. | A circuit that detects the power supply voltage requirement of each voltage domain in an IC includes 1) a ring oscillator in each voltage domain, and 2) a power module. Two different circuit implementations of the power module may provide a precise reference voltage to on-chip voltage regulators (LDO or DC-DC switching buck converter). The power module supports DVFS and can provide the desired power supply voltage for advanced CMOS technology nodes (45 nm and beyond) in less than 100 ns. The voltage detection circuit clamps the voltage to the desired level to address power supply voltage variations due to PVT and ageing. The proposed technique has minimal power and area overhead to compensate for the power supply voltage variation, thus reducing power supply voltage margins which yields higher power saving. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally concerns a process of granulation and an apparatus therefor, and more particularly it concerns an improved process of granulation for obtaining comparatively large granules and apparatus therefor.
2. Description of the Prior Art
There are known in the art apparatus with a large capacity for mass-producing small sized granules and capable of manufacturing high quality products with a single unit. For instance, in the prilling system used in granulation of urea, etc., one unit has a capacity as large as 2,000 t/day or more. However, it is impossible with such an apparatus to increase the granule diameter of the product beyond a certain limit because of the physical properties of the melt to be granulated.
The reason for this is because, if the diameter of the nozzle for the melt is increased, the melt flows continuously and the liquid drops cannot be formed. If the liquid drops become larger, on the other hand, the vertically falling distance of the liquid drops required for solidification becomes excessive. According to the prilling process, the average diameter of ca. 2 mm is the limit for granular urea.
There are known in the art granulation apparatus for large diameter granules and these are of the rolling type, compression molding type, casting type, or mechnical processing type. These are however not suitable for mass production.
In the case of apparatus for manufacturing large diameter granules, the quantity of the substance which is necessary to make up the granules is from several times to several hundred times greater than that for making small diameter granules, and generally the granule particle size distribution is broad in such apparatus. Therefore, technologically speaking it is particularly more difficult to obtain products with uniform particle size and shape which have a large diameter than product with a smaller diameter.
Accordingly, in the above-mentioned conventional granulation apparatus, the maximum production per unit apparatus is as small as 500 t/day although the costs for the facilities and the operation are unchangeably high.
There are sometimes demands for products with granule diameter of more than 2 mm for convenience in use, handling or storage, and there are also demands for a method and apparatus which facilitate production of large sized granular products of an arbitrary diameter in large quantities and at less cost in order to meet the need of mixing small sized and large sized granules in a suitable ratio to increase the bagged amount per unit volume and to facilitate handling during use. This will be most convenient for storage, transportation and use of granule products of the same or the different quality.
SUMMARY OF THE INVENTION
An object of the present invention is to provide an improved granulation process which enables efficient production on a mass industrial scale of large diameter granule products having a substantially spherical-shape like pearls and an apparatus therefor.
Another object of the present invention is to provide a granulation apparatus which can effectively combine the prilling system the capacity of which may be increased but which cannot manufacture the large diameter products, and the spouted bed granulation system the capacity of which cannot be increased but which can manufacture large diameter granules.
According to the present invention there is provided the following granulation process:
A process for manufacturing large diameter granular products comprising the steps of dropping as liquid droplets the melt of a substance solidifiable by cooling or drying through a zone having a sufficient vertical distance for solidifying the said liquid droplets by the countercurrent contact with a gas stream for cooling or drying the said drops, fluidizing the thus solidified droplets also known as prills at the bottom of the said zone with a gas stream to form a fluidized bed, spraying the melt of a substance solidifiable by cooling or drying into the said fluidized bed as fine liquid grains along with a gas stream thereby forming a spouted bed of the said solidified droplets in fluidized bed, coating and enlarging the said solidified droplets with the said fine grains in the said spouted streams to form granules of a large diameter, and then discharging the said large diameter granules from the fluidized bed.
There is also provided the following apparatus for conducting the above-described granulation process:
A granulation apparatus comprising a cylindrical member positioned vertically for providing a sufficient space for the liquid droplets of a substance solidifiable by cooling or drying which droplets fall through the inside of the cylinder to become solidified by being cooled or dried; exhaust means provided at the top of the said cylindrical member; droplet supply means provided at the top of the said cylindrical member for discharging the liquid droplets of the substance solidifiable by cooling or drying into a rising gas stream inside the said cylindrical member; a perforated plate for the fluidized bed provided at the bottom of the said cylindrical member; spray nozzle means opening on the same plane as the surface of said perforated plate, or at a position below or above the said perforated plate for discharging the fine liquid grains of the substance solidifiable by cooling or drying, supply means for a gas stream to form the spouted bed of the said solidified drops in the fluidized bed centering the said spraying nozzle means; supply means for a gas stream below the said perforated plate for forming the fluidized bed over the said perforated plate, and means for discharging granules from the said fluidized bed.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1(A) is a vertical cross-sectional view showing one embodiment of the present invention apparatus;
FIG. 1(B) is a cross-sectional view along the line A--A of FIG. 1(A); and
FIG. 2 is a vertical cross-sectional view showing another embodiment of the present invention apparatus where the spray nozzles are provided on the same horizontal surfaces as the perforated plate.
DETAILED DESCRIPTION OF THE INVENTION
In the prilling system, the melt of the substance solidifiable by cooling or drying is pressed downward through the nozzles to naturally drop through the cooling medium and becomes granules while falling and while being cooled or dried. As mentioned above, even if the diameter of the nozzle is increased in size, the physical properties of the substance being processed may be such that the melt flows out in a continuous flow and does not become spherical, or the cooling effect is excessively hindered due to the decrease in the specific surface area. Thus, it is impossible to obtain granules with the desired large diameters. However, as far as the manufacture of granules having a diameter less than the specified size is concerned, the capacity of the system may easily be increased by increasing the number of holes in the nozzle to enlarge the horizontal cross-section of the space for dropping the drops.
Furthermore, with the prilling system the fine grains of the substance solidifiable by cooling or drying become adhered to the granules as they are spouted inside the grain layer being circulated within the said system or inside the spouted bed formed inside the fluidized bed, the said granules being passed repeatedly through the spouted bed and becoming solidified, thus forming large diameter granules. In order for the fine seed granules, nuclei for large diameter granules, to grow into the granules of a desired diameter, it is necessary to provide a certain operational time parameter. As the number of times they pass through the spouted bed varies depending on the individual grains, the grain size distribution of the granules formed becomes non-uniform, and there are many granules which do not grow sufficiently to reach the desired diameter range. Thus, it is extremely difficult to improve the capacity and the efficiency of the process. Moreover, the spouted bed is limited in its size for supporting the bed itself and for smooth supply and passage of the grains which pass therethrough repeatedly.
In the present invention, the above mentioned two types of granulation systems are combined. Surprisingly, it was found that this combination facilitates the manufacture of large sized granules with just a single apparatus unit by synergistically exploiting the advantages of the two systems and by removing the disadvantages thereof.
As the granule product of the prilling system has a narrow particle size distribution range and can be used as seed grains the efficiency of the granulation is remarkably increased when the grains are used as the seed grains for the spouted bed type granulation system.
In the present invention process, various solid substances are used as substances solidifiable by cooling or drying. Various types of fertilizers such as urea, ammonium nitrate, and mixtures of these substances with ammonium phosphate or potassium chloride are particularly applicable. Such substances in other words may be both dropped as liquid droplets through the zone, and/or they may be sprayed as fine liquid grains from the bottom of the zone. The melt of these materials includes a substantially anhydrous melt, a hot aqueous solution and a slurry. A melt solution may contain up to 40 weight % of water, and its temperature is generally 80°-170° C.
Various gas streams may be used both for fluidizing the solidified droplets at the bottom of the zone and for spraying the melt from the bottom of the zone and forming the spouted bed of the solidified droplets. The choice of gas stream depends on the purpose intended, but generally atmospheric air is used. The temperature of the air stream is generally set within the range of 0°-150° C.
The zone through which the droplets of the melt fall and solidify varies depending on the type of substance to be used, but usually it is suitably selected within the range of 10 m to 70 m.
The ratio of the melt dropped as droplets to the melt sprayed as fine grains is set to be between 1:4 and 4:1.
Other substances to be added in the product granules may be fine grains supplied to the fluidized bed or mixed in the melt.
If there is a need for obtaining a product of a uniform grain diameter, the granules formed may be classified, and those smaller than the desired diameter are left as they are while those with a larger diameter than that desired are suitably pulverized and returned to the fluidized bed.
The grain diameter of the solidified droplets is preferably below 2 mm, and more particularly it is preferred to be 1 to 2 mm. The diameter of the drops which have become enlarged and solidified as the fine grains of the sprayed melt have adhered thereto and solidified is preferred to be 1 to 5 times greater than the original diameter.
The preferred embodiments of the present invention will now be explained reference being made to FIGS. 1 and 2. There are provided exhaust outlets 2 at the top of the cylindrical member 1. There are similarly provided melt supply vessel 3 which have a plurality of nozzles to spray the solution downwardly or let the drops fall by gravity. There is provided a perforated plate 4 at the bottom of the cylindrical member 1 defining the lower limit or floor base of the fluidized bed to be formed thereupon.
Positioned below the surface of the perforated plate 4 are provided spray nozzles 5, the nozzles spraying the melt upwardly as fine grains. In the embodiment shown in FIG. 1, the spray nozzles are provided at the bottom of the inverted truncated cone shaped vessel 9 opening on the plane of the perforated plate 4. The embodiment shown in FIG. 2 provides the spray nozzles 5 on the same plane as the surface of the perforated plate 4. There is provided a pipe 6 beneath the respective spray nozzles for supplying the air current which maintains a uniform contact between the fine spray from nozzles 5 and the granules to be coated and enlarged. There is further provided a chamber 7 for supplying the air current for forming the fluidized bed beneath the perforated plate. At the lower portion of the cylindrical member 1 there is provided a discharge pipe 8 for granule products.
The functions of the apparatus shown in the drawings will now be explained. There is formed a fluidized bed of granules to be coated and enlarged on the perforated plate by the air current which passes upwardly from the air supply chamber 7. The granules inside the fluidized bed successively enters the spouted bed formed by the air current supplied through the pipes 6, and become enlarged as the fine grains sprayed through the spray nozzles 5 become adhered thereon. The air current, which is flowing from the pipes 6 and the air supply chamber 7 to form the spouted bed and the fluidized bed, rises inside the cylindrical member 1, contacts the droplets introduced from the nozzles of the melt supply vessel 3 and falling therefrom to cool or dry them, and finally discharges outside the apparatus from the exhaust outlets 2.
The droplets falling inside the cylindrical member 1 become solidified, and mix into the fluidized bed. The granules which these solidified drops form are abundant and their diameter and shape are substantially uniform, and remarkably improve the efficiency of the grain growth inside the spouted bed.
The granules inside the fluidized bed eventually overflow and are discharged from the apparatus, through exhaust pipe 8.
The apparatus according to the present invention will now be explained by way of example.
EXAMPLE
In the example, urea granules of 3 to 5 mm diameter are manufactured.
The vertical distance from the nozzle plate beneath the melt supply means 3 inside the cylindrical member 1 to the fluidization base floor below is 40 m, and the spouted beds are arranged at four points on the perforated plate, while the vessels of inverted truncated conical shape positioned around the respective jet streams have an opening of 0.9 m diameter on the perforated plate.
The distance between centers of the adjacent spouted beds is 1.4 m. The 35° C. air is supplied to the supply chamber 7 at the rate of 60,000 Nm 3 /hour, and the 40° C. air is supplied from the four pipes 6 at the rate of 40,000 Nm 3 /hour, to form a fluidized bed of urea granules having a depth of 0.1 m on the perforated plate. The molten urea of 138° C. is supplied from the melt supply vessel 3 at the flow rate of 17.5 t/hour, and is also supplied from the four spray nozzles 4 at 7.5 t/hour. The 111° C. air is discharged from the exhaust outlet 2 at the rate of 100,000 Nm 3 /hour to be introduced into a fine grain collector (not shown). The urea granules of 3 to 5 mm diameter of 60° C. are discharged at 25 t/hour from the discharge pipe 8.
Although the example shown relates to urea granules, the present invention may be applicable to granulation of other substances. The present invention is also useful for coating or covering the surface of granules with other substances.
The advantages of the present invention may therefore be summarized as follows:
(1) Large diameter granules are mass produced efficiently.
(2) The quantity of material retained in the various stages in the granulation apparatus and affiliated facilities is small.
(3) Product granules tend remarkably toward a true spherical shape.
(4) The allowable water content in the melt used as the raw material may be high.
(5) The minor improvement to the lower portion of the conventional prilling tower enables mass production of large diameter granules. | There is disclosed a process of granulation comprising dropping as liquid droplets the melt of a substance solidifiable by cooling or drying through a zone having a sufficient vertical distance to allow solidification of the droplets, forming a fluidized bed of the solidified droplets on the bottom of the said zone, spraying the same or a different melt from the above mentioned substance as fine liquid grains along with a gas stream into the fluidized bed thereby forming a spouted bed of the solidified droplets in the fluidized bed, coating and enlarging the solidified droplets with the fine liquid grains inside the spouted bed, and discharging the obtained large sized granules from the fluidized bed. There is also disclosed an apparatus for practicing the process. | 2 |
TECHNICAL FIELD
[0001] The illustrative embodiments generally relate to a method and apparatus for scheduling vehicle startup.
BACKGROUND
[0002] Many vehicles come equipped with remote start capabilities. In these vehicles, the user will engage a feature on a key fob and a vehicle will respond by engaging the engine. Some remote start features may include automatically setting a vehicle temperature and engaging certain vehicle climate features. Automatic locking of vehicle doors may also be provided, so that a started vehicle cannot be driven away. While convenient, users may forget to start the vehicle on certain mornings, even if starting the vehicle remotely is typically part of a morning routine.
[0003] U.S. Pat. No. 7,542,827 generally relates to a method for scheduling the remote starting of an engine of a vehicle. The vehicle includes a remote starting device and a controller coupled to a communication device and to the remote starting device. The remote starting device is responsive to commands from the controller. The method includes a first step of defining a schedule of starting times. A next step includes entering the schedule in the controller. A next step includes controlling an operation of the remote starting device in accordance with the schedule.
[0004] U.S. Pat. No. 8,489,085 generally relates to a system and method for a vehicle remote starter with an advanced dynamic scheduling system. The system and method utilizes a cellular telephone, interfacing with standard scheduling software, and capable of communicating with the Internet to gather real time data and communicating through a wireless telecommunication network with a vehicle to send vehicle remote start and other commands; an electronic scheduling system utilized within or accessible by the cellular telephone; a cellular telephone based and/or vehicle based GPS location module for determining the location of the vehicle and the cellular telephone at any particular point in time; a set of coded instructions that actively queries the Internet for real time data and that queries the electronic scheduling system to determine the time and location of a scheduled meeting, evaluating various vehicle operational parameters, the distance of the cellular phone from a vehicle, various environmental parameters, the distance from a vehicle to meeting location, the travel time required to timely travel and attend the scheduled meeting, and either prompting the user to actively send a remote start command signal to the vehicle or automatically sending the remote start command signal.
SUMMARY
[0005] In a first illustrative embodiment, a computer implemented method includes logging vehicle startup information. The method also includes determining, via a computer, if timing commonalities exist between logged vehicle startup information instances. Further, the method includes recommending automatic vehicle startup, based on a threshold number of timing commonalities. The method also includes formulating recommended start times based on logged vehicle startup information instances having timing commonalities. The method additionally includes presenting a schedule including recommended start times to a vehicle user and scheduling automatic vehicle startups upon vehicle user acceptance of the presented schedule.
[0006] In a second illustrative embodiment, a computer implemented method includes logging vehicle startup information. The method also includes determining, via a computer, if timing commonalities exist between logged vehicle startup information instances. The method further includes recommending automatic vehicle startup, based on a threshold number of timing commonalities. The method further includes formulating recommended start times based on logged vehicle startup information instances having timing commonalities. Also, the method includes presenting a schedule including recommended start times to a vehicle user and scheduling automatic vehicle startups upon vehicle user acceptance of the presented schedule.
[0007] In a third illustrative embodiment, a system includes a processor configured to log vehicle start times. The processor is also configured to determine if timing variances over a timing threshold exist between logged vehicle startup times and scheduled start times. Further, the processor is configured to recommend a change to the scheduled start times, based on a threshold number of timing variances over the timing threshold. The processor is also configured to formulating new recommended start times based on logged vehicle startup information instances having timing commonalities. The processor is additionally configured to present a new schedule including new recommended start times to a vehicle user and rescheduling automatic vehicle startups upon vehicle user acceptance of the new schedule.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 shows an illustrative vehicle computing system;
[0009] FIG. 2 shows an illustrative vehicle-side process for recommending scheduling a vehicle start;
[0010] FIG. 3 shows an illustrative server-side process for recommending scheduling a vehicle start;
[0011] FIG. 4 shows an illustrative vehicle-side process for recommending changing a schedule; and
[0012] FIG. 5 shows an illustrative server-side process for recommending changing a schedule.
DETAILED DESCRIPTION
[0013] As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various and alternative forms. The figures are not necessarily to scale; some features may be exaggerated or minimized to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention.
[0014] FIG. 1 illustrates an example block topology for a vehicle based computing system 1 (VCS) for a vehicle 31 . An example of such a vehicle-based computing system 1 is the SYNC system manufactured by THE FORD MOTOR COMPANY. A vehicle enabled with a vehicle-based computing system may contain a visual front end interface 4 located in the vehicle. The user may also be able to interact with the interface if it is provided, for example, with a touch sensitive screen. In another illustrative embodiment, the interaction occurs through, button presses, spoken dialog system with automatic speech recognition and speech synthesis.
[0015] In the illustrative embodiment 1 shown in FIG. 1 , a processor 3 controls at least some portion of the operation of the vehicle-based computing system. Provided within the vehicle, the processor allows onboard processing of commands and routines. Further, the processor is connected to both non-persistent 5 and persistent storage 7 . In this illustrative embodiment, the non-persistent storage is random access memory (RAM) and the persistent storage is a hard disk drive (HDD) or flash memory. In general, persistent (non-transitory) memory can include all forms of memory that maintain data when a computer or other device is powered down. These include, but are not limited to, HDDs, CDs, DVDs, magnetic tapes, solid state drives, portable USB drives and any other suitable form of persistent memory.
[0016] The processor is also provided with a number of different inputs allowing the user to interface with the processor. In this illustrative embodiment, a microphone 29 , an auxiliary input 25 (for input 33 ), a USB input 23 , a GPS input 24 , screen 4 , which may be a touchscreen display, and a BLUETOOTH input 15 are all provided. An input selector 51 is also provided, to allow a user to swap between various inputs. Input to both the microphone and the auxiliary connector is converted from analog to digital by a converter 27 before being passed to the processor. Although not shown, numerous of the vehicle components and auxiliary components in communication with the VCS may use a vehicle network (such as, but not limited to, a CAN bus) to pass data to and from the VCS (or components thereof).
[0017] Outputs to the system can include, but are not limited to, a visual display 4 and a speaker 13 or stereo system output. The speaker is connected to an amplifier 11 and receives its signal from the processor 3 through a digital-to-analog converter 9 . Output can also be made to a remote BLUETOOTH device such as PND 54 or a USB device such as vehicle navigation device 60 along the bi-directional data streams shown at 19 and 21 respectively.
[0018] In one illustrative embodiment, the system 1 uses the BLUETOOTH transceiver 15 to communicate 17 with a user's nomadic device 53 (e.g., cell phone, smart phone, PDA, or any other device having wireless remote network connectivity). The nomadic device can then be used to communicate 59 with a network 61 outside the vehicle 31 through, for example, communication 55 with a cellular tower 57 . In some embodiments, tower 57 may be a WiFi access point.
[0019] Exemplary communication between the nomadic device and the BLUETOOTH transceiver is represented by signal 14 .
[0020] Pairing a nomadic device 53 and the BLUETOOTH transceiver 15 can be instructed through a button 52 or similar input. Accordingly, the CPU is instructed that the onboard BLUETOOTH transceiver will be paired with a BLUETOOTH transceiver in a nomadic device.
[0021] Data may be communicated between CPU 3 and network 61 utilizing, for example, a data-plan, data over voice, or DTMF tones associated with nomadic device 53 . Alternatively, it may be desirable to include an onboard modem 63 having antenna 18 in order to communicate 16 data between CPU 3 and network 61 over the voice band. The nomadic device 53 can then be used to communicate 59 with a network 61 outside the vehicle 31 through, for example, communication 55 with a cellular tower 57 . In some embodiments, the modem 63 may establish communication 20 with the tower 57 for communicating with network 61 . As a non-limiting example, modem 63 may be a USB cellular modem and communication 20 may be cellular communication.
[0022] In one illustrative embodiment, the processor is provided with an operating system including an API to communicate with modem application software. The modem application software may access an embedded module or firmware on the BLUETOOTH transceiver to complete wireless communication with a remote BLUETOOTH transceiver (such as that found in a nomadic device). Bluetooth is a subset of the IEEE 802 PAN (personal area network) protocols. IEEE 802 LAN (local area network) protocols include WiFi and have considerable cross-functionality with IEEE 802 PAN. Both are suitable for wireless communication within a vehicle. Another communication means that can be used in this realm is free-space optical communication (such as IrDA) and non-standardized consumer IR protocols.
[0023] In another embodiment, nomadic device 53 includes a modem for voice band or broadband data communication. In the data-over-voice embodiment, a technique known as frequency division multiplexing may be implemented when the owner of the nomadic device can talk over the device while data is being transferred. At other times, when the owner is not using the device, the data transfer can use the whole bandwidth (300 Hz to 3.4 kHz in one example). While frequency division multiplexing may be common for analog cellular communication between the vehicle and the internet, and is still used, it has been largely replaced by hybrids of Code Domain Multiple Access (CDMA), Time Domain Multiple Access (TDMA), Space-Domain Multiple Access (SDMA) for digital cellular communication. These are all ITU IMT-2000 (3G) compliant standards and offer data rates up to 2 mbs for stationary or walking users and 385 kbs for users in a moving vehicle. 3G standards are now being replaced by IMT-Advanced (4G) which offers 100 mbs for users in a vehicle and 1 gbs for stationary users. If the user has a data-plan associated with the nomadic device, it is possible that the data-plan allows for broad-band transmission and the system could use a much wider bandwidth (speeding up data transfer). In still another embodiment, nomadic device 53 is replaced with a cellular communication device (not shown) that is installed to vehicle 31 . In yet another embodiment, the ND 53 may be a wireless local area network (LAN) device capable of communication over, for example (and without limitation), an 802.11g network (i.e., WiFi) or a WiMax network.
[0024] In one embodiment, incoming data can be passed through the nomadic device via a data-over-voice or data-plan, through the onboard BLUETOOTH transceiver and into the vehicle's internal processor 3 . In the case of certain temporary data, for example, the data can be stored on the HDD or other storage media 7 until such time as the data is no longer needed.
[0025] Additional sources that may interface with the vehicle include a personal navigation device 54 , having, for example, a USB connection 56 and/or an antenna 58 , a vehicle navigation device 60 having a USB 62 or other connection, an onboard GPS device 24 , or remote navigation system (not shown) having connectivity to network 61 . USB is one of a class of serial networking protocols. IEEE 1394 (FireWire™ (Apple), i.LINK™ (Sony), and Lynx™ (Texas Instruments)), EIA (Electronics Industry Association) serial protocols, IEEE 1284 (Centronics Port), S/PDIF (Sony/Philips Digital Interconnect Format) and USB-IF (USB Implementers Forum) form the backbone of the device-device serial standards. Most of the protocols can be implemented for either electrical or optical communication.
[0026] Further, the CPU could be in communication with a variety of other auxiliary devices 65 . These devices can be connected through a wireless 67 or wired 69 connection. Auxiliary device 65 may include, but are not limited to, personal media players, wireless health devices, portable computers, and the like.
[0027] Also, or alternatively, the CPU could be connected to a vehicle based wireless router 73 , using for example a WiFi (IEEE 803.11) 71 transceiver. This could allow the CPU to connect to remote networks in range of the local router 73 .
[0028] In addition to having exemplary processes executed by a vehicle computing system located in a vehicle, in certain embodiments, the exemplary processes may be executed by a computing system in communication with a vehicle computing system. Such a system may include, but is not limited to, a wireless device (e.g., and without limitation, a mobile phone) or a remote computing system (e.g., and without limitation, a server) connected through the wireless device. Collectively, such systems may be referred to as vehicle associated computing systems (VACS). In certain embodiments particular components of the VACS may perform particular portions of a process depending on the particular implementation of the system. By way of example and not limitation, if a process has a step of sending or receiving information with a paired wireless device, then it is likely that the wireless device is not performing the process, since the wireless device would not “send and receive” information with itself. One of ordinary skill in the art will understand when it is inappropriate to apply a particular VACS to a given solution. In all solutions, it is contemplated that at least the vehicle computing system (VCS) located within the vehicle itself is capable of performing the exemplary processes.
[0029] In each of the illustrative embodiments discussed herein, an exemplary, non-limiting example of a process performable by a computing system is shown. With respect to each process, it is possible for the computing system executing the process to become, for the limited purpose of executing the process, configured as a special purpose processor to perform the process. All processes need not be performed in their entirety, and are understood to be examples of types of processes that may be performed to achieve elements of the invention. Additional steps may be added or removed from the exemplary processes as desired.
[0030] The illustrative embodiments contemplate that a system for scheduling a remote start to a vehicle already exists. As can be seen from the prior art, several extra-vehicular devices can be programmed to communicate with a vehicle to schedule remote starting. Other examples of possible remote start scheduling include schedules stored within a vehicle memory itself, or storing a schedule on the cloud and communicated to the vehicle.
[0031] These schedules are typically set by a user. If Jim knows that he will need to use his vehicle, Monday through Friday, at six AM, then he may use a web or vehicle interface to create a schedule that starts the vehicle at 5:50 AM on the specified days. Unfortunately, Jim may not know that such a feature exists on his vehicle, and, accordingly, may instead use a remote start option every day at 5:50 AM.
[0032] In the illustrative embodiments, it is proposed that a system will “notice” when a vehicle is started and, based on a certain number of common start events at a common time, the process will recommend to a user, through a vehicle interface for example, that a schedule be established. This will both notify the user of the existence of the feature and, at the same time, provide the user with a schedule based on common remote start times.
[0033] Also, in the illustrative embodiments, a system may notice a change in start up times, if the user is starting the vehicle at times other than typically scheduled. Further, the process will check existing schedules and may suggest modifications to these schedules if appropriate, based on observed user usage of the vehicle.
[0034] FIG. 2 shows an illustrative vehicle-side process for recommending scheduling a vehicle start. With respect to the illustrative embodiments described in this figure, it is noted that a general purpose processor may be temporarily enabled as a special purpose processor for the purpose of executing some or all of the exemplary methods shown herein. When executing code providing instructions to perform some or all steps of the method, the processor may be temporarily repurposed as a special purpose processor, until such time as the method is completed. In another example, to the extent appropriate, firmware acting in accordance with a preconfigured processor may cause the processor to act as a special purpose processor provided for the purpose of performing the method or some reasonable variation thereof.
[0035] In this illustrative example, the process transfers start data to the cloud, for analysis on the cloud. In other examples, however, the cloud-based processes can be run on the vehicle directly, and analysis and recommendations can be generated within the vehicle computing system itself.
[0036] As shown in FIG. 2 , the process is initiated when a vehicle startup is detected 201 . This can be a start using a vehicle system, or it can be a start using a remote start feature. Once the start data has been detected, the process stores the start data in a local storage 203 . This data can be used by the vehicle directly, if the analysis process is performed on-board, or the data can be sent to the cloud for analysis 205 .
[0037] In this process, the local system sends the data to the cloud for analysis 205 . The system then waits for a response from the remote system 207 . While the process spools, waiting for a response, it is possible that the process may time-out if too much time passes. If a response is received 207 , the process may also receive notification that an auto-start schedule is suggested 209 . If no such indication is received, the process may exit.
[0038] If the process receives notification that the auto-start is suggested, the process may receive data relating to the scheduling of an auto-start 211 . This data may include, but is not limited to, recommended start times and recommended days of the week for the corresponding start times.
[0039] The process checks to see if the user has blocked scheduling recommendations 213 . If the recommendations have been blocked, the process exits. If the recommendations have not been blocked, the process may present a suggestion to the user that the auto start feature be engaged 215 . This presentation can be made, for example, via a vehicle interface, or could, for example, be made on a user device working in conjunction with a vehicle-related application. Any suitable means of presenting the recommendation may be used.
[0040] If the user accepts the recommended start schedule, the process can schedule a start time 219 . In this example, the start time is scheduled in the vehicle and a low level of power may be utilized to maintain a clock, which can be used to trigger the startup. In another example, the start time may be scheduled remotely, and a low level of power can be used to keep a communication device active, which can communicate with the remote server to receive start up instructions.
[0041] Once the schedule has been updated on the vehicle, the process may also update the cloud with the new schedule 225 , so that the cloud can track current vehicle schedules. If the user does not accept the recommended schedule, the user may also be provided with an option to block the recommendation process 221 . If the process is not blocked, the system may notify the cloud that there was no block and that no schedule was accepted. If the process was blocked, a block parameter 223 may be set locally, and the cloud may also be updated with the block parameter. In this example, the local process checks for the block, but in another example the cloud may check for the block before performing any analysis or recommendation processing on the vehicle data (since it is not necessary, if the recommendations are blocked anyhow).
[0042] FIG. 3 shows an illustrative server-side process for recommending scheduling a vehicle start. With respect to the illustrative embodiments described in this figure, it is noted that a general purpose processor may be temporarily enabled as a special purpose processor for the purpose of executing some or all of the exemplary methods shown herein. When executing code providing instructions to perform some or all steps of the method, the processor may be temporarily repurposed as a special purpose processor, until such time as the method is completed. In another example, to the extent appropriate, firmware acting in accordance with a preconfigured processor may cause the processor to act as a special purpose processor provided for the purpose of performing the method or some reasonable variation thereof.
[0043] In this illustrative example, the remote server, residing in the cloud, connects to a particular vehicle 301 . The remote server will receive, for example, startup data from the vehicle 303 . This data can be added to a remote database of records designated for the particular vehicle 305 . In addition to the startup data, the process may also receive vehicle identifying information that allows the remote server to identify the vehicle to which the records correspond.
[0044] The remote process may also load schedule setting parameters 307 . These parameters may be set by an individual user, or they may be set by an original equipment manufacturer (OEM). By allowing the OEM to set parameters, even users who do not even know of the existence of the system can benefit from the processes described herein, without having to set the vehicle parameters first.
[0045] The parameters can specify, among other things, a threshold number of times that a startup should be observed before a recommendation is made. In another example, the parameters may specify a threshold variance between startup times, over which all times will be considered to be the “same” time. This could be set at, for example, 10 minutes, so that all startups within 10 minutes of each other are considered as a basis for a recommendation. The parameters could also specify how the exact start time is determined, for example, by taking a mean or median time from the observed start times. Any other suitable parameters may be used as appropriate for observing start times and providing recommendations.
[0046] The observed start times can be compared to the loaded parameters 309 to determine if a match that meets the set criteria has been established 311 . If an appropriate match is established, the process may create a start schedule for the user based on the criteria 313 . The start schedule can be based on some or all of the observed start times and/or actual times of vehicle use. For example, if a vehicle is started between 5:40 and 5:55 every day, and is used at 6:00 every day, the process can base the start time on the common usage time, as opposed to the varied startup times. In other instances, the start times may be based on the actual startup times.
[0047] The start schedule as established, may be sent to the vehicle 315 for presentation to the user and adaption by the vehicle system. The process may then wait for a response from the vehicle 317 . As with the wait in the vehicle, the process may timeout if no response is received. On the other hand, if a response is received, the process also receive an update, including, for example, the schedule, from the vehicle 319 . The process may also then update remote storage with the received information, allowing the remote storage to track the schedule set for the vehicle.
[0048] FIG. 4 shows an illustrative vehicle-side process for recommending changing a schedule. With respect to the illustrative embodiments described in this figure, it is noted that a general purpose processor may be temporarily enabled as a special purpose processor for the purpose of executing some or all of the exemplary methods shown herein. When executing code providing instructions to perform some or all steps of the method, the processor may be temporarily repurposed as a special purpose processor, until such time as the method is completed. In another example, to the extent appropriate, firmware acting in accordance with a preconfigured processor may cause the processor to act as a special purpose processor provided for the purpose of performing the method or some reasonable variation thereof.
[0049] In this illustrative example, the process will provide a suggested adjustment to an already set schedule. Changes in a user's time schedule may result in observed vehicle usage that varies from the usage on which the startup schedule was based. These changes may result in a recommended schedule that changes to the new schedule based on the varied new schedule.
[0050] In this example, after vehicle start data has been sent to the remote server, the process on the vehicle may determine if a change is recommended 209 . If the change is not recommended, the process may also determine if a change in schedule is recommended. If the schedule had already been set, and the current usages deviated from the recommended schedule as set, the process may resultantly recommend a change to a current schedule 401 .
[0051] If so, the process may receive the recomemneded changes to the current schedule from the remote server 403 . As with the previous process, any and all determinations may also be made by a local process as opposed to on the remote server.
[0052] Once the changed schedule has been received, the process may load a current schedule set on the vehicle 405 . This may be done so that the new schedule can be compared to the local schedule on the vehicle to determine if the user, for example, has already set the new schedule on the vehicle and the remote server simply did not know about the vehicle. As long as there is a difference in the schedules 407 , the process may proceed, otherwise the process may exit. As with before, the process may check to see if the user has blocked changes to the schedule 409 . If the user has blocked changes, the process may exit.
[0053] If the change suggestion is not blocked, the process may present new suggested start times and current times (if desired) 411 . By presenting both new and current times, the process can show the user what the current schedule is, and what the new schedule will be. If the user accepts the changes 413 , the process can set a new schedule on the vehicle 415 . If the user rejects the schedule 413 , the process can provide an option to block the schedule.
[0054] If the user opts to block the schedule 421 , the process can set a block parameter 419 . In either event, the server can be updated with the changes selected by the user 417 . Even if the schedule is not selected and if the block is not set, the server can still be set with the parameters unchanged.
[0055] FIG. 5 shows an illustrative server-side process for recommending changing a schedule. With respect to the illustrative embodiments described in this figure, it is noted that a general purpose processor may be temporarily enabled as a special purpose processor for the purpose of executing some or all of the exemplary methods shown herein. When executing code providing instructions to perform some or all steps of the method, the processor may be temporarily repurposed as a special purpose processor, until such time as the method is completed. In another example, to the extent appropriate, firmware acting in accordance with a preconfigured processor may cause the processor to act as a special purpose processor provided for the purpose of performing the method or some reasonable variation thereof
[0056] In this illustrative example, the remote process will also determine if a change to a current schedule should be implemented. After receiving the start up data from the vehicle, the process checks to see if a time proximate to the current startup time is set 501 . The proximate definition here, may be, for example, 45 minutes to an hour, representing a wide latitude in possible schedule changes. Since, in this example, a proximate time set will result in a check for a change in schedule, the proximate time definition may be broad.
[0057] In other examples, other checks can be made in lieu of this check, such as a check to see if the vehicle was actually used at an anticipated time (and this startup is just ancillary to the normal startup). Other suitable checks may also be made, to determine if a schedule already exists and whether or not the schedule comports with the actual observed usages.
[0058] If the current usage appears to be a deviation from the planned usage, based on the suitable tests, the process may load parameters for usage to check for suitable data to change a schedule. These parameters can define variances such as, but not limited to, variances in predicted and actual usage times, variances in days of usage, and number of times a variance should be observed before a change should be made.
[0059] The newly observed and different times can be compared to the currently predicted times 505 to see if the parameters for a change are met 507 . If the parameters are met, the process can create a new schedule 509 . The new schedule, which can be an amendment of the current schedule, is then sent to the vehicle 511 .
[0060] The process then waits for a response from the vehicle 513 . If the response is not received from the vehicle, the process can continue to wait. Otherwise, the process receives a response from the vehicle and receives any updates that are sent by the vehicle 515 . The updates sent to the vehicle can then be used to update a remote schedule in accordance with the received updates.
[0061] While exemplary embodiments are described above, it is not intended that these embodiments describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention. Additionally, the features of various implementing embodiments may be combined to form further embodiments of the invention. | A computer implemented method includes logging vehicle startup information. The method also includes determining, via a computer, if timing commonalities exist between logged vehicle startup information instances. Further, the method includes recommending automatic vehicle startup, based on a threshold number of timing commonalities. The method also includes formulating recommended start times based on logged vehicle startup information instances having timing commonalities. The method additionally includes presenting a schedule including recommended start times to a vehicle user and scheduling automatic vehicle startups upon vehicle user acceptance of the presented schedule. | 6 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to PCT international patent application PCT/SE2008/050094 filed Jan. 28, 2008.
FIELD OF THE INVENTION
[0002] This invention relates to a vehicle safety system, and in particular concerns a system for protecting vehicle occupants during various types of crash situation.
BACKGROUND OF THE INVENTION
[0003] While most vehicles are typically equipped with safety devices to protect vehicle occupants in the event of a side impact occurring. In general, in a sideways direction the distance between a vehicle occupant and the exterior of the vehicle is relatively small, since the sides of the vehicle are thin. It is therefore important that safety devices, such as internal side air-bags, which are adapted to protect occupants during side impacts, are activated at the earliest possible stage.
[0004] In some instances, it is possible to detect that a side impact is imminent, for instance by using radar or lidar detection, and to activate one or more appropriate vehicle safety systems before the impact has occurred. In other circumstances, impact sensors are used to detect side impacts, and hence deployment of the vehicle safety systems will not occur until the impact has actually happened.
[0005] Deployment of the safety systems will be controlled by an on-board processor, in accordance with a deployment algorithm. There are, however, competing priorities which must be taken into account when formulating the algorithm. On the one hand, as discussed above, the relevant side impact safety systems must be activated as swiftly as possible in the event of a crash situation occurring. On the other hand, the algorithm must be robust against “false positive” determinations, which could lead to the side impact safety systems being deployed unnecessarily. Such situations may include the door of a vehicle being slammed with above average force, and low-impact crashes that are unlikely to cause harm to vehicle occupants. It will therefore be understood that deployment algorithms are generally a compromise between these two competing priorities.
[0006] It is an object of the present invention to seek to provide an improved safety system of this type.
[0007] Accordingly, one aspect of the present invention provides a vehicle safety system comprising: at least one occupant safety device for protecting an occupant of the vehicle in the event of a side impact; and a control unit operable to receive information from one or more vehicle sensors and to provide a trigger signal to activate the occupant safety device, wherein: under normal driving conditions, a default deployment algorithm is used by the control unit to determine whether the trigger signal should be generated; and if it is determined that loss of control of the vehicle is occurring, or is expected to occur, and the longitudinal speed of the vehicle exceeds a first threshold, the control unit employs a first further deployment algorithm to determine whether the trigger signal should be generated, the first further deployment algorithm being adapted to cause the trigger signal to be generated a shorter time after the initiation of a side impact than is the case for the default deployment algorithm.
[0008] Advantageously, it is determined that loss of control of the vehicle is occurring, or is expected, if it is determined that the vehicle is undergoing one or more of understeer, oversteer, a lateral skid, avoidance manoeuvring, emergency braking, and departure from the road on which the vehicle is travelling.
[0009] Preferably, the control unit is provided with criteria for evaluating whether one or more of understeer, oversteer, lateral skid avoidance manoeuvring, emergency braking, or road departure are occurring, from signals generated by the one or more vehicle sensors.
[0010] Conveniently, a second further deployment algorithm is adopted if both the longitudinal and lateral speeds of the vehicle exceed respective thresholds, and it is determined that loss of control of the vehicle is occurring, or is expected to occur.
[0011] Advantageously, the second further deployment algorithm is adapted to cause the trigger signal to be generated a shorter time after the initiation of a side impact than is the case for the first alternative deployment algorithm.
[0012] Preferably, the preset threshold for vehicle speed is between 5 and 20 km/h.
[0013] Conveniently, the preset threshold is 15 km/h.
[0014] Another aspect of the present invention provides a method of controlling an occupant safety device of a vehicle for protecting an occupant of the vehicle in the event of the side impact, the method comprising the steps of: receiving information from one or more vehicle sensors; and analysing the signals in accordance with a deployment algorithm and providing a trigger signal to activate the occupant safety device if it is determined that activation of the safety device is necessary, wherein: under normal driving conditions, a default deployment algorithm is employed to determine whether the trigger signal should be generated; and if it is determined that loss of control of the vehicle is occurring, or is expected to occur, and the longitudinal speed of the vehicle exceeds a first threshold, employing a first further deployment algorithm to determine whether the trigger signal should be generated, the first further deployment algorithm being adapted to cause a trigger signal to be generated a shorter time after the initiation of a side impact than is the case for the default deployment algorithm.
[0015] A further aspect of the invention provides a computer program comprises computer program code adapted to perform all of the steps as claimed above wherein the program is run on a computer.
[0016] Another aspect of the invention provides a computer program as claimed above is embodied on a computer readable medium
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] In order that the present invention may be more readily understood, embodiments thereof will now be described, by way of example, with reference to the accompanying drawings, in which;
[0018] FIG. 1 is a schematic view of a vehicle having a safety system embodying the present invention; and
[0019] FIG. 2 is a schematic view of a decision-making process for a system embodying the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0020] With reference firstly to FIG. 1 , a schematic view of a vehicle 1 is shown. As is known in the art, the vehicle 1 is provided with a number of sensors which are adapted to sense position, movement and control of the vehicle 1 . These sensors include a set of accelerometers 2 , to measure acceleration a x of the vehicle 1 in the longitudinal direction x, a y in the lateral direction y, and a z in the vertical direction (pointing directly away from the page in FIG. 1 ). The speed of the vehicle 1 in various directions can also be determined from outputs from these accelerometers 2 , and the longitudinal v x of the vehicle can be derived from the speedometer. The accelerometers 2 also include a yaw sensor to measure the yaw rate ω z . A GPS or other positioning system 3 is provided to determine the position of the vehicle 1 on the Earth's surface. Sensors 4 are further provided to detect the angle α of the steering wheel, the angle β of the throttle, and the brake pressure p that is applied to a brake pedal of the vehicle 1 .
[0021] Side impact sensors 5 are mounted along the sides of the vehicle 1 , and are each configured to output a signal which is indicative of the lateral acceleration of the sensor 5 .
[0022] The vehicle 1 also comprises one or more safety devices, such as a side air-bag 6 , to protect a vehicle occupant in the event of a side impact. A control unit 7 , which comprises one or more processors, interprets signals output by the sensors 2 , 3 , 4 , 5 and determines whether the safety devices should be triggered.
[0023] Using the information derived from some or all of these sensors 2 , 3 , 4 , 5 it is possible to make a determination as to whether the vehicle 1 is in a situation where it is likely to be involved in a harmful side impact. In particular, such an impact is more likely to occur where control of the vehicle has been lost, or appears likely to be lost. Such a situation may be indicated by understeer of the vehicle 1 , by oversteer of the vehicle 1 , or by lateral slip of the vehicle 1 (i.e. where the vehicle 1 skids in a lateral direction). Loss of control may also be occurring, or be likely to occur, if the vehicle 1 is undergoing avoidance manoeuvring or emergency braking, or if it appears that the vehicle 1 has left the road on which it is travelling.
[0024] If any of these conditions are met, the likelihood of the vehicle 1 being involved in a harmful side impact is increased. In addition, the likelihood of a harmful side impact occurring is increased if the longitudinal speed of the vehicle 1 is relatively high. For instance, if the vehicle's speed is in excess of 5 km/h, and particularly if the speed is in excess of 15 km/h, it may be determined that the likelihood of harmful impact is high. The lowest limit is chosen so that, below this speed, even if a side impact occurs the probability of vehicle occupants being harmed is low.
[0025] Vehicle safety systems embodying the present invention comprise a default deployment algorithm, which is adapted to interpret data from at least the side impact sensors 5 and make a determination as to whether one or more safety devices should be deployed to protect an occupant of the vehicle from a side impact. Depending on the type of a particular safety device, the algorithm may also determine the mode in which the safety device is activated. This default deployment algorithm may be similar to conventional deployment algorithms, and may cause deployment of the safety device if the integrated lateral acceleration exceeds a threshold Th 3 .
[0026] The vehicle's control unit 7 also comprises at least a first further deployment algorithm, which is used when it is determined that the likelihood of the vehicle 1 being involved in a harmful side impact is high. If such a determination is made, then the threshold for integrated lateral acceleration above which deployment will occur is decreased to a lower value Th 4 .
[0027] In preferred embodiments a second further deployment algorithm is also available, which may be adopted when a determination is made that there is a further increased likelihood of a harmful side impact occurring. When the second further deployment algorithm is used the threshold for integrated lateral acceleration above which deployment will occur is further decreased to a still lower value Th 5 .
[0028] As described above, the threshold Th 3 for the default algorithm must be set so that the safety systems is unlikely to be triggered by any inappropriate events, for instance the violent slamming of a door of the vehicle 1 , or a low-impact crash that is unlikely to cause harm to any occupants of the vehicle 1 .
[0029] However, if it is determined that the vehicle 1 is in a situation where a harmful side impact appears to be likely, it is possible to lower the threshold against which integrated value of the lateral acceleration of the impact sensor 5 is compared, as the benefit obtained from early triggering of safety systems will outweigh the potential risk of the safety systems being triggered erroneously.
[0030] For instance, if the driver of the vehicle 1 attempts to negotiate a sharp corner at too high a speed, the vehicle 1 may skid sideways off the road. In this case, the control unit 7 may determine, from information output by the vehicle's sensors 2 , 3 , 4 , one or more of: that an understeer situation has occurred; that the vehicle is involved in lateral slip; and that the vehicle has left the road. In such circumstances, the vehicle 1 may travel in a generally sideways direction at relatively high speed, and there is a large danger that the vehicle 1 may strike a pole, tree or similar object, and that such an impact would be harmful to vehicle occupants.
[0031] Under these circumstances, the risk of events such as the slamming of a door of the vehicle, which might lead to erroneous triggering of the safety systems, is very small.
[0032] In preferred embodiments of the invention, the first further deployment algorithm is adopted in situations where loss of control of the vehicle 1 has occurred, or is expected to occur, and where the vehicle's longitudinal speed exceeds a preset safe longitudinal speed threshold Th 1 .
[0033] In advantageous embodiments, the second further deployment algorithm is used in situations where loss of control of the vehicle has occurred, or is expected to occur, and where both the vehicle's longitudinal and lateral speed exceed preset safe thresholds Th 1 , Th 2 .
[0034] With reference to FIG. 2 , a schematic view of the decision-making process to decide which deployment algorithm to employ is shown.
[0035] The decision making process includes several decision-making elements which are adapted to provide a determination as to whether a particular vehicle behaviour, which may be indicative of loss of vehicle control or likely loss of vehicle control, is occurring.
[0036] An oversteer/understeer decision-making element 8 may receive inputs from one or all of the yaw rate sensor 2 , the steering wheel angle sensor 4 , and information regarding the longitudinal speed of the vehicle 1 , to reach a determination that the vehicle 1 is understeering or oversteering.
[0037] A body slip decision-making element 9 may take information from one or all of the yaw rate sensor 2 , the sensed acceleration of the vehicle 1 in a lateral direction, and the longitudinal speed of the vehicle 1 , to reach a determination as to whether the vehicle 1 is undergoing a sideways skid.
[0038] A road departure decision-making element 10 receives information from one or both of the positioning system 4 , and vertical acceleration a, of the vehicle 1 , to make a determination as to whether the vehicle 1 has left the road on which it is travelling.
[0039] An emergency braking decision-making element 11 receives information from one or both of the brake pressure p that is applied to a brake pedal of the vehicle, and the rate of change of the angle β of the throttle pedal, to arrive at a determination as to whether the driver of the vehicle 1 is performing an emergency braking manoeuvre.
[0040] An avoidance manoeuvring decision-making element 12 has as input one or both of a rate of change of the steering wheel angle α, and the longitudinal speed of the vehicle 1 , to reach a determination as to whether the driver of the vehicle 1 is performing an avoidance manoeuvring procedure.
[0041] Any combination of some of these criteria may be used and the invention is not limited to considering all of these criteria.
[0042] The outputs from each of these decision-making elements 8 , 9 , 10 , 11 , 12 are input to a first OR element 13 which provides a positive output if any of the decision-making units 8 , 9 , 10 , 11 , 12 provides a positive output, indicating that the vehicle conditions relating to that decision-making element 8 , 9 , 10 , 11 , 12 are satisfied.
[0043] In addition, a longitudinal speed decision-making element 14 receives information regarding the longitudinal speed of the vehicle 1 , and compares this value with the safe longitudinal speed threshold Th 1 , to arrive at a determination as to whether the longitudinal speed of the vehicle 1 is above a preset safe level.
[0044] A lateral speed decision-making element 15 receives information regarding the yaw rate ω z of the vehicle, as well as the acceleration a y of the vehicle 1 in the lateral direction y, to reach a determination as to whether the lateral speed of the vehicle 1 exceeds the safe lateral speed threshold Th 2 .
[0045] The longitudinal and lateral speed decision-making elements 14 , 15 each give a positive output if it is determined that either of these speeds exceed the respective safe thresholds Th 1 , Th 2 .
[0046] Outputs from the understeer/oversteer decision-making element 8 , the body slip decision-making element 9 and the road departure decision-making element 10 are fed into a second OR element 16 .
[0047] Outputs from the longitudinal and lateral speed decision-making elements 14 and 15 , as well as the output from the second OR element 16 , are inputted into a first AND element 17 , whose output will be positive if each of the three inputs is positive. The output from the longitudinal speed decision-making element 14 and the first OR element 13 are inputted into a second AND element 18 , which once again will only provide a provide output if both of the inputs are positive.
[0048] Integrated data from a side impact sensor 5 , or from one or more other suitable sensors, is fed to three separate comparators 19 , 20 , and 21 , which each compare the integrated lateral acceleration a y against respective thresholds. The first comparator 19 compares the integrated acceleration with the threshold Th 3 of the default algorithm. The second comparator 20 compares the integrated acceleration against the lowered threshold Th 4 which is used by the further deployment algorithm. The third comparator 21 compares the integrated acceleration against a further lowered threshold Th 5 which is used by the second further deployment algorithm.
[0049] A third OR element 22 is provided, which has three inputs. If any of the inputs to the third OR element 22 are positive, the third OR element 22 will output a positive signal, which will trigger the deployment of the side air-bag 6 .
[0050] If the integrated lateral acceleration a y determined by the first comparator 19 is in excess of the threshold Th 3 used by the default deployment algorithm, this will provide a positive input to the third OR element 22 . Thus, if the integrated lateral acceleration a y exceeds this default threshold Th 3 , the side air-bag 6 will be triggered irrespective of the outputs from any other sensors.
[0051] The output from the second comparator 20 will be positive if it is determined by the second comparator 20 that the integrated lateral acceleration a y exceeds the lowered threshold Th 4 used by the first further deployment algorithm. The output from the second comparator 20 is inputted into a third AND element 23 , which also has as an input the output of the second AND element 18 . The output of the third AND element 23 provides an input to the third OR element 22 . It will therefore be understood that, if the integrated lateral acceleration a y exceeds the lowered threshold Th 4 used by the first further deployment algorithm, and the longitudinal speed v x of the vehicle exceeds the appropriate safe threshold Th 1 , and it is determined that the vehicle is undergoing one or more of understeering/oversteering, body slip, road departure or emergency braking or avoidance, the side air-bag 6 will be triggered.
[0052] The output of the third comparator 21 is fed to a fourth AND element 24 , which also has as an input the output from the first AND element 17 .
[0053] Thus, it will be understood that if the integrated lateral acceleration a y exceeds the further lowered threshold Th 5 used by the second further deployment algorithm, and the respective safe thresholds Th 1 , Th 2 for longitudinal and lateral speed are both exceeded, and it is determined that one of oversteer/understeer, body slip, or road departure is occurring, then the side air-bag 6 will be triggered.
[0054] As discussed above, when the first or second further deployment algorithm is used, the threshold against which the integrated lateral acceleration a y is compared is lowered, so that in effect the further deployment algorithms are more sensitive to potential side impacts, with the result that safety systems will be activated at an earlier stage in the event of a real side impact.
[0055] In general, it will be understood that any number of different further deployment algorithms may be used, in which a lowered threshold is used to determine the level of integrated lateral acceleration (or indeed any other quantity) which must be detected if a safety device is to be triggered, with various additional criteria that must also be satisfied.
[0056] If it is determined that the vehicle 1 is in a situation in which a harmful side impact is likely, but no side impact occurs and the vehicle 1 reaches a halt safely, or resumes travelling in a safe manner, the conditions described above will no longer be met, and it will be determined that the vehicle 1 is no longer in a situation where a harmful side impact is likely. In this case, therefore, the default deployment algorithm for side-impact safety systems will once again be used.
[0057] In the embodiments described above, the further deployment algorithms are made more sensitive to potential side impacts by reducing the threshold against which the integrated lateral acceleration a y is compared. However, the invention is not limited to this, and any appropriate threshold or criterion for assessing the likelihood that a side impact is occurring, or is likely to occur, may be reduced or adapted to make the further deployment algorithm more sensitive to side impacts.
[0058] It will be understood that embodiments of the present invention will provide a flexible system for triggering side-impact safety systems in the most appropriate manner depending on the circumstances, which may lead to a significant improvement in passenger safety.
[0059] The features disclosed in the foregoing description, or the following claims, or the accompanying drawings, expressed in their specific forms or in terms of a means for performing the disclosed function, or a method or process for attaining the disclosed result, as appropriate, may, separately, or in any combination of such features, be utilised for realising the invention in diverse forms thereof. | A vehicle safety system comprising: at least one occupant safety device ( 6 ) for protecting an occupant of the vehicle ( 1 ) in the event of a side impact; and a control unit ( 7 ) operable to receive information from one or more vehicle sensors ( 2, 3, 4, 5 ) and to provide a trigger signal to activate the occupant safety device ( 6 ). Under normal driving conditions, a default deployment algorithm is used by the control unit ( 7 ) to determine whether the trigger signal should be generated; and if it is determined that loss of control of the vehicle ( 1 ) is occurring, or is expected to occur, and the longitudinal speed of the vehicle ( 1 ) exceeds a first threshold, the control unit ( 7 ) employs a first further deployment algorithm to determine whether the trigger signal should be generated. The first further deployment algorithm being adapted to cause the trigger signal to be generated a shorter time after the initiation of a side impact than is the case for the default deployment algorithm. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to an exhaust apparatus of an outboard motor.
In known art, Japanese Patent Laid-open Publication No. HEI 6-129224 discloses one example of an exhaust apparatus of an outboard motor in which an exhaust passage connected to an exhaust port of a cylinder head is integrally formed in a cylinder block, and Japanese Utility Model Laid-open Publication No. HEI 4-134626 also discloses an exhaust apparatus of an outboard motor in which a separate exhaust manifold is disposed between a cylinder head and an oil pan which is formed with an exhaust passage.
However, in the known art mentioned above, in the exhaust apparatus in which the exhaust passage is integrally formed in the cylinder block, the cylinder block is increased in size and in weight, and its shape is complicated, which increases manufacturing costs. Further, since the exhaust passage is formed in the vicinity of the cylinder, the exhaust heat may thermally deform the cylinder, which is not preferable. Furthermore, since the cylinder and the exhaust apparatus commonly use the same cooling water jacket, it is impossible to adjust the temperature of only the exhaust apparatus.
In order to eliminate the above defects in the prior art, it may be possible to use a separate exhaust manifold. However, since an exhaust port is normally disposed at a location close to a rear portion of the engine, if the exhaust manifold is connected to the exhaust port, a width of the engine is increased, being disadvantageous in terms of layout, and moreover, a shape of an engine cover having stream line (substantially elliptic shape) section may be deformed.
SUMMARY OF THE INVENTION
An object of the present invention is to substantially eliminate defects or drawbacks encountered in the prior art mentioned above and to provide an exhaust apparatus of an outboard motor having an engine with reduced width.
Another object of the present invention is to provide an exhaust apparatus of an outboard motor capable of properly adjusting a temperature of only the exhaust apparatus.
These and other objects can be achieved according to the present invention by providing an exhaust apparatus of an outboard motor having an engine in which a cylinder head is disposed behind, in a state of an outboard motor mounted to a hull, a cylinder block formed with a plurality of vertically disposed cylinders, in which an exhaust apparatus connected to the cylinder head is disposed near a center portion of the engine.
In a preferred embodiment, a cam chain case is disposed below the engine, the cam chain case being provided with an exhaust passage constituting the exhaust apparatus and the exhaust apparatus further comprises an exhaust manifold connected to the cylinder head, the exhaust manifold being connected to the exhaust passage. The exhaust passage is formed at a portion near a central portion of the engine having most wide width in association with a lower end portion of the exhaust manifold.
The exhaust manifold is formed with a water jacket and the exhaust passage is formed with another water jacket, the water jackets being in communication with each other. The water jacket of the exhaust manifold is in communication with an upper end of the exhaust manifold and the exhaust apparatus further comprises a cooling water outlet serving as a water checking port for cooling water.
In a more specified aspect, there is provided an exhaust apparatus of an outboard motor which includes an engine holder, an engine disposed above the engine holder and comprising a cylinder block provided with a plurality of cylinders, a cylinder head disposed behind the cylinder block, in an installed state of the outboard motor, a crankcase, a cam chain case through which the engine is mounted on the engine holder, and an exhaust apparatus operatively connected to the cylinder head,
the exhaust apparatus comprising an exhaust passage formed to the cam chain case, an exhaust manifold connected to the cylinder head, a water jacket formed to the exhaust manifold and another water jacket formed to the exhaust passage, wherein the exhaust passage is formed at a portion near a central portion of the engine having most wide width in association with a lower end portion of the exhaust manifold.
According to the structure of the exhaust apparatus of the outboard motor, the exhaust apparatus is disposed near the central portion of the engine so as to reduce the increasing of the width thereof, and the two water jackets are formed independently, so that the temperature of the exhaust apparatus can be adjusted alone.
The nature and further characteristic features of the present invention will be made more clear from the following descriptions made with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings:
FIG. 1 is a left side longitudinal sectional view of an outboard motor of an embodiment provided with an exhaust apparatus of the present invention;
FIG. 2 is a right side view of the outboard motor shown in FIG. 1;
FIG. 3 is a plan view of the outboard motor shown in FIG. 1;
FIG. 4 is a sectional view taken along the line IV--IV in FIG. 1;
FIG. 5 is a plan view of a cam chain case of the embodiment shown in FIG. 1;
FIG. 6 is a bottom view of the cam chain case; and
FIG. 7 is an enlarged sectional view of a connecting portion of an exhaust manifold.
DESCRIPTION OF THE PREFERRED EMBODIMENT
An embodiment of the present invention will be described hereunder with reference to the accompanying drawings.
Referring to FIGS. 1 and 2, an outboard motor 1 includes an engine holder 2 and an engine 3 disposed above the engine holder 2. The engine 3 is a water-cooled three-cylinder engine and comprises a cylinder head 4, a cylinder block 5, a crankcase 6 and the like. The engine 3 is mounted on the engine holder 2 through a cam chain case 7.
The cylinder block 5 is disposed in a rearward position (right side in FIG. 1) of the crankcase 6. A cylinder head 4 is disposed in a rearward position of the cylinder block 5. The cam chain case 7 is disposed below the crankcase 6, the cylinder block 5 and the cylinder head 4.
A crankshaft 8 is vertically disposed within the crankcase 6, and an oil pan 9 is disposed below the engine holder 2. An engine cover 10 covers an area from the engine 3 to the oil pan 9.
A drive shaft housing 11, in which a drive shaft is accommodated, is disposed below the oil pan 9. An upper end portion of the drive shaft 12 is, for example, spline-fitted to a lower end portion of the crankshaft 8. The drive shaft 12 extends downward in a shaft pipe 13 formed within the drive shaft housing 11, and the drive shaft 12 drives a propeller 15 through a bevel gear and a propeller shaft (both not shown) in a gear case 14 provided below the drive shaft housing 11.
FIG. 3 is a plan view of the outboard motor 1, and FIG. 4 is a sectional view taken along the line IV--IV in FIG. 1. As shown in FIGS. 3 and 4, the engine components are designed such that substantially the center portion of the engine 3 has the widest width and the engine 3 is tapered toward front and rear portions thereof. Shapes and designs of the engine components are set so that they can be accommodated within the engine cover 10 having stream line (substantially elliptic shape) horizontal section.
As shown in FIGS. 1 to 4, three cylinders 16 each formed horizontally are vertically arranged within the cylinder block 5 in a state of the outboard motor mounted to a hull, for example. A combustion chamber 17 which is aligned with the cylinders 16 is formed in the cylinder head 4, and a spark plug 18 is coupled from the outside of the combustion chamber 17. A piston 19 is slidably inserted into each of the cylinders 16 in a horizontal direction, and the piston 19 and the crankshaft 8 are connected through a connecting rod 20. Reciprocal stroke of the piston 19 is converted into a revolutional movement of the crankshaft 8.
An intake port 21 and an exhaust port 22 are formed in the cylinder head 4. An intake valve 23 and an exhaust valve 24 for opening and closing the intake port 21 and the exhaust port 22, respectively, are disposed in the cylinder head 4, and a camshaft 25 for opening and closing these valves 23 and 24 is disposed in a rear portion of the cylinder head 4. A cam chain (not shown) is disposed in the cam chain case 7, and the camshaft 25 and the crankshaft 8 are operatively connected by means of the cam chain. A rear portion of the cylinder head 4 is covered with a cylinder head cover 26.
As shown in FIGS. 2 to 4, an electrical component box 28 accommodating an electrical component 27, an intake apparatus 29, an exhaust apparatus 30 and the like are disposed around the engine 3. The intake apparatus 29 is disposed on the one side of the engine 3, and the electrical component box 28 and the exhaust apparatus 30 are disposed on the other side of the intake apparatus 29.
An exhaust manifold 31 constituting the exhaust apparatus 30 is connected to the exhaust port 22. The exhaust manifold 31 once extends in a lateral direction toward the center portion of the engine 3 having the widest width and then extends downward.
A water jacket 32 for cooling the exhaust manifold 31 is formed around the exhaust manifold 31. A cooling water outlet 33 which is in communication with the water jacket 32 is provided at an upper end of the exhaust manifold 31. Further, the cooling water outlet 33 is designed as as to also function as a water checking port for the cooling water.
FIG. 5 is a plan view of the cam chain case 7 and FIG. 6 is a bottom view of the cam chain case 7. As shown in FIGS. 2 and 5, an exhaust passage 34 constituting the exhaust apparatus 30 is formed such that it vertically passes through the cam chain case 7, the engine holder 2 and the oil pan 9. The exhaust passage 34 is disposed in the engine 3 closer to the center portion thereof having the widest width in accordance with a position of a lower end portion of the exhaust manifold 31.
A connection portion 34a is formed on an upper end of the exhaust passage 34 formed in the cam chain case 7, and a lower end portion of the exhaust manifold 31 is connected to the connection portion 34a. A lower end of the exhaust passage 34 is opened toward an exhaust expansion chamber 11a formed in the drive shaft housing 11. A water jacket 35 is formed around the exhaust passage 34.
FIG. 7 is an enlarged cross section of the connection portion 34a of the exhaust manifold 31. As shown in FIG. 7, upper and lower separate seal members 36 are provided in the connection portion 34a. The water jacket 32 of the exhaust manifold 31 and the water jacket 35 of the exhaust passage 34 are in communication with each other, and cooling water is introduced into a space 37 between the upper and lower seal members 36.
The exhaust apparatus of the outboard motor of the structure described above will operates as follows.
As shown in FIG. 1, for example, cooling water is pumped up from a water intake 39 of the gear case 14 by a water pump 38 which is driven by the drive shaft 12 and is introduced into a relief valve 41 provided at a lower portion of the oil pan 9 through a water pipe 40 and is then introduced into the water jacket 35 of the exhaust passage 34. The cooling water, which has cooled the exhaust passage 34, then cools a portion between the seal members 36 of the connection portion 34a of the exhaust manifold 31, and then, the cooling water is introduced into the water jacket 32 of the exhaust manifold 31. The cooling water which has cooled the exhaust manifold 31 is discharged from the cooling water outlet 33 formed in the upper end of the exhaust manifold 31.
As mentioned above, the engine components are designed so that the center portion of the engine 3 has the widest width, and the exhaust manifold 31 and the exhaust passage 34 are disposed around the center portion of the engine 3. Therefore, the width of the engine 3 is not increased, and the stream line section of the engine cover 10 can be maintained.
Further, the exhaust manifold 31 is connected to the connection portion 34a on the upper end of the exhaust passage 34 formed in the cam chain case 7, the water jacket 32 of the exhaust manifold 31 and the water jacket 35 of the exhaust passage 34 are in communication with each other, and the cooling water outlet 33 is provided at the upper end of the exhaust manifold 31. Therefore, since the cooling system of the exhaust apparatus 30 is separated from other cooling systems of the engine 3, it is possible to independently adjust the temperature of the exhaust apparatus 30.
Since the cooling water outlet 33 is designed so as to also function as the water checking port for the cooling water, it is unnecessary to newly form a water checking port, so that the number of parts and costs can be reduced.
Further, the connection portion 34a of the exhaust manifold 31 is provided with the upper and lower double seal members 36, and the cooling water is introduced into the space 37 between these seal members 36. Therefore, as a material of the seal member 36, a rubber having a high sealing property can be used although it has a low heat resistance. As a result, the sealing property and a reliability of the connection portion 34a are enhanced.
It is to be noted that the present invention is not limited to the described embodiment and many other changes and modifications may be made without departing from the scopes of the appended claims. | An outboard motor includes an engine holder, an engine disposed above the engine holder and the engine includes a cylinder block provided with a plurality of cylinders, a cylinder head disposed behind the cylinder block and a crankcase, a cam chain case through which said engine is mounted on the engine holder, and an exhaust apparatus operatively connected to the cylinder head. The exhaust apparatus includes an exhaust passage formed to the cam chain case, an exhaust manifold connected to the cylinder head, a water jacket formed to the exhaust manifold and another water jacket formed to the exhaust passage. The exhaust passage is formed at a portion near a central portion of the engine having most wide width in association with a lower end portion of the exhaust manifold. | 5 |
BACKGROUND OF INVENTION
The field of the invention relates to lean burn engine control in internal combustion engines.
lean burn engine systems can have different cylinder groups, each having a close-coupled catalytic converter. These cylinder groups come together in a y-pipe configuration before entering a under-body catalyst. The catalyst can store oxidants (including NOx) when operating lean, and release and reduce the oxidants with incoming reductants when operating rich. In this way, emissions are minimized while operating lean by also periodically operating rich. One such system is described in U.S. Pat. No. 5,970,707. In this system, lean and rich operation of the cylinder groups is generally synchronized during normal operation.
The inventors herein have recognized that while the Y-type configuration has some advantages, there may not be enough freedom to optimize exhaust system tuning. In particular, the underbody catalyst typically places a constraint on the location of the Y-pipe to provide optimal temperature window operation for the underbody catalyst.
On the other hand, the inventors herein have also recognized that having a dual exhaust system where two underbody catalysts are used with a Y-pipe joining them afterwards, provides more flexibility in positioning the Y-pipe joint. Therefore, there is more freedom for optimizing the exhaust system tuning.
Finally, the inventors herein have recognized that maintaining synchronous lean and rich engine operation of the dual catalyst path system may not fully use the catalyst's storage ability. In particular, due to component variation of the underbody catalysts, bank to bank variation of engine exhaust gas properties, and different aging rates of components, the catalysts on the different banks may not behave identically. The potential difference in catalyst conversion and storage/regeneration, if coupled with synchronous operation of the banks between lean and rich air fuel ratios, may therefore lead to degraded performance. For example, one catalyst may finish releasing or reducing stored NOx and oxygen before the other one does. In this case, if the rich operation of the two banks continue, there may be hydrocarbon and carbon monoxide break through from the catalyst that has already completely released stored oxidants. If the rich operation stops, on the other hand, the storage capacity of the other catalyst may not be fully regenerated, thereby leading to degraded performance in subsequent operation. In either case, the fuel economy and emissions may be negatively impacted.
SUMMARY OF INVENTION
Disadvantages of prior approaches are overcome by a method for controlling an engine having a first and second group of cylinders, the first group coupled to a first catalyst and the second group coupled to a second catalyst. The method comprises: concurrently operating the first and second cylinder groups rich of stoichiometry; in response to a first indication that said rich operation of at least one of the first and second catalysts should be ended, operating the group coupled to the at least one catalyst near stoichiometry while continuing operation of the other group rich of stoichiometry; and in response to a second indication that said rich operation of the other catalyst should be ended, ending rich operation of the other group. By operating the cylinder group coupled to the catalyst that has depleted stored oxidants near stoichiometry, HC and CO breakthrough are minimized while at the same time minimizing any torque imbalance between the two cylinder groups, i.e., since one bank is operating rich and the other near stoichiometry (with the same amount of air per cylinder), engine torque is substantially maintained since the additional fuel in the rich cylinder does not burn to make torque. Any slight torque increase in torque can be compensated for by ignition retard on the rich cylinder bank. In this way, the other catalyst can also be depleted of stored oxidants. Therefore, the full potential of both catalysts is achieved without sacrificing emission performance or driveability.
An advantage of the above aspect of the invention is therefore improved emissions and more efficient use of catalysts in separate exhaust streams.
Also note that the indications provided above may be given in a variety of ways such as based on air-fuel ratio sensors coupled downstream of the catalyst, based on estimates using other operating parameters, or various other indications.
Other advantages of the present invention will be readily appreciated by the reader of this specification.
BRIEF DESCRIPTION OF DRAWINGS
The object and advantages of the invention claimed herein will be more readily understood by reading an example of an embodiment in which the invention is used to advantage with reference to the following drawings wherein:
FIGS. 1A and 1B are a block diagrams of an embodiment in which the invention is used to advantage;
FIG. 2 is a block diagram of an embodiment in which the invention is used to advantage;
FIG. 3 is high level flowchart which perform a portion of operation of the embodiment shown in FIGS. 1A, 1 B, and 2 ; and
FIGS. 4A and 4B are graphs depicting results using the present invention.
DETAILED DESCRIPTION
Direct injection spark ignited internal combustion engine 10 , comprising a plurality of combustion chambers, is controlled by electronic engine controller 12 . Combustion chamber 30 of engine 10 is shown in FIG. 1A including combustion chamber walls 32 with piston 36 positioned therein and connected to crankshaft 40 . In this particular example, piston 36 includes a recess or bowl (not shown) to help in forming stratified charges of air and fuel. Combustion chamber, or cylinder, 30 is shown communicating with intake manifold 44 and exhaust manifold 48 via respective intake valves 52 a and 52 b (not shown), and exhaust valves 54 a and 54 b (not shown). Fuel injector 66 A is shown directly coupled to combustion chamber 30 for delivering liquid fuel directly therein in proportion to the pulse width of signal fpw received from controller 12 via conventional electronic driver 68 . Fuel is delivered to fuel injector 66 A by a conventional high pressure fuel system (not shown) including a fuel tank, fuel pumps, and a fuel rail.
Intake manifold 44 is shown communicating with throttle body 58 via throttle plate 62 . In this particular example, throttle plate 62 is coupled to electric motor 94 so that the position of throttle plate 62 is controlled by controller 12 via electric motor 94 . This configuration is commonly referred to as electronic throttle control (ETC), which is also utilized during idle speed control. In an alternative embodiment (not shown), which is well known to those skilled in the art, a bypass air passageway is arranged in parallel with throttle plate 62 to control inducted airflow during idle speed control via a throttle control valve positioned within the air passageway.
Exhaust gas oxygen sensor 76 is shown coupled to exhaust manifold 48 upstream of catalytic converter 70 . In this particular example, sensor 76 provides signal EGO to controller 12 which converts signal EGO into two-state signal EGOS. A high voltage state of signal EGOS indicates exhaust gases are rich of stoichiometry and a low voltage state of signal EGOS indicates exhaust gases are lean of stoichiometry. Signal EGOS is used to advantage during feedback air/fuel control in a conventional manner to maintain average air/fuel at stoichiometry during the stoichiometric homogeneous mode of operation.
Conventional distributorless ignition system 88 provides ignition spark to combustion chamber 30 via spark plug 92 in response to spark advance signal SA from controller 12 .
Controller 12 causes combustion chamber 30 to operate in either a homogeneous air/fuel mode or a stratified air/fuel mode by controlling injection timing. In the stratified mode, controller 12 activates fuel injector 66 A during the engine compression stroke so that fuel is sprayed directly into the bowl of piston 36 . Stratified air/fuel layers are thereby formed. The strata closest to the spark plug contains a stoichiometric mixture or a mixture slightly rich of stoichiometry, and subsequent strata contain progressively leaner mixtures. During the homogeneous mode, controller 12 activates fuel injector 66 A during the intake stroke so that a substantially homogeneous air/fuel mixture is formed when ignition power is supplied to spark plug 92 by ignition system 88 . Controller 12 controls the amount of fuel delivered by fuel injector 66 A so that the homogeneous air/fuel mixture in chamber 30 can be selected to be at stoichiometry, a value rich of stoichiometry, or a value lean of stoichiometry. The stratified air/fuel mixture will always be at a value lean of stoichiometry, the exact air/fuel being a function of the amount of fuel delivered to combustion chamber 30 . An additional split mode of operation wherein additional fuel is injected during the exhaust stroke while operating in the stratified mode is also possible.
Nitrogen oxide (NOx) absorbent or trap 72 is shown positioned downstream of catalytic converter 70 . NOx trap 72 absorbs NOx when engine 10 is operating lean of stoichiometry. The absorbed NOx is subsequently reacted with HC and CO and catalyzed during a NOx purge cycle when controller 12 causes engine 10 to operate in either a rich homogeneous mode or a near stoichiometric homogeneous mode.
Controller 12 is shown in FIG. 1A as a conventional microcomputer, including microprocessor unit 102 , input/output ports 104 , an electronic storage medium for executable programs and calibration values shown as read only memory chip 106 in this particular example, random access memory 108 , keep alive memory 110 , and a conventional data bus. Controller 12 is shown receiving various signals from sensors coupled to engine 10 , in addition to those signals previously discussed, including measurement of inducted mass air flow (MAF) from mass air flow sensor 100 coupled to throttle body 58 ; engine coolant temperature (ECT) from temperature sensor 112 coupled to cooling sleeve 114 ; a profile ignition pickup signal (PIP) from Hall effect sensor 118 coupled to crankshaft 40 ; and throttle position TP from throttle position sensor 120 ; and absolute Manifold Pressure Signal MAP from sensor 122 . Engine speed signal RPM is generated by controller 12 from signal PIP in a conventional manner and manifold pressure signal MAP from a manifold pressure sensor provides an indication of vacuum, or pressure, in the intake manifold. During stoichiometric operation, this sensor can give and indication of engine load. Further, this sensor, along with engine speed, can provide an estimate of charge (including air) inducted into the cylinder. In a preferred aspect of the present invention, sensor 118 , which is also used as an engine speed sensor, produces a predetermined number of equally spaced pulses every revolution of the crankshaft.
In this particular example, temperature Tcat of catalytic converter 70 and temperature Ttrp of NOx trap 72 are inferred from engine operation as disclosed in U.S. Pat. No. 5,414,994, the specification of which is incorporated herein by reference. In an alternate embodiment, temperature Tcat is provided by temperature sensor 124 and temperature Ttrp is provided by temperature sensor 126 .
Continuing with FIG. 1A, camshaft 130 of engine 10 is shown communicating with rocker arms 132 and 134 for actuating intake valves 52 a , 52 b and exhaust valve 54 a , 54 b . Camshaft 130 is directly coupled to housing 136 . Housing 136 forms a toothed wheel having a plurality of teeth 138 . Housing 136 is hydraulically coupled to an inner shaft (not shown), which is in turn directly linked to camshaft 130 via a timing chain (not shown). Therefore, housing 136 and camshaft 130 rotate at a speed substantially equivalent to the inner camshaft. The inner camshaft rotates at a constant speed ratio to crankshaft 40 . However, by manipulation of the hydraulic coupling as will be described later herein, the relative position of camshaft 130 to crankshaft 40 can be varied by hydraulic pressures in advance chamber 142 and retard chamber 144 . By allowing high pressure hydraulic fluid to enter advance chamber 142 , the relative relationship between camshaft 130 and crankshaft 40 is advanced. Thus, intake valves 52 a , 52 b and exhaust valves 54 a , 54 b open and close at a time earlier than normal relative to crankshaft 40 . Similarly, by allowing high pressure hydraulic fluid to enter retard chamber 144 , the relative relationship between camshaft 130 and crankshaft 40 is retarded. Thus, intake valves 52 a , 52 b , and exhaust valves 54 a , 54 b open and close at a time later than normal relative to crankshaft 40 .
Teeth 138 , being coupled to housing 136 and camshaft 130 , allow for measurement of relative cam position via cam timing sensor 150 providing signal VCT to controller 12 . Teeth 1 , 2 , 3 , and 4 are preferably used for measurement of cam timing and are equally spaced (for example, in a V-8 dual bank engine, spaced 90 degrees apart from one another) while tooth 5 is preferably used for cylinder identification, as described later herein. In addition, controller 12 sends control signals (LACT,RACT) to conventional solenoid valves (not shown) to control the flow of hydraulic fluid either into advance chamber 142 , retard chamber 144 , or neither.
Relative cam timing is measured using the method described in U.S. Pat. No. 5,548,995, which is incorporated herein by reference. In general terms, the time, or rotation angle between the rising edge of the PIP signal and receiving a signal from one of the plurality of teeth 138 on housing 136 gives a measure of the relative cam timing. For the particular example of a V-8 engine, with two cylinder banks and a five-toothed wheel, a measure of cam timing for a particular bank is received four times per revolution, with the extra signal used for cylinder identification.
Sensor 160 provides an indication of both oxygen concentration in the exhaust gas as well as NOx concentration. Signal 162 provides controller a voltage indicative of the O 2 concentration while signal 164 provides a voltage indicative of NOx concentration.
Note that FIGS. 1A (and 1 B) merely shows one cylinder of a multi-cylinder engine, and that each cylinder has its own set of intake/exhaust valves, fuel injectors, spark plugs, etc.
Referring now to FIG. 1B, a port fuel injection configuration is shown where fuel injector 66 B is coupled to intake manifold 44 , rather than directly cylinder 30 .
The engine 10 operates in various modes, including lean operation, rich operation, and “near stoichiometric” operation. “Near stoichiometric” operation refers to oscillatory operation around the stoichiometric air fuel ratio. Typically, this oscillatory operation is governed by feedback from exhaust gas oxygen sensors. In this near stoichiometric operating mode, the engine is operated within one air fuel ratio of the stoichiometric air fuel ratio.
As described above, feedback air-fuel ratio is used for providing the near stoichiometric operation. Further, feedback from exhaust gas oxygen sensors can be used for controlling air-fuel ratio during lean and during rich operation. In particular, a switching type HEGO sensor can be used for stoichiometric air-fuel ratio control by controlling fuel injected (or additional air via throttle or VCT) based on feedback from the HEGO sensor and the desired air-fuel ratio. Further, a UEGO sensor (which provides a substantially linear output versus exhaust air-fuel ratio) can be used for controlling air-fuel ratio during lean, rich, and stoichiometric operation. In this case, fuel injection (or additional air via throttle or VCT) is adjusted based on a desired air-fuel ratio and the air-fuel ratio from the sensor.
Also note that various methods can be used according to the present invention to maintain the desired torque such as, for example, adjusting ignition timing, throttle position, variable cam timing position, and exhaust gas recirculation amount. Further, these variables can be individually adjusted for each cylinder to maintain cylinder balance among all the cylinder groups.
Referring now to FIG. 2, engine 10 is shown in a system including the exhaust system. Engine 10 is shown with first and second cylinder groups 210 and 212 , respectively. In this particular example, each of groups 210 and 212 has two cylinders. However, the engine groups need not have the same number of cylinders and may include even only one cylinder. First cylinder group 210 is coupled to exhaust manifold 48 A, while second cylinder group 212 is coupled to exhaust manifold 48 B. Further, exhaust manifold 48 A is coupled to first catalytic converter 70 A and second catalytic converter 72 A. Also, exhaust gas oxygen sensor 170 A is coupled downstream of catalyst 72 A. Similarly, exhaust manifold 48 B is coupled to catalyst 70 B and 72 B and exhaust gas oxygen sensor 170 B. The outlet of catalysts 72 A and 72 B are coupled to a Y-pipe, which leads to the tailpipe of the vehicle. Sensor 160 is coupled downstream of the Y-pipe. Note that while this is one potential configuration, each cylinder group may be coupled to only a single catalyst. Also, sensor 160 downstream of the Y-pipe may be excluded. Further still, estimates of engine exhaust parameters can be substituted for the measurements provided by sensors 170 A and 170 B.
Referring now to FIG. 3, a routine for controlling engine operation is described. First, in step 310 , the determination is made as to whether operating conditions are such that lean engine operation is desired. In particular, these engine operating conditions may include, for example, vehicle speed, engine torque, engine load, engine speed, engine temperature, catalyst temperature, time since engine start, or various other conditions. When the answer to step 310 is no, the routine continues to step 312 where both the first and second cylinder groups are operated near stoichiometry. For example, fuel injected into the first and second cylinder groups via the fuel injectors is adjusted using a proportional integral controller based on feedback from exhaust gas sensors when 70 A, 70 B, and further based on an open-loop estimate of air flow in any of the cylinders. This open-loop estimate of air flowing in the cylinders is based on, for example, engine speed and manifold pressure, or mass airflow from the mass airflow sensor.
When the answer to step 310 is yes, the first and second cylinder groups are operated lean of stoichiometry in step 314 . In this case, airflow entering the cylinders is adjusted via the electronically controlled throttle 62 . Then, in step 316 , a set point of NOx grams/mile (tailpipe NOx per distance traveled of the vehicle) is determined based on operating conditions. Note that in an alternative embodiment, a set point amount of NOx stored in the catalysts is determined based on operating conditions. Next, in step 318 , a determination is made as to whether the set point has been exceeded on either cylinder group. In other words, a determination is made as to whether either cylinder group is producing higher NOx out of the tailpipe per distance of the vehicle than the set point. In an alternative embodiment, determination is made as to whether the amount of NOx stored in the catalysts of either group is greater than the set point. Further still, a determination as to whether the total NOx exiting the each of the tailpipes per distance of the vehicle exceeds a threshold. When the answer to step 318 is no, the routine repeats. When the answer to step 318 is yes, the routine continues to step 320 . In other words, a determination is made on a per cylinder (or per catalyst) basis to determine if either of the separate exhaust paths” catalysts needs to be operated with a rich exhaust air-fuel ratio. Note that there are various other ways to trigger rich operation, such as, for example, based on catalyst deterioration and a learned catalyst rich operating duration.
In Step 320 , both cylinder groups are operated with a rich air-fuel ratio. Then, in step 322 , sensors 170 A and 170 B are read. Then, in step 324 , a determination is made as to whether either sensor downstream of catalysts 72 A and 72 B indicates a rich air-fuel ratio. In other words, a determination is made as to whether an indication has been provided that at least one of the first and second catalysts has depleted the stored oxidants (e.g., NOx and O 2 ). Note that there are various alternatives for providing this indication, such as, for example: whether exhaust oxygen concentration is below a threshold value, whether exhaust hydrocarbon or CO concentration is greater than a threshold value, and various others. For example, one alternative, which operates in a different way and provides different results than the previous alternatives, is to determine whether the integrated amount of reductant exiting a catalyst is greater than a threshold.
When an indication is provided in step 324 that either the first or second catalysts has depleted stored oxidants (or an indication that either first or second catalysts should discontinue operation with a rich air-fuel ratio) the routine continues to step 326 . Otherwise, the routine returns to step 322 .
In step 326 , the routine operates the cylinder group coupled to the catalyst whose rich operation should end at a near stoichiometric air-fuel ratio, while continuing rich operation of the other cylinder group. In other words, if, for example, an indication is provided that the first catalyst has depleted stored oxidants (or that the first catalyst should no longer be operated rich) the cylinder group coupled to the first catalyst is operated at the near stoichiometric air-fuel ratio, while continuing operation of the other cylinder group at a rich air fuel ratio to continue the releasing and reducing operation of the second catalyst. In this way, break through of reductants (hydrocarbons and carbon monoxide) is minimized, while maintaining optimal operation of each catalyst. Further, engine torque can be maintained at the desired level (and torque imbalance between the cylinder groups minimized) since the additional fuel injected during the rich operation only minimally may increase engine torque. As described below, if this small torque increase is present, ignition timing retard can be used to further maintain engine torque balance between the two cylinder groups.
Continuing with FIG. 3, in step 328 , the sensors downstream of the catalyst are read. Then, in step 330 , a determination is made as to whether the other catalyst (i.e., the catalyst that continued rich operation) has depleted oxidant its storage (or whether rich operation of this catalyst should end). As described above, there are various alternative approaches to providing an indication that rich operation of the cylinder group coupled to the other catalysts should be discontinued, and each of this, as well as other alternatives, can again be used here.
When the answer to step 330 is no, the routine continues to step 328 and repeats. When the answer to step 330 is yes, rich operation of the other cylinder group is terminated and the routine proceeds to step 332 . At this time, the engine may operate both cylinder groups near stoichiometry, or may return both cylinder groups to lean operation depending on operating conditions as described above in step of 310 . After step 332 , the routine is complete and is exited.
Thus, according to the present invention, it is possible to provide synchronous lean operation of the cylinder groups and a synchronized transition between lean to rich operation of both cylinder groups, but, asynchronous termination of the rich operation of the two cylinder groups. In particular, whichever cylinder group is coupled to a catalyst that has substantially depleted (or depleted to a certain amount) its oxidant storage, rich operation of the cylinder group coupled to that catalyst should be terminated. Further, that cylinder group is operated near stoichiometry while the rich cylinder operation of the other cylinder group is continued. In this way, optimal performance of the two catalysts is obtained even when the catalysts have different storage release and efficiency characteristics. Once rich operation of both catalysts should be terminated, the engine is then returned to lean operation, or near stoichiometric operation.
As described above, an alternative embodiment uses a set point amount of NOx stored in the catalysts to determine when rich operation should be commenced. In this embodiment, individual catalyst models can be used to determine the NOx storage of each catalyst individually. Also, in step 320 , when the engine cylinder groups are both operated rich of stoichiometry, adjustment of the throttle and exhaust gas recirculation valves can be used along with fuel and spark scheduling to maintain engine torque at a desired level. Also, in step 324 , as described above, there are various alternatives. Additional alternatives can be used depending on the type of exhaust gas sensor placed downstream of catalysts 72 A and 72 B. For example, a HEGO sensor can be used as well as a UEGO sensor can be used. Further as described above, estimation models can be used to determine rich operating times which are adjusted based on feedback from sensors 170 A and 170 B. Also note that if indications are provided simultaneously that rich operation for both cylinder groups should be terminated, then the ending of the rich operation may be synchronized.
Example operation according to the present invention is as now described with respect to the graphs in FIGS. 4A and 4B. First, the Figures show that the engines are concurrently being operated lean of stoichiometry. Note that the engines do not need to be operated at the same lean air fuel ratio, which is shown in the Figure. Rather, the engines may be operated at different lean air-fuel ratios. Further, the banks do not have to operate a fixed lean air-fuel ratios as shown in the Figure. Rather, the lean air-fuel ratios can vary over time and operating conditions. Then, at time T 1 , an indication is provided that both cylinder groups should be operated at a rich air-fuel ratio. Again, note that the cylinder groups do not need to be operated at the same rich air-fuel ratio or constant air-fuel ratios. Rather, the rich air-fuel ratios between the groups can vary, as can the rich air-fuel ratio in one of the groups. As with the lean banks, the variation can be based on time or operating conditions.
Continuing with the Figure, the indication provided at time T 1 can be based on NOx stored in the catalysts, NOx stored in only one of the catalysts, NOx exiting the tailpipe of the vehicle per distance of the per distance travel, or any other method as described above herein or suggested by this disclosure. In particular, in one example operation according to the present invention, when the amount of estimated NOx stored in one of the catalysts reaches a predetermined limit, both banks are switched to rich operation even though the amount of NOx stored in the other catalyst has not reached a predetermined NOx limit value.
Then, at time T 2 , an indication is provided that the catalysts coupled to group 2 should terminate the rich operation. At this time, cylinder group 2 is operated near stoichiometry. Then, at time T 3 , an indication is provided that the catalysts coupled to cylinder group 1 should terminate rich operation. At this time, both cylinder groups are returned to lean operation. Then, at time T 4 , an indication is provided that both cylinder groups should be operated rich. Then, at time T 5 , both cylinder groups simultaneously indicate that the rich operation should be terminated. At this time, both cylinder groups are returned to normal lean operation. Note, as described above, near stoichiometric operation may be selected after termination of the rich operation of both cylinder groups.
Note that there are various other alternatives to practicing the present invention, including those described above. Accordingly, it is intended that the present invention be defined only according to the following claims. | A method for controlling an engine having multiple banks with separate catalysts is described. In particular, coordinate lean and rich operation between the banks is utilized. However, termination of rich operation may be different between the banks to prevent breakthrough of rich exhaust gasses due to lack of stored oxidants. In this situation, the bank that terminated rich operation is operated near stoichiometric. This minimizes breakthrough of emissions, while at the same time minimizing a torque imbalance between the cylinder banks. In particular, the torque imbalance can be further minimized by retarding ignition timing on the rich bank while the other operates near stoichiometry. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to umbrellas and more particularly pertains to a new pneumatic umbrella with shell for providing an umbrella which is automatically opened and closed and further forms a shell when closed.
2. Description of the Prior Art
The use of umbrellas is known in the prior art. More specifically, umbrellas heretofore devised and utilized are known to consist basically of familiar, expected and obvious structural configurations, notwithstanding the myriad of designs encompassed by the crowded prior art which have been developed for the fulfillment of countless objectives and requirements.
Known prior art includes U.S. Pat. Nos. 5,235,997, 4,766,920, 4,747,422; 5,224,505; 2,705,967; 2,503,032; 2,224,882; U.S. Patent Des. 361,198, French No. 347,564, and French No. 2,238,448.
In these respects, the pneumatic umbrella with shell according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in so doing provides an apparatus primarily developed for the purpose of providing an umbrella which is automatically opened and closed and further forms a shell when closed.
SUMMARY OF THE INVENTION
In view of the foregoing disadvantages inherent in the known types of umbrellas now present in the prior art, the present invention provides a new pneumatic umbrella with shell construction wherein the same can be utilized for providing an umbrella which is automatically opened and closed and further forms a shell when closed.
The general purpose of the present invention, which will be described subsequently in greater detail, is to provide a new pneumatic umbrella with shell apparatus and method which has many of the advantages of the umbrellas mentioned heretofore and many novel features that result in a new pneumatic umbrella with shell which is not anticipated, rendered obvious, suggested, or even implied by any of the prior art umbrellas, either alone or in any combination thereof.
To attain this, the present invention generally comprises a lower tube, an upper tube slidably coupled with the lower tube and a slider assembly including a slider slidably mounted along the upper tube. Also included is a retractable assembly mounted on the upper tube and connected to the slider of the slider assembly. The retractable assembly has a raised orientation for deploying the retractable assembly and a lowered orientation for retracting the retractable assembly. Also included is a pneumatic extender connected to the slider of the slider assembly for forcing the same to the raised orientation. When the retractable assembly is retracted, the same forms a protective shell about the tubes.
There has thus been outlined, rather broadly, the more important features of the invention in order that the detailed description thereof that follows may be better understood, and in order that the present contribution to the art may be better appreciated. There are additional features of the invention that will be described hereinafter and which will form the subject matter of the claims appended hereto.
In this respect, before explaining at least one embodiment of the invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and to the arrangements of the components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced and carried out in various ways. Also, it is to be understood that the phraseology and terminology employed herein are for the purpose of description and should not be regarded as limiting.
As such, those skilled in the art will appreciate that the conception, upon which this disclosure is based, may readily be utilized as a basis for the designing of other structures, methods and systems for carrying out the several purposes of the present invention. It is important, therefore, that the claims be regarded as including such equivalent constructions insofar as they do not depart from the spirit and scope of the present invention.
Further, the purpose of the foregoing abstract is to enable the U.S. Patent and Trademark Office and the public generally, and especially the scientists, engineers and practitioners in the art who are not familiar with patent or legal terms or phraseology, to determine quickly from a cursory inspection the nature and essence of the technical disclosure of the application. The abstract is neither intended to define the invention of the application, which is measured by the claims, nor is it intended to be limiting as to the scope of the invention in any way.
It is therefore an object of the present invention to provide a new pneumatic umbrella with shell apparatus and method which has many of the advantages of the umbrellas mentioned heretofore and many novel features that result in a new pneumatic umbrella with shell which is not anticipated, rendered obvious, suggested, or even implied by any of the prior art umbrellas, either alone or in any combination thereof.
It is another object of the present invention to provide a new pneumatic umbrella with shell which may be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide a new pneumatic umbrella with shell which is of a durable and reliable construction.
An even further object of the present invention is to provide a new pneumatic umbrella with shell which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such pneumatic umbrella with shell economically available to the buying public.
Still yet another object of the present invention is to provide a new pneumatic umbrella with shell which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
Still another object of the present invention is to provide a new pneumatic umbrella with shell for providing an umbrella which is automatically opened and closed and further forms a shell when closed.
Even still another object of the present invention is to provide a new pneumatic umbrella with shell that includes a lower tube, an upper tube slidably coupled with the lower tube and a slider assembly including a slider slidably mounted along the upper tube. Also included is a retractable assembly mounted on the upper tube and connected to the slider of the slider assembly. The retractable assembly has a raised orientation for deploying the retractable assembly and a lowered orientation for retracting the retractable assembly. Also included is a pneumatic extender connected to the slider of the slider assembly for forcing the same to the raised orientation. When the retractable assembly is retracted, the same forms a protective shell about the tubes.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be made to the accompanying drawings and descriptive matter in which there are illustrated preferred embodiments of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings wherein:
FIG. 1 is a side view of a new pneumatic umbrella with shell according to the present invention.
FIG. 2 is a side view of the present invention in a retracted orientation.
FIG. 3 is a top view of the present invention in a deployed orientation.
FIG. 4 is a side view of the present invention.
FIG. 5 is a side cross-sectional view of the tubes and slider assembly of the present invention, wherein the slider assembly is in a deployed orientation.
FIG. 6 is a side cross-sectional view of the tubes and slider assembly of the present invention, wherein the slider assembly is in a retracted orientation.
FIG. 7 is a detailed cross-sectional view of the slider assembly locked within the raised orientation by the plungers.
FIG. 8 is a detailed cross-sectional view of the tubes locked with respect to each other in the extended orientation.
FIG. 9 is a detailed cross-sectional view of the handle and pressurized air generator of the present invention.
FIG. 10 is a top cross-sectional view of the upper tube and slider assembly of the present invention taken along line 10 — 10 shown in FIG. 5 .
FIG. 11 is a top cross-sectional view of the lower tube and slider assembly of the present invention taken along line 11 — 11 shown in FIG. 6 .
DESCRIPTION OF THE PREFERRED EMBODIMENT
With reference now to the drawings, and in particular to FIGS. 1 through 11 thereof, a new pneumatic umbrella with shell embodying the principles and concepts of the present invention and generally designated by the reference numeral 10 will be described.
The present invention, designated as numeral 10 , includes a lower tube 12 with a hollow cylindrical configuration having a first diameter. A pair of diametrically opposed slits are formed in the lower tube and extend along a length thereof. As shown in FIG. 11 and similar to that shown in FIG. 10, one of the side edges of each of the slits has a resilient lip extending therefrom for covering the associated slit. As such, the lower tube is maintained sufficiently air tight. The lower tube has a bottom end with a hollow cylindrical handle 14 mounted thereon. This handle is equipped with a plurality of concentric undulations formed in an outer surface thereof. Further, a top end of the lower tube has an inwardly extending annular lip 16 formed in an inner surface thereof.
Next provided is an air pressure generator 18 positioned within the handle for reasons that will soon become apparent. The air pressure generator has a push button 20 mounted on the outer surface of the handle. This button serves for excreting air from the handle and into the lower tube upon the depression thereof. To accomplish this purpose, the air pressure generator preferably includes a blower with a motor attached, but may take the form of any type of apparatus for generating pressurized air such as a pressurized carbon dioxide tank or the like.
Associated with the lower tube is an upper tube 22 with a hollow cylindrical configuration. The upper tube has an inner surface with a second diameter less than the first diameter and an outer surface with a third diameter greater than the first diameter. Similar to the lower tube and as shown in FIG. 10, the upper tube has a pair of diametrically opposed slits 24 formed therein with resilient lips 26 which maintain the upper tube air tight. Ideally, the lips 26 abut the opposing half of the tube to afford the foregoing seal.
The upper tube further has a concentric recess 28 formed between the inner surface and the outer surface of the upper tube. Such concentric recess extends between a central extent of the upper tube and a lower end of the upper tube. As shown in FIGS. 5 & 8, the lower end of the upper tube has an inwardly extending annular flange 30 coupled to the inner surface of the upper tube. An outwardly extending annular flange 32 is mounted within the concentric recess. Note again FIGS. 5 & 8. For reasons that will soon become apparent, an outwardly extending annular stop 34 is formed on the outer surface of the upper tube.
In use, the top end of the lower tube is slidably received within the concentric recess between a retracted orientation shown in FIG. 6 and an extended orientation shown in FIG. 5 . In the extended orientation, the outwardly extending annular flange of the upper tube remains in engagement with the inwardly extending annular lip of the lower tube. Further, the slits of the upper tube and the lower tube remain in alignment. This may be accomplished by a slot and groove combination or the like.
Also included is a slider assembly 38 having a hollow cylinder 40 slidably mounted along the outer surface of the upper tube. The cylinder of the slider assembly includes a pair of radially spaced tangs 42 extending outwardly therefrom at an upper edge thereof. Next provided is a piston 44 slidably positioned within the upper tube with a pair of diametrically opposed arms 48 coupled thereto and extending therefrom through the slits of the tubes. Such arms are coupled to an inner surface of the hollow cylinder for moving coincidentally therewith. As the arms pass through the tubes, the aforementioned lips 26 are biased outwardly only slightly to allow minimal loss of air within the tube. Ideally, the arms have an L-shaped cross-section for affording an optimal seal of the associated tube. Note FIG. 10 . In use, the plunger is prevented from leaving the upper tube by the inwardly extending flange. Mounted on an upper end of the upper tube is a cap 50 . It should be noted that the upper tube may be sealed by any desired means.
FIGS. 1-4 show a canopy assembly 52 including a plurality of radially spaced upper inboard arms 54 hingably coupled at inboard ends thereof to the cap and extending outwardly therefrom. A plurality of lower inboard arms 56 with lengths greater than that of the upper inboard arms are also provided. Such lower inboard arms 56 are pivotally coupled at inboard ends thereof to the tangs of the cylinder of the slider assembly. The lower inboard arms are further pivotally coupled at central extents thereof to outboard ends of the upper inboard arms. As bests shown in FIG. 4, a plurality of intermediate arms 60 have inboard ends pivotally coupled to the upper inboard arms.
The canopy assembly further includes a plurality of uniquely designed metal or plastic outboard arms 62 each pivotally coupled to outboard ends of the intermediate arms and the lower inboard arms. The outboard arms are each constructed from a resilient material and have an outer surface with an arcuate lateral cross-section and an inner surface with a similar arcuate lateral cross-section. A pair of side edges of the outboard arms are corrugated with a plurality of cut outs 64 of any shape.
The canopy assembly further includes flexible elastic sheet 66 mounted on the arms for defining a hemispherical configuration when the cylinder of the slider assembly is in a raised orientation. When the cylinder of the slider assembly is in such orientation, the outboard ends arms of the canopy assembly are biased to form an arcuate configuration. Upon the cylinder of the slider assembly being in a lowered orientation, the side edges of the outboard arms straighten out and interlock to define a cylindrical shell 68 which encompasses the tubes in concentric relationship.
Also included is a pair of diametrically opposed spring biased plungers 70 . As shown in FIGS. 4-7, the plungers are mounted within the upper tube between the inner surface and the outer surface thereof. In use, the plungers extend radially outward from the tubes. Ideally, the plungers are spring loaded transducers of electromagnetic solenoids adapted to retract only upon the receipt of an activation signal.
In use, upon the depression of the button of the air generator, pressure forces the piston and the cylinder of the slider assembly to the raised orientation. Ideally, the air pressure generated and the seal within the tubes is sufficient enough to raise the plunger into the upper tube. When raised, the cylinder of the slider assembly is locked in place via the spring biased plungers. Further, the aforementioned pressure forces the tubes to transfer to the extended orientation. The umbrella is thus ready for use as shown in FIG. 4 .
Upon the sliding of the cylinder of the slider assembly to the raised orientation, a pressure builds between the cap and the piston. The purpose of this pressure is two-fold one of which is to damp the upward movement of the plunger and cylinder of the slider assembly. This pressure and the elastic material of the sheet further serve to force the cylinder of the slider assembly to the lowered orientation upon release of the cylinder of the slider assembly by the spring biased plungers. It should be noted that the slits of the tubes allow the pressure within the upper and lower tubes to equalize shortly after deployment of the canopy thereby ensuring that the pressurized air between the plunger and the cap and the elasticity of the sheet is capable of retracting the canopy assembly. When desired, the release of the plungers may be accomplished by positioning a button and battery adjacent the plungers or on the handle with a coiled wire or radio transceiver for communicating the aforementioned activation signal. It should be noted that retraction of the lower tube into the upper tube may be effected in several ways such as manual retraction, reversal of the air generator within the handle, or any other method. It should be noted that in other embodiments, the concepts of the present invention may be applied to satellite reflectors and the like. Other drive mechanisms such as hydraulic, motorized, or electromagnetic systems may be used to mechanize the present invention. Further options include a combination lock or the like and additional spring loaded plungers for keeping the upper and lower tubes extended.
As to a further discussion of the manner of usage and operation of the present invention, the same should be apparent from the above description. Accordingly, no further discussion relating to the manner of usage and operation will be provided.
With respect to the above description then, it is to be realized that the optimum dimensional relationships for the parts of the invention, to include variations in size, materials, shape, form, function and manner of operation, assembly and use, are deemed readily apparent and obvious to one skilled in the art, and all equivalent relationships to those illustrated in the drawings and described in the specification are intended to be encompassed by the present invention.
Therefore, the foregoing is considered as illustrative only of the principles of the invention. Further, since numerous modifications and changes will readily occur to those skilled in the art, it is not desired to limit the invention to the exact construction and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | An umbrella is provided including a lower tube, an upper tube slidably coupled with the lower tube and a slider assembly including a slider slidably mounted along the upper tube. Also included is a retractable assembly mounted on the upper tube and connected to the slider of the slider assembly. The retractable assembly has a raised orientation for deploying the retractable assembly and a lowered orientation for retracting the retractable assembly. Also included is a pneumatic extender connected to the slider of the slider assembly for forcing the same to the raised orientation. When the retractable assembly is retracted, the same forms a protective shell about the tubes. | 0 |
RIGHTS OF THE GOVERNMENT
The invention described herein may be manufactured, used and licensed by or for the United States Government for Governmental purposes without payment to us of any royalty thereon.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to Multiple Integrated Laser Engagement System ("MILES") type training devices and more particularly to an explosive device simulator system for the miles which responds to devices that generate acoustic signals upon simulated explosion.
2. Description of the Prior Art
The Multiple Integrated Laser Engagement System ("MILES") has revolutionized the way in which armies train for combat. MILES has been fielded with armies of many nations around the world and has become the international standard against which all other Tactical Engagement Simulation ("TES") systems are measured. For the U.S. Army and Marine Corps, MILES is the keystone for their opposing force, free-lay TES Program. It is highly valued in its ability to accurately assess battle outcomes and to teach soldiers the skills required to survive in combat and destroy the enemy.
With MILES, commanders at all levels can conduct opposing force free-play tactical engagement simulation training exercises which duplicate the lethality and stress of actual combat.
The MILES system uses laser bullets to simulate the lethality and realism of the modern tactical battlefield. Eye-safe Gallium Arsenide (GaAs) laser transmitters, capable of shooting pulses of coded infrared energy, simulate the effects of live ammunition. The transmitters are easily attached to and removed from all hand-carried and vehicle mounted direct fire weapons. Detectors located on opposing force troops and vehicles receive the coded laser pulses. MILES decoders then determine whether the target was hit by a weapon which could cause damage (hierarchy of weapons effects) and whether the laser bullet was accurate enough to cause a casualty. The target vehicles or troops are made instantly aware of the accuracy of the shot by means of audio alarms and visual displays, which can indicate either a hit or a near miss.
The coded infrared energy is received by silicon detectors located on the target. In the case of ground troops, the detectors are installed on webbing material which resembles the standard-issue load-carrying lift harness. Additional detectors are attached to a web band which fits on standard-issue helmets. For vehicles, the detectors are mounted on belts which easily attach to the front, rear, and sides. The detectors provide 360 degree coverage in azimuth and sufficient elevation coverage to receive the infrared energy during an air attack. The arriving pulses are sensed by detectors, amplified, and then compared to a threshold level. If the pulses exceed the threshold, a single bit is registered in the detection logic. Once a proper arrangement of bits exists, corresponding to a valid code for a particular weapon, the decoder decides whether the code is a near miss or a hit. If a hit is registered, a hierarchy decision is then made to determine if this type of weapon can indeed cause a kill against this particular target and, if so, what the probability of the kill might be.
While great success has been enjoyed with weapons that can be aimed there has been no convenient or economic way for the military to train with grenades that interact with the MILES system. This is because a grenade rotates during its ballistic flight path and would require several laser emitters so that at least one would be pointed at a target. However, even a large number of emitters would not assure a hit. Due to these difficulties, no grenade exists that interacts with the present MILES system. Consequently, there is a great need to find a way in which grenades and other ballistic or variable-directional flight path type weapons can be used in training exercises with MILES.
SUMMARY OF THE INVENTION
Accordingly, it is an object of the present invention to provide a MILES simulator system that interacts with variable-directional weapons such as grenades.
It is another object of the present invention to provide a variable-directional weapon simulator system that interacts with MILES without having to radically change the MILES.
It is still another object of the invention to provide a variable-directional weapon simulator system that interacts with MILES in an economical and efficient way.
The present invention achieves these objectives by using a predetermined acoustic signal to simulate an explosion in combination with receiver circuitry sensitive to the acoustic signal and operatively connected to the existing MILES power supply. A special feature, commonly referred to as the tampering circuit, presently incorporated in the MILES provides for an audible alarm to be activated upon removal and reinsertion of the MILES power source. This feature prevents someone from cheating by deactivating his MILES receiver during simulated combat. When the power source (typically a battery) is reinstalled an audible alarm is sounded. Consequently, by momentarily removing the MILES power source from the circuit for a brief instant and then reconnecting it back into the circuit the present invention is able to indicate a kill on MILES. This operation is performed when receiver circuitry detects a predetermined acoustic signal of sufficient amplitude and duration or can even be a coded acoustic signal. An acoustic signal overcomes the disadvantage of highly directional laser pulses because of its substantially omnidirectional propagation characteristics.
Consequently, a grenade, or other variable-directional explosive type device, that incorporates a sonic device or buzzer will be able to interact with the MILES that have been fitted with the present invention. The use of a pull pin and switch arrangement provides soldiers with a realistic grenade for use in training operations. An optional "safety" lever pivotally attached to the grenade can be used to hold the switch open and provide realistic operation. A grenade that generates an audible signal is described in a copending application, Ser. No. 07/608,923, entitled "TRAINING GRENADE" and is assigned to same assignee, the U.S. Government, as in this case.
The acoustic signal generated by the grenade is detected by receiver circuitry located and operatively connected to the power supply source for the MILES. The operational sequence of the simulator system is as follows. When a grenade is activated there is approximately a three second delay before a flash bulb fires. A flash may be used to provide a visual means for indicating that an explosion has occurred but, it is not essential. A delay is also advantageous so that the thrower does not activate his own receiver circuitry. After the flash fires a buzzer sounds for approximately three seconds. Obviously, other time periods may be selected. A means for detecting the acoustic signal, for example a microphone, is located on each target which has been fitted with a MILES. Targets can be vehicles, soldiers, buildings, etc. The microphone that detects the sound generated by the grenade is connected to receiver and identification circuitry. The output of the receiver is used as a trigger signal to momentarily remove the MILES power source from the rest of the MILES circuit. This results in the MILES audible alarm being activated.
The present invention is not limited to using a grenade. Various training devices, particularly ones that have variable-directional flight paths, can be designed to generate a predetermined audible signal simulative of an explosion. However, the present disclosure will primarily be directed towards the use of an audible grenade and its interaction with the simulator receiver circuitry.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, aspects, uses and advantages of the present invention will be more fully appreciated as the same becomes better understood when considered in connection with the following detailed description of the present invention and in conjunction with the accompanying drawings, in which:
FIG. 1 shows a cross sectional view of a training grenade that can be used to generate an acoustic signal according to an aspect of the invention.
FIG. 2 shows an electrical schematic diagram of a training grenade as depicted in FIG. 1.
FIG. 3 shows an electrical schematic diagram of a basic embodiment of the receiver circuitry according to an aspect of the invention.
FIG. 4 shows a partial electrical schematic diagram of decoding circuitry as added to the circuitry as shown in FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawings, like reference numerals represent identical or corresponding parts throughout the several views. Before a description is given on the receiver circuitry a description of an audible grenade of the type that can be used in the present invention will be described.
A cross sectional view of a grenade 100, having a barrel shape as used in many fragmentation grenades, is shown in FIG. 1. The housing 102 may be made from a transparent or translucent, synthetic, flexible or shock resistant material. The grenade 100 contains a power supply or standard 9 volt battery 104 to power an electronic circuit mounted on circuit board 106 which fires a light emitting device 108 which then triggers a buzzer 110. Obviously, the grenade 100 need not be transparent nor translucent if a flash bulb is not used. If a flash bulb is used it illuminates the translucent housing 102 of the grenade 100. The light emitting device 108 could be, for example, a common type camera flash bulb such as a Sylvania Blue Dot, a light emitting diode, or a xenon flash beacon. Removing the pull ring 112 and safety pin 113 causes a phone type switch 114 to close, thereby providing power to the circuit.
The electronic circuit mounted on circuit board 106 is shown in schematic form in FIG. 2 and comprises a phone type switch 114, a flash bulb 108, a buzzer 110, and activation means 116. The activation means 116 comprises battery 104, a timing means 118 which may comprise a resistor 120 (R1), resistor 122 (R2) and capacitor 124 (C1) network, and a Motorola MC1455 monolithic timing circuit 126. Upon removal of the safety pin 113, by pulling on a safety pin pull ring 112, the switch 114, in series combination with battery 104, closes. The removal of the safety pin 113 starts the charging of timing means 118 within the activation means 116. After approximately a three second delay the flash bulb 108 is fired. This causes the buzzer 110 to sound for approximately three seconds thereby simulating the spread of fragments.
FIG. 3 shows a schematic of the receiver or MILES interface circuitry which comprises a quad operational amplifier (LMC 660) 200, a phase lock loop (LM 567) 202, a timer circuit (MC 1455G) 204, a microphone 206 and various discrete components. A rechargeable power section 201 provides voltage to the applicable circuitry. All of the functions performed by the receiver circuitry are accomplished using conventional, off the shelf, components with values shown as merely exemplary of an operational device.
When an acoustic signal is received from an acoustic training device, such as the grenade previously described, the signal is detected by the microphone 206. A conventional hearing aid may be used as the microphone 206. The output of the microphone 206 is fed to the quad amplifier 200. The quad amplifier 200 is configured as two cascaded bandpass filters followed by an active high pass filter. The filters are frequency adjusted to center around the emitting frequency of the acoustic training device and to amplify the microphone output. The output (pin 8) of the quad amplifier 200 is fed to the input (pin 3) of phase lock loop 202. The phase lock loop 202 is configured as a narrow band tone detector. The output (pin 8) of the phase lock loop 202 goes low when a signal of the proper frequency is presented to the input (pin 3) of the phase lock loop 202. The output (pin 8) of the phase lock loop going low causes the base on transistor 208 to go low which allows capacitor 210 to charge. If the output (pin 8) of the phase lock loop 202 stays low long enough for capacitor 210 to charge beyond a set threshold, power supplied (by pin 3) to the MILES through timer 204 is removed. The MILES is thus supplied power through the output of timer 204 in place of the normal battery in the MILES. Power remains removed from the MILES until the acoustic signal is no longer received from the acoustic training device. When the acoustic signal is no longer being received power is restored to the MILES and the tampering circuit activates an internal audible alarm indicating a "hit" has taken place. Recall that the audible alarm is activated if the power to the MILES is momentarily removed and then reconnected.
Another embodiment of the present invention is shown in FIG. 4 and includes an additional phase lock loop 212. An additional phase lock loop provides for receiving coded pulse modulated signals transmitted from the acoustic training device. Only that portion of the circuit centered around the additional circuitry is shown. The remaining portion is identical as provided in FIG. 3.
The circuity preceeding the input (pin 3) of phase lock loop 202 remains the same as shown in FIG. 3. The input signal comes from the quad amplifier 200. The output (pin 8) of phase lock loop 202 goes high and low at the pulse modulation rate of the acoustic training device. A second phase lock loop 212 is inserted between phase lock loop 202 and transistor 208 and acts as a tone decoder that only locks on to a signal at the modulation frequency. The output (pin 8) of phase lock loop 212 goes low when an acoustic signal of the right frequency and modulation rate is received. The remaining portion of the circuit is identical and operates as that shown in FIG. 3.
Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. | An acoustic receiver for interfacing indirect-fire weapons with the Multi Integrated Laser Engagement System ("MILES") responds to the presence of a device when the device generates a predetermined acoustic signal upon simulated explosion. The simulator then momentarily disconnects the MILES power supply from the rest of the MILES circuit. This action causes the MILES to generate an audible alarm indicating a hit by the explosive device. | 5 |
BACKGROUND OF THE INVENTION
Advanced Process Control (APC) and Multivariable Predictive Control (MVPC) are considered established technologies in the large scale processing and power industries with a plethora of published material, e.g. Qin S. Joe and Thomas A. Badgwell, “An Overview of Industrial Model Predictive Control,” AIChE Conference, 1996, J. A. Rossiter, “Model-Based Predictive Control: A Practical Approach,” 2003 and Eduardo F. Camacho and Carlos Bordons, “Model Predictive Control,” 2007.
Recently a lot of attention was paid to optimal operation of multi-unit plants, e.g. a white paper by Honeywell, “Optimization Solution White Paper: an Overview of Honeywell's Layered Optimization Solution”, 2009, and another white paper by ABB, “Lifecycle Optimization for Power Plants,” 2004, followed by ABB's news release in 2012 titled “Life cycle management and service”. Additionally, IBM has been promoting its Smarter Planet for energy and utilities, see, for example, white paper, “The State of Smarter Energy and Utilities,” 2010.
As equipment performance, production demands, and process and ambient conditions all fluctuating, determine the optimal operating mode across multi-unit plants are complicated. Control and data acquisition systems provide an extensive quantity of process data. However, the multidimensional analysis required to achieve optimal operation are often beyond human ability.
Some of the challenges addressed in these publications are the inefficiencies existing in current large scale processing and power generation providers and the need for holistic control, not just geared towards specific units, but for the entire plant operation or even a plant network, involving multi-unit designs, which ultimately provides optimal process operation.
Examples of multi-unit plants in large scale processing and power industries include:
Oil field operations with a large number of surface pumping units, oil pipe line networks, well test gathering stations, and storages. Gas and oil pipeline networks, equipped with a large number of pumping stations and pumping units. Steam flood operations with a large number of steam generating stations and steam generators. Hydrocarbon processing plants. Power Generation plants equipped with gas/steam turbine driven generators, heat recovery steam generators, and boilers. Power distribution network with a large amount of electrical producers and consumers. Water treatment plants and water distribution network.
The benefits of APC/MVPC (with basic foundations described well in U.S. Pat. No. 5,740,033 issued on April 1998 to Wassick et al. as well as U.S. Pat. No. 5,519,605 issued on May 1996 to Cawlfield) systems implementation into multi-unit plants include the following:
Assistance in achieving optimal operation by accurately responding to real time demands and limitations. Process optimization to reduce energy consumption in meeting delivery commitments. Enhancing companies' ability to manage data and make better operating and prospecting decisions. Improving process stability, allowing operation closer to target, constraint and optimum values. Forecasting, process simulation, determining the ability to meet obligations.
The large scale processing and power industries exhibit high demand for a decision support system that encompasses all of the above automation functions for plant networks, that is loaded with the state-of-the-art algorithms and models, and that is ultimately able to effectively communicate its performance and recommendations to decision makers throughout the organization. The current invention is the cost effective solution to this demand.
SUMMARY OF THE INVENTION
A system and method of Advanced Process Control for optimal operation of multi-unit plants in large scale processing and power generation industries is provided. The disclosed invention consists of continuous real time dynamic process simulation running in parallel to real process, automatic coefficient adjustment of dynamic and static process models, automatic construction of transfer functions, determination of globally optimal operating point specific to current conditions, provision of additional optimal operating scenarios through a variety of unit combinations, and calculation of operational forecasts in accordance with planned production.
All components of the invention, including forecasting, simulation, control, and optimization, rely heavily on process model accuracy. The disclosed process model is a set of differential and algebraic equations, which describes and solves representations of a large scale technological process. In other words, the process model is a combination of material and energy balances, which are statements on conservation of mass and energy, respectively. These models represent functional dependencies between highly interconnected (both linearly and nonlinearly) multiple inputs, multiple outputs and multiple losses and are used by the optimization applications for finding, recommending, and deploying improvements of the process.
The first major component of the disclosed invention is the Continuous Real Time Dynamic Process Simulation. Its objective is to create a virtual process that can be investigated or manipulated. The benefits of having such simulation are described well in U.S. Publication No. 2007/0168057 A1 published in July 2007 by Blevins et al. The uniqueness of the proposed invention lies in the method and apparatus for accomplishing this for large scale multi-unit systems. Process simulation occurs concurrently with process operation and reflects process dynamics. First, it is used to compare simulated and measured variables in order to determine model accuracy and adjust model's coefficients. Second, it is a cost effective method of determining transfer functions, discussed below, that avoids costly step testing. Because of high degree of accuracy of process models, the dynamic simulation accurately represents the process and can include all the major control loops; thus, it becomes possible to verify behavior of various events at initial system design and to analyze occurring transient processes.
The second major component of the disclosed invention is the Automatic Coefficient Adjustment across all static and dynamic process models. The need to adjust model coefficients exists whenever process changes occur, driven either by ambient event occurrences, equipment failure or changes in operational demand. This is well described in U.S. Pat. No. 6,826,521 issued in November 2004 to Hess et al. What makes this invention unique is that model coefficients are adjusted in online mode, depending on severity of process changes. Static models are described by algebraic equations, which are second, or fourth order polynomials acquired through ordinary least squares or partial least squares methods. Dynamic models are described by differential equations. The polynomial and dynamic models coefficients are adjusted automatically using particle filters, also known as Sequential Monte Carlo (SMC) methods, which are model estimation techniques based on simulation. The criteria for models coefficient adjustment is based on the comparison of the current measured process variables values with its simulated value.
The third major component of the disclosed invention is the Automatic Transfer Function Generation. A transfer function is a relationship between input and output signals within a system. The proposed optimization module empirically generates input/output transfer functions using data obtained from the simulated open-loop steps performed on the current model structure. For control purposes, transfer functions are described by first order plus time delay form, described in detail below. The proposed invention accommodates for various structural forms of transfer functions including parallel, in series, and combination input/output designs. In particular, transfer functions are automatically generated when system input is an ambient process disturbance.
The fourth major component of the disclosed invention is the Operating Mode Optimization. The optimization system uses automatically generated transfer functions to find the optimal mode based on the given optimization criteria. Standard optimization techniques, such as branch and bound, are used to find the global optimum. For differentiable process models, the partial derivatives are computed in domain and the objective function values are recorded. At the plant level, the optimization problem is solved either by unit shut down/start up or unit load sharing. The criteria for optimal load sharing is based on the comparison of the current objective function value with its value computed using the static model after the planned change in loads. Further reference to benefits of optimizing operational processes is well laid out in U.S. Publication No. 2009/0157590 A1 published in June 2009 by Mijares et al. What makes this invention unique is that the optimization system uses automatically generated transfer functions to find the optimal mode.
Finally, the fifth major component of the disclosed invention is Optimal Planning and Scheduling. This capability allows to solve major business problems including sequencing, scheduling of equipment operation, and load distribution over a planned period. The algorithm consists of two steps: finding optimal operating scenario (as a combination of unit start-ups/shut-downs, for example) based on predicted future conditions over an operator defined time horizon and creating an optimal forecast using time series and regression techniques for the same time frame. Ultimately, the best operating mode is suggested given current and future conditions, and is continuously updated based on process changes.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows Large Scale Process Optimization and Optimal Planning Based on Dynamic Simulation Conceptual design.
FIG. 2 shows Plant Optimization and Scheduling System architecture.
FIG. 3 shows the algorithm of the Multi Variable Predictive Controller (MVPC).
FIG. 4 shows supported structure of input/output transfer functions including parallel, in-series, combination, and ambient disturbance elements.
FIG. 5 shows the algorithm of the Real-Time Optimization Module (RTO).
FIG. 6 shows the algorithm of the Scheduling Module.
FIG. 7 shows the algorithm of the Coefficient Adjustment Module.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The invention's conceptual design is shown and described in FIG. 1 . The proposed system mathematically determines static and dynamic characteristics of the real process 11 by creating a concurrent virtual process 13 . This is achieved by building accurate process models via automated coefficient adjustment 12 . At any given point of time, historical information is used for real time simulation 14 to dynamically forecast the process behavior based on the mathematical models. Then, optimization 15 is used to simulate control actions that correspond to optimization criteria. Optimization criteria can be one or a combination of goals, such as least cost, minimum emission, maximum production, or the like. The Optimization and Scheduling Modules determine optimal set-points for all process components across multi-unit plants. Finally, optimal mode is found and either supplied to an operator for manual entry or control actions are executed in real time by the Multi Variable Process Control (MVPC) 16 .
The overall system architecture is described in FIG. 2 . The left hand side of FIG. 2 shows a typical Distributed Control System (DCS) 21 , which comprises an I/O module, logic controllers, and operator stations. An operator 22 uses the graphic workstation (Human/Machine Interface, HMI) 23 , to monitor and control the process 24 . The logic controllers provide the interface with process I/O and execute sequential and regulatory control functions. The data management and gateway functions are distributed on a plant control network 25 to ensure system integrity and timely data transmission. Plant control network 25 connects the Operating and Control levels of the system allowing uninterrupted access to real-time process information, alarms, and events.
Plant Optimization and Scheduling System 26 is installed on separate servers, which are also connected to the plant control network 25 in order to have full access to real time and historical operation data for all production units. Data needed for optimal operation of the Plant Optimization and Scheduling System 26 includes process data, plant-wide equipment conditions, critical operating parameters, and performance conditions. The system utilizes modeled information (described in detail below), real time and historical data to perform optimization and planning functions, and sends set point information to logic controllers. The Plant Optimization and Scheduling System 26 also provides presentation of plant-wide simulation, optimal scenarios, and optimal schedules on operator workstations 23 .
FIG. 3 shows the algorithm of the Multi Variable Predictive Controller (MVPC), which is a simulation-based predictive and optimizing control module capable of handling control problems with multiple independent inputs and with multiple outputs that have significant interactions. The key to successful operation of the MVPC is an accurate process model, which in this case is built as the mass and energy balancing model.
Referring to FIG. 3 , the algorithm starts with the Operator 31 configuring the initial model coefficients 32 , which can be estimated from equipment manufacturer specifications. The Operator 31 also specifies optimization criteria (e.g. maximize revenue or minimize cost), which is provided to the system in terms of an Objective Function 33 and sets the Controlled Variables Set Points (CV SP) 34 . To help the Operator make necessary decisions, the system is equipped with two visual interfaces. One is supplied by the DCS 35 and one is supplied by the MVPC via a built-in Visualization Module 36 . The integrated Visualization Module 36 provides real time content 37 to the Operator 31 and allows the Operator 31 to manage MVPC control actions via a PC-based graphical user interface. More specifically, the Visualization Module 36 diagram displays an operating envelope, showing the location of process operating points in relation to the constraints. The station Visualization Module provides calculations, lookup tables, process real time (RT) capabilities diagrams 37 , and performance testing information.
The MVPC algorithm then proceeds as follows. The Model Construction Module 38 receives real time values of Manipulated Variables (MV), Controlled Variables (CV) and Disturbance Variables (DV) 39 from the DCS 35 . It uses predictive modeling and data mining techniques, such as ordinary least squares regression (OLS), partial least squares regression (PLS), decision trees (DT), and artificial neural networks (ANN) to simultaneously identify static and dynamic process characteristics. The resulting Process Model 310 is a collection of equations in steady-state working conditions that describe the interdependencies between units and process variables.
The static equations are given by standard multivariable formulas in the form
y=f ( x 1 , . . . ,x n )
where y is the dependent variable and x 1 , . . . , x n is a set of independent variables influencing y. In case of OLS, f is usually a polynomial of degree two or four. In case of PLS, f is also characterized by a polynomial, however, x 1 , . . . , x m are now projections of original independent variables (aka factors), with m<n. PLS is often used when highly correlated independent variables are detected. In case of DT, the equation is replaced by “if-then” binning rules of all predictor variables that maximize the explained variability of the target. In case of ANN, the activation functions are characterized by
h
j
=
tanh
(
b
j
+
∑
i
w
ij
x
i
)
where b and w are the estimates/weights and j is the number of hidden units in the network. The dynamic model is a collection of differential equations that describe the process transitional state.
Additionally, the MVPC algorithm also has a built-in process shift detection algorithm (utilizing time series and six sigma techniques) that allows it to identify the severity of process changes so that models can be re-calibrated (i.e. the model coefficients adjusted) either in offline or online modes using real-time and historical data.
The resulting process model is then fed into the Optimization Module 311 and the Visualization Module 36 for monitoring purposes. The Optimization Module 311 also receives real time data from the DCS 35 along with the operator chosen Objective Function 33 and CV SP 34 . Optimization Module 311 uses both steady-state and dynamic modeled information to predict how the process will respond to changes in each of the independent variables. Ultimately, the Optimization Module 311 provides two types of output: adjusted transfer functions 312 (described in detail below), which are generated through online simulation testing of the dynamic model and adjusted objective function 313 , which is the operator provided objective function with optimized coefficients.
The next step of the algorithm loads the Optimization Module 311 output directly into MVPC 314 . In addition, the MVPC 314 receives real time data from the DCS 35 as well as operator provided CV SP 34 . MVPC 314 uses the steady optimal values of Manipulated Variables (MV) as targets and calculates future moves that will maintain the operation at specified targets. The MVPC 314 predicts future changes in controlled variables (CV) and determines past changes in MV and disturbance variables (DV). Then MVPC 314 calculates new changes in MV in order to ensure that targets for CV (CV SP) are reached and account for Operator chosen optimization criteria.
Specifically, the objective function that serves as input to the MVPC algorithm can be described by the following formula:
U (MV 1 , . . . ,MV n ,DV 1 , . . . ,DV m )
The Input/Output transfer functions are described by
W (MV 1 , . . . ,MV n ,DV 1 , . . . ,DV m )
Setting J to be the Time to Steady State, for each j=1, . . . , J transfer functions can be defined by
W j (MV 1 , . . . ,MV n ,DV 1 , . . . ,DV m )
Then the optimization problem can be stated as follows:
(
SPCV
-
∑
i
W
j
(
MV
i
DV
i
)
)
2
->
0
and
U (MV 1 , . . . ,MV n ,DV 1 , . . . ,DV m )→min
Subject to constraints provided by the Operator 31 , which are integrated into the objective function via multipliers. In case of differentiable objective functions (which is often the case with OLS output), the solution (set of optimal MVs) is found at the point where the partial derivatives of the objective function are zero. The algorithm continuously repeats to ensure accuracy of current process representation. Ultimately, the MVPC sends set points 315 to Distributed Control System process controllers 35 .
As displayed in FIG. 3 , one of the key system components is the Model Construction Module 38 . The dynamic models generated by the module can be described by a collection of differential equations that characterize the transitional state of the process. Process simulation is analytically achieved using this set of differential equations. The ultimate goal of process simulation is to determine transfer functions that relate input disturbances to output changes over time. The Real-time Optimization Module (RTO, see FIG. 5 for details) empirically generates Input/Output transfer functions using data obtained from the simulated open-loop step performed on the current dynamic process model.
Specifically, RTO simulates a DV and MV step change test such as DVs and MVs are changed separately to observe the CV response. As most processes tend to be nonlinear, several open-loop step change tests are performed for each variable to obtain the most accurate transfer function. For each individual transfer function, RTO identifies the Time to Steady State, Time Delay, Process Gain, and Time Constant (discussed in detail below). Once the Input/Output transfer function is known, it is possible to predict the system's reaction after any disturbance and at any given time. Also, it is possible to compute the MV value so that the integrated (over time) deviation of CVs from the set point would be minimal.
FIG. 4 shows a variety of transfer functions that can be generated by the RTO. For control purposes, transfer functions are described by first order plus time delay form 41 :
W
(
s
)
=
k
p
ⅇ
-
sv
τ
p
s
+
1
where k p is the process gain, t p is the process time constant, and u is process time delay. The Input/Output transfer function may assume a number of structural forms. First form is Parallel 42 .
CV
=
∑
i
=
1
z
W
i
MV
i
Second form is in series 43
CV 2 =W 1 W 2 MV 1
For systems with more than one output, the Input/Output transfer function has the third combined form 44 , where the outputs are related to the inputs as follows:
CV 1 =W 11 MV 1 +W 22 MV 2
CV 2 =W 12 MV 1 +W 21 MV 2
Processes are influenced by external disturbances, such as changes in ambient conditions, changes in the fuel quality, etc. To accommodate these effects, process disturbances are incorporated into the model with disturbance transfer functions of the fourth form 45 :
CV 1 =W d1 DV 1 +W 11 MV 1 +W 22 MV 2
CV 2 =W d2 DV 2 +W 12 MV 1 +W 21 MV 2
Referring now to FIG. 5 , the Real-Time Optimization Module (RTO) is implemented with the following algorithm. Similar to MVPC, the RTO algorithm starts with the Operator 51 configuring the initial model coefficients 52 . This step can be accomplished as part of the MVPC set up as well. For a given optimization problem, the Operator 51 is also expected to set the Objective Function 53 , the Controlled Variables Set Points (CV SP) 54 as well as the overall Process Set Points 55 . The RTO module also utilizes the Visualization Module available in MVPC and receives visual feedback from the DCS 56 .
The RTO algorithm proceeds similarly to the MVPC algorithm. The Model Construction Module 57 receives real time values of Manipulated Variables (MV), Controlled Variables (CV) and Disturbance Variables (DV) 58 from the DCS 56 and has the same modeling toolkit as the Model Construction Module in the MVPC algorithm.
Next, the Optimization Module 59 uses DCS supplied real time data 58 along with the operator chosen Objective and Constraint Functions 53 , with coefficients provided by the Model Construction Module 57 , and CV SP 54 to optimize the process. The RTO module uses a standard suite of optimization methods to globally optimize the objective function subject to the provided constraints. These methods include, but are not limited to, the following: integer programming, linear programming, mixed integer programming, mixed integer non-linear programming, quasi-Newton method, Nelder-Mead Simplex Method, and Lagrange multipliers (that transform the constrained optimization problem into an unconstrained problem).
Ultimately, RTO calculates the steady optimal values of manipulated variables (MV) and provides these values to the Operator 51 as Suggested Scenarios 510 . These suggested Scenarios 510 may include a number of requests for unit shut-down/start-up as well as unit load sharing strategy. All available optimal scenarios (based on a range of expected future conditions) are relayed to the Operator 51 along with economic assessments that provide support for operating decisions.
FIG. 6 shows the algorithm of the Scheduling Module, which is the key component of the overall system. The Scheduling Module balances production with a range of constraints on daily, weekly, and monthly bases and builds process operating forecast in accordance with planned production and consumption. The Scheduling Module integrates with the other components of the system in a fashion similar to MVPC and RTO modules.
Referring now to FIG. 6 , the first step requires the Operator 61 to provide information necessary for the schedule to be created. This information is the initial model coefficients 62 , the function to be optimized along with its constraints 63 , CV SP and DV forecast (demand, for example) 64 , and the overall Process Set Points 65 . To help assist in decision making, the Operator 61 also has access to the MVPC Visualization Module and the DCS Visualization Module 66 .
During the second step, the Model Construction Module 67 receives real time values for all MVs, CVs and DVs 68 from the DCS 66 and builds models using the same modeling toolkit available in the MVPC and RTO modules.
For the third step, the Optimization Module 69 uses the operator chosen Objective and Constraint Functions 63 with coefficients 610 provided by the Model Construction Module 67 along with demand predicted by the Scheduling Module 611 to find optimal scenarios within an operator defined time period. As described above, for each defined time period, the RTO provides optimal MV values to the Operator as well as to the Scheduling Module 611 as a set of Suggested Scenarios 612 , which include unit shut down and start-up requests as well as load sharing strategies.
During the fourth step, the Scheduling Module 611 employs genetic algorithms to find optimal solutions to efficient operating mode problems as well as forecast parameter search problems. The Scheduling Module 611 evaluates the fitness of each Suggested Scenario 612 according to following criteria:
objective function is satisfied while none of the constraints are violated; number of requests for unit shut down/start-up is minimal and satisfies shut down/start-up limits; controlled variables meet predicted demand; and most profitable and optimal operation is ensured.
This algorithm repeats and updates itself until incremental improvements are no longer financially viable. Finally, the Scheduling Module 611 provides the optimal schedule and forecast 613 to the Operator 61 .
Referring now to FIG. 7 , the model Coefficient Adjustment module is implemented with the following algorithm. Each real time input signal 72 provided by the DCS/Process 71 via OPC Connectivity 73 is regarded as a measurable variable 74 . Each measurable variable 74 is filtered by a one-dimensional filter 75 , using any one of the standard signal processing techniques including Kalman filters, exponential smoothing, and auto-regressive models among others.
The smoothed measured process variables 76 are fed into the Data Justification Module 77 . The module rejects data points (outliers) whenever they fall beyond a specified distance from expected model values or whenever user-defined criteria is exceeded. The output of the Data Justification Module 77 is the set of all accepted measured process variables values (MV) 78 .
Process simulation occurs concurrently with the live process. Information about current operating mode 79 is fed into Online Simulation Module 710 which also receives Baseline Plant Model's 711 current coefficients 712 . Of note, the Baseline Plant Model 711 coefficients 712 are created by the Configurator/Operator 713 supplied Manufacturer data 714 . Online Simulation Module 710 provides simulated process variables (SV) 715 for every time scan corresponding to measured variable values 78 .
The ultimate goal of the algorithm is to automatically adjust process model coefficients to reflect current operating mode and ensure model accuracy at any given time. The algorithm uses particle filtering methods that are based on dynamic state space models described by the following set of equations:
{
x
t
=
f
(
x
t
-
1
)
y
t
=
g
(
x
t
)
where f and g are estimated using polynomial regression, x t is a vector of state parameters at time t and y t are observed (measured) variables. Then x t is estimated using sequential importance sampling or sequential Monte Carlo sampling (from a simulated distribution), with general concepts of such simulation described well in A. Doucet et al, “Sequential Monte—Carlo Methods in Practice”, Springer—Verlag, 2000.
Referring back to FIG. 7 , the difference between the smoothed measured variable value and its corresponding simulated variable value dP 716 is minimized using the OLS method of fitting above mentioned function g. Effectively, the algorithm iteratively changes the sample weights such that the following occurs:
dP
=
∑
t
=
1
N
(
y
t
-
g
(
x
t
)
)
2
->
min
The coefficients of function are thus adjusted by the module 717 to reflect the most accurate relationship between the simulated variable values and the measured variable values. The adjusted coefficients 718 are provided to the Plant Model 719 and overall algorithm repeats whenever process changes occur. | This invention provides a system and method of Advanced Process Control for optimal operation of multi-unit plants in large scale processing and power generation industries. The invention framework includes the following components: continuous real time dynamic process simulation, automatic coefficient adjustment of dynamic and static process models, automatic construction of transfer functions, determination of globally optimal operating point specific to current conditions, provision of additional optimal operating scenarios through a variety of unit combinations, and calculation of operational forecasts in accordance with planned production. | 6 |
FIELD OF THE INVENTION
The invention is related to polyurethane adhesives which may be used in applications which of necessity dictate the use of materials having good heat transfer properties, compatibility with foam insulation, and a relative insensitivity to temperature changes between -20° F. and 230° F.
BACKGROUND OF THE INVENTION
Urethane adhesives are known in the art. U.S. Pat. No. 4,318,837 describes a urethane adhesive composition consisting of 100 parts of a saturated polyester and 5 to 150 parts of unsaturated a polyester containing 5 to 15 parts of an organic polyisocyanate, which is suitable for adhering wood to vinyl film. U.S. Pat. No. 4,323,491 discloses a urethane adhesive composition comprising a prepolymer of polydiethylene glycol adipate and tolylene diisocyanate, polyisocyanate, trichloroethylphosphate, and a mixture of water, urea, and sodium sulphoricinate, the object being to upgrade the strength of an adhesive joint at negative temperatures and reduce the reactive volatile components in the adhesive composition. U.S. Pat. No. 4,698,408 discloses a two component adhesive system comprising a mixture of an isocyanate prepolymer and a polyepoxide and a mixture of a polyol, a urethane curing catalyst and an epoxy curing catalyst, the stated advantages of such a system being significantly improved high temperature thermal stability and immediate nonsagging behavior. U.S. Pat. No. 4,748,781 describes a method of bonding structural support channels to a panel using a polyurethane adhesive foam which among other advantages provides resistance to heat flow.
BRIEF SUMMARY OF THE INVENTION
This invention relates to a urethane adhesive. More particularly this invention relates to a urethane adhesive which has good heat transfer properties and thermal stability between about -20° F. and about 230° F., and a method of bonding cooling/condensing coils or tubes to metal walls of a refrigerator.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings, FIG. 1 illustrates a general structural diagram of a refrigeration cabinet 10 as described in the present invention having an outer cabinet 14, and an inner wall 12. Attached to the inside wall of the outer cabinet 14 are the condensing coils 16.
Referring now to FIG. 2, a cut-away view of the refrigeration cabinet 10. The condensing coils 16 are attached to the outer cabinet 14 by the urethane adhesive 20 which comes in intimate contact with both the outer cabinet 14 and the insulating urethane foam 18.
Today's changes and advances in refrigerator design have necessitated the development of an improved means of fastening cooling/condensing coils or tubes to surfaces within the cabinet of the refrigeration unit itself. Previously the condensing coils were located at the rear of the cabinet on the outside. New designs attach the condensing coils along the inside wall of the outer cabinet. The coils are between the cabinet wall and the insulating urethane foam. This design requires a means of attachment which will provide as little impediment to heat transfer between the coils and the cabinet as possible. Furthermore, the means of attachment must be compatible with the insulating foam and exhibit good thermal stability between about -20° F. and about 230° F. Adhesives currently used for freezer cabinets are materials that have poor temperature stability and retard heat flow. The urethane adhesives of the present invention display good adhesion at high and low temperatures, good heat transfer properties and are compatible with present urethane insulating foams.
The adhesives used in the present invention are prepared using known techniques. Isocyanates are reacted with a polyol-containing resin in the presence of a catalyst. The adhesive formulation itself, comprises;
a) a polyol selected from the group comprising polyoxyethylene/polyoxpropylene block copolymers, polyoxypropylene adducts of an alkylene radical having at least two isocyanate reactive hydrogens, a polyethylene terephthalate based aromatic polyester polyol or mixtures thereof,
b) an isocyanate in which all the isocyanate groups are aromatically bound,
c) a water scavenger,
d) a catalyst capable of promoting urethane formation, and
e) optionally a chain extender and plasticizer.
Suitable polyoxyethylene/polyoxpropylene copolymers and polyoxypropylene adducts are polyether polyols having a functionality of at least two. These polyether polyols are produced in accordance with well known methods by reacting one or more alkylene oxides with 2 to 4 carbon atoms in the alkylene radical with initiator molecules containing from 2 to 8 reactive hydrogen atoms. Suitable alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide. Initiator molecules are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,2-butane diol, 1,3-butane diol, 1,4-butane diol, 1,2-pentane diol, 1,4-pentane diol, 1,5-pentane diol, 1,6-hexane diol, 1,7-heptane diol, glycerol, 1,1,1-trimethyol propane, 1,1,1-trimethyol ethane, 1,2,6-hexane triol, o-methyl glucoside, pentaerythritol, sorbitol, and sucrose. Other initiator molecules include amines such as trialkanolamine, triethanolamine, triisopropanolamine, aliphatic, cycloaliphatic and aromatic diamines with 2 to 15 carbon atoms such as ethylene diamine, 1,3-propanediamine, propylene diamine 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-diaminocyclohexane, 4,4'-2,4' and 2,2'-diaminodiphenylmethane.
The polyethylene terephthalate based aromatic polyester polyols used in the instant invention may be obtained from a variety of waste materials, such as used photographic films, X-ray films, and the like; synthetic fibers and waste materials generated during their manufacture; used plastic bottles and containers such as the soft plastic beverage containers now widely used by the soft drink industry; and waste materials from the production of other products made from polyalkylene terephthalate polymers. These waste materials are digested and reacted with suitable polyols. The complete method for preparing these polyester polyols is disclosed in U.S. Pat. No. 4,701,477 which is incorporated herein by reference.
Suitable isocyanates include those in which the isocyanate groups are aromatically bound. Representatives of these types of isocyanates includes, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate (MDI), mixtures of 4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate and 3,3'-dimethyldiphenyl methane-4,4'-diisocyanate; and polymeric polyisocyanates such as polymethylene polyphenylenes polyisocyanates (polymeric MDI). Included within the useable isocyanates are those modifications containing carbodiimide, allophonate, urethane or isocyanurate structures. Unmodified polymeric MDI and mixtures of polymeric MDI and pure 2,4 and 4,4' MDI and carbodiimide modified MDI are preferred. These polyisocyanates are prepared by conventional methods known in the art, e.g. phosgenation of the corresponding organic amine.
Water scavengers are a necessary part of the invention. Suitable scavengers include molecular sieves and zeolites. Zeolites are preferred. The zeolites used in the present invention are crystalline aluminosilicates, composed of silica and alumina in various proportions plus metallic oxides. They are produced by hydrothermal treatment of a solid aluminosilicate or of a gel obtained by the reaction of sodium hydroxide, alumina hydrate and sodium silicate. The initially obtained product, or a naturally occurring analog, may be partially ion-exchanged to introduce other cations. The preferred zeolites of the present invention are potassium analogs in the form of a paste with the carrier being castor oil. Baylith Paste and Zeolite Paste are examples of the preferred zeolite.
Any suitable catalyst or mixture of catalysts may be used including tertiary amines such as for example, triethylenediamine, N-methylmorpholine, N-ethylmorpholine, diethylethanolamine, N-cocomorpholine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxypropyldimethylamine, N,N,N-trimethylisopropyl propylenediamine, 3-diethylamino-propyldiethylamine, dimethylbenzylamine, and the like. Other suitable catalysts are, for example, stannous chloride, dibutyltin-di-2-ethyl hexonate, potassium hexanoate, stannous oxide, as well as other organometallic compounds such as are disclosed in U.S. Pat. No. 2,846,408.
Chain extending agents which may be employed in the preparation of the polyurethane adhesives include those compounds having at least two functional groups bearing active hydrogen atoms such as, hydrazine, primary and secondary diamines, amino alcohols, amine acids, hydroxy acids, glycols, or mixtures thereof. A preferred chain extender when used is ethylene glycol.
Other optional additives which fall within the spirit of the present invention included stabilizers against aging and weathering, fillers, and plasticizers. Plasticizers used in the present invention include castor oil and its derivatives, e.g. methyl ricinoleate.
The following illustrates the nature of the invention. All parts are by weight unless otherwise indicated.
______________________________________Polyol A is a polyoxyethylene/polyoxpropylene block copolymer having a molecular weight of about 2000.Polyol B is a polyoxypropylene adduct of propylene glycol having a molecular weight of about 1040.Polyol C is a polyethylene terephthalate based aromatic polyester polyol having an equivalent weight of about 160.Polyol D is a polyethylene terephthalate based aromatic polyester polyol having a equivalent weight of about 144.Baylithe Paste is a Zeolite Paste sold by Mobay.Zeolite Paste is a Zeolite Paste sold by EM Scientific.DABCO 33LV is an amine catalyst sold by Air Products.T-12 is a tin catalyst sold by Air Products.Castor Oil is a plasticizer.ISO A is a polymethylene polyphenylisocyanate having a functionality of about 27.ISO B is a mixture of polymethylene polyphenyl isocyanate containing minor amounts of a carbodimide modified 4,4'-diphenylmethane diisocyanate, and 2,4- and 4,4'-diphenylmethane diisocyanate.______________________________________
TABLE 1______________________________________Resin 1 2 3______________________________________Polyol A 50.0 10.0 --Polyol B -- -- 10.0Polyol C -- 63.0 --Polyol D -- 27.0 --Ethylene Glycol -- -- 5.0Baylithe Paste 0.4 2.0 --Zeolite Paste -- -- 2.0DABCO 33LV 1.0 1.0 --T-12 -- -- 0.1Castor Oil -- -- 20.0IsocyanateISO A -- 100.0 51.7ISO B 10.0 -- --______________________________________
All samples were prepared in like manner. Initially, the resin components were thoroughly mixed at room temperature. The isocyanate was added to the resin and mixed. The adhesive composition was at that point was a flowable liquid.
All samples cured to a hard, impact resistant tack-free state. Sample 1 in Table 1 was tested to determine thermal conductivity (ASTM C518) and softening temperature (ASTM D1525). Sample 1 exhibited excellent heat transfer capabilities with a reported K-factor of 1.033. It also exhibited no sag up to 200° F.
Polyethylene terephthalate based aromatic esters were added to the resin component in example 2. This addition resulted in a very hard polymer which had increased temperature resistance, exhibiting no sag to about 230° F. (ASTM D1525). Example 3 contained no polyester, but had a plasticizer added. The heat transfer characteristics (K-factor 0.765, ASTM C518), were less than example 1 however the adhesive when cured was not as hard. | The invention relates to urethane polymers exhibiting excellent heat transfer properties. Specifically these polymers are used as adhesives for the purpose of adhering cooling/condensing tubes to metal panels for the manufacture of freezer and refrigerator cabinets. | 2 |
This application is a National Stage Filing of PCT/IL99/00273, filed May 24, 1999.
FIELD OF THE INVENTION
The present invention relates to a novel taste enhancer. The present invention more particularly relates to a natural taste enhancer having taste enhancing properties as good as if not better than commercially available taste enhancers without the problems associated with the popular taste enhancers, in use by the food industry.
BACKGROUND OF THE INVENTION
The food industry uses flavor enhancers in a variety of savory products. These enhancers consist of monosodium glutamate (hereinafter MSG), hydrolyzed vegetable proteins, disodium salts of the 5′-nucleotides inosine monophosphate (IMP), guanosine monophosphate (GMP) and adenosine monophosphate (AMP), as well as autolysed yeasts. While all have disadvantages, the major enhancer, MSG, suffers from the problem known as Chinese Restaurant Syndrome.
The literature on taste enhancers is very large. A sample reference cited to show the various taste enhancers known is: S. Fuke and Y. Ueda, “Interactions between umami and other flavor characteristics”, in Trends in Food Science & Technology, Special Issue on Flavor Perception, December, 1996 (Vol. 7), Elsevier Sciences Ltd.
In the processing of tomatoes described in IL 107,999 w have obtained two fractions: serum and pulp where the serum is further concentrated:
After removing from the tomato juice the pulp, the serum is concentrated to a value that is higher than 4.5° Bx which is the normal value of crushed tomatoes to reach a Bx value of 80 Bx. It can then be hydrolyzed (or hydrolyzed and then concentrated). This product is commonly referred to as Clear Tomato Concentrate (CTC)—although it is clear only when it is in the 4.5° Bx region while at higher Bx values it becomes opaque.
OBJECTIVE OF THE INVENTION
The objective of the present invention is to afford a novel taste enhancer the Clear Tomato Concentrate which lacks the dominant tomato flavor to enable it to be used in a variety of savory food and beverage products and not only those based on tomatoes. It is a further objective of the present invention to afford a taste enhancer with little of no chance of causing Chinese Restaurant Syndrome.
STATEMENT OF THE INVENTION
A taste enhancer comprising clear tomato concentrate, and a method of enhancing the flavor of foods comprising adding a clear tomato concentrate to the food in an amount sufficient to enhance the flavor.
DETAILED DESCRIPTION OF THE INVENTION
Tomato Serum Concentrate contains 8-10% soluble proteins and free amino acids. By hydrolyzing the proteins, one can increase the concentration of free amino acids, an in this way intensity the flavor enhancing properties of the concentrate where the hydrolysis occurs due to the presence of natural tomato acids. The rate of hydrolysis increases by heating, and depends on the time and temperature. The results of acid hydrolysis of the Tomato Serum Concentrate are shown in Table 1.
The tomato proteins (in the concentrate or in the serum prior to concentration) can also be hydrolyzed by enzymes at relatively low temperatures.
For this we have used fungal, protease/peptidase enzyme formualation developed by Novo Nordisk, and sold under the name of “flavourzyme”. Almost complete protein hydrolysis was obtained after one-hour enzyme treatment at 50°. The enzyme was subsequently inactivated by heating at 80° for a short period. The results of enzymatic hydrolysis of the Tomato Serum Concentrate are shown in Table 2.
Hydrolysis before or after concentration of the Tomato Serum yielde essentially the same results—namely an excellent food flavor enhancer.
A further embodiment of the invention is to use the flavor enhancer in powder form. Thus the Clear Tomato Concentrate, after the steps of hydrolysis and concentration, is either sprayed dried or dried using any other conventional dehydration techniques used by the food industry. The Clear Tomato Concentrate can be dried on a variety of materials such as maltodextrins, starches, sugars, carbohydrates, their derivatives or salts used as carriers to facilitate drying.
EXAMPLE 1
Clear Tomato Concentrate In Powder Form
Clear Tomato Concentrate and maltodextrine 19 DE (dextrose equivalent) were diluted with water to the appropriate viscosity and sprayed dried to a free flowing powder containing 3-5% moisture.
EXAMPLE 2
Flavor Enhancin Properties of Clear Tomato Concentrate
The food and flavor enhancing properties of the hydrolyzed and concentrated (in either order) Clear Tomato Concentrate are demonstrated in taste trials in which three different types of products (namely hamburger, Paolla rice, and vegetable soup) were prepared in three versions:
1. Control (with no flavor enhancers). 2. Product plus pure MSG (0.3% in the final product). 3. Product plus Clear Tomato Concentrate, 60° Bx (0.5% in end Product).
Fifteen tasters were asked to answer two questions for each product:
1. Which of the three samples is substantially different? 2. Which one of the remaining products do you prefer?
The results of the first question was as follows:
Hamburger: All 15 participants recognized the control as different and inferior. Paolla Rice: All 15 participants recognized the control as different and inferior. Vegetable Soup: All 15 participants recognized the control as different and inferior.
The results for the second question were as follows:
Hamburger: participants preferred the hamburger with MSG; 9 preferred the hamburger with the Clear Tomato Concentrate; and 3 had no preference. Paolla Rice: One participant preferred the sample with MSG; 12 participants preferred the sample with Clear Tomato Concentrate; and 2 had no preference. Vegetable Soup: Six participants preferred the soup with MSG; 5 participants preferred the sample with Clear Tomato Concentrate and 4 had no preference.
From this taste panel we see that the Clear Tomato Concentrate containing a total of 4-5% glutamic acid and glutamine is equal to or better than pure MSG with no problem of the Chinese Restaurant Syndrome. It is believed that this superior enhancing property is due to synergism between the glutamic acid and glutamine on the one hand and the various other amino acids present in the clear Tomato Concentrate on the other hand.
TABLE 1
CONCENTRATION OF FREE AMINO ACIDS IN TOMATO
SERUM (60° Bx) AFTER ACID HYDROLYSIS
Compound
CONC mg/kg
Aspartic acid
11904.12
Threonine
1117.25
Serine
1279.80
Asparagine
5684.74
Glutamic acid
26501.90
Glutamine
12942.68
Proline
276.54
Glycine
280.20
Alanine
4574.41
Valine
440.16
Methionine
152.93
Isoleucine
531.46
Leucine
623.99
Tyrosine
419.01
Phenylalanine
1567.32
Gamma aminobutyric
9908.32
Ethanolamine
148.30
Tryptophane
16.56
Lysine
1010.62
Histidine
1036.93
Arginine
905.63
Total
80321.87
TABLE 2
CONCENTRATION OF FREE AMINO ACIDS IN TOMATO
SERUM (60° Bx) AFTER ENZYMATIC HYDROLYSIS
Compound
CONC mg/kg
Aspartic acid
12393.07
Threonine
1186.59
Serine
1370.29
Asparagine
4565.77
Glutamic acid
26647.74
Glutamine
11464.92
Proline
280.31
Glycine
332.54
Alanine
4570.03
Valine
488.21
Methionine
156.60
Isoleucine
522.86
Leucine
612.15
Tyrosine
435.35
Phenylalanine
1598.48
Gamma aminobutyric
10271.85
Ethanolamine
167.84
Tryptophane
26.97
Lysine
1058.58
Histidine
1061.20
Arginine
926.63
Total
79016.99 | The present invention relates to a taste enhancer comprising clear tomato concentrate. The present invention also relates to a method of enhancing the flavor of foods comprising adding a clear tomato concentrate to the food in an amount sufficient to enhance the flavor. | 0 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of co-pending U.S. patent application Ser. No. 11/761,229, filed Jun. 11, 2007, which claims benefit of U.S. provisional patent application Ser. No. 60/804,547, filed Jun. 12, 2006. Each of the aforementioned related patent applications is herein incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] Embodiments of the present invention generally relate to a wellbore tool for selectively isolating a zone in a wellbore. More particularly, the invention relates to a flapper latch for use with the wellbore tool.
[0004] 2. Description of the Related Art
[0005] A completion operation typically occurs during the life of a well in order to allow access to hydrocarbon reservoirs at various elevations. Completion operations may include pressure testing tubing, setting a packer, activating safety valves or manipulating sliding sleeves. In certain situations, it may be desirable to isolate a portion of the completion assembly from another portion of the completion assembly in order to perform the completion operation. Typically, a ball valve, which is referred to as a formation isolation valve (FIV), is disposed in the completion assembly to isolate a portion of the completion assembly.
[0006] Generally, the ball valve includes a valve member configured to move between an open position and a closed position. In the open position, the valve member is rotated to align a bore of the valve member with a bore of the completion assembly to allow the flow of fluid through the completion assembly. In the closed position, the valve member is rotated to misalign the bore in the valve member with the bore of the completion assembly to restrict the flow of fluid through the completion assembly, thereby isolating a portion of the completion assembly from another portion of the completion assembly. The valve member is typically hydraulically shifted between the open position and the closed position.
[0007] Although the ball valve is functional in isolating a portion of the completion assembly from another portion of the completion assembly, there are several drawbacks in using the ball valve in the completion assembly. For instance, the ball valve takes up a large portion of the bore in the completion assembly, thereby restricting the bore diameter of the completion assembly. Further, the ball valve is susceptible to debris in the completion assembly which may cause the ball valve to fail to operate properly. Additionally, if the valve member of the ball valve is not fully rotated to align the bore of the valve member with the bore of the completion assembly, then there is no full bore access of the completion assembly.
[0008] There is a need therefore, for a downhole tool that is less restrictive of a bore diameter in a completion assembly. There is a further need for a downhole tool that is debris tolerant. There is a further need for a downhole tool having a flapper latch assembly that is configured to maintain a flapper valve in a closed position.
SUMMARY OF THE INVENTION
[0009] The present invention generally relates to a method and an apparatus for selectively isolating a portion of a wellbore. In one aspect, an apparatus for isolating a zone in a wellbore is provided. The apparatus includes a body having a bore. The apparatus further includes a first flapper member and a second flapper member disposed in the bore, each flapper member selectively rotatable between an open position and a closed position multiple times, wherein the first flapper member is rotated from the open position to the closed position in a first direction and the second flapper member is rotated from the open position to the closed position in a second direction. Additionally, the apparatus includes a flapper latch assembly disposed in the bore, the flapper latch assembly movable between an unlocked position and a locked position, wherein the flapper latch assembly is configured to hold the first flapper member in the closed position when the flapper latch assembly is in the locked position.
[0010] In another aspect, a method for selectively isolating a zone in a wellbore is provided. The method includes positioning a downhole tool in the wellbore, the downhole tool having a body, a first flapper member, a second flapper member and a flapper latch assembly, whereby each flapper member is initially in an open position. The method also includes moving the first flapper member to a closed position by rotating the first flapper member in a first direction. Further, the method includes moving the second flapper member to a closed position by rotating the second flapper member in a second direction. Additionally, the method includes moving a flapper latch assembly from an unlocked position to a locked position, whereby the flapper latch assembly is configured to hold the first flapper member in the closed position when the flapper latch assembly is in the locked position.
[0011] In yet a further aspect, a flapper latch assembly for use with a flapper valve is provided. The flapper latch assembly includes a body rotatable between an unlocked position and a locked position, wherein the body includes an end configured to engage a portion of the flapper valve when the flapper valve is in a closed position and the body is in the locked position. Additionally, the method includes a biasing member attached to the body, wherein the biasing member is configured to bias the body in the locked position.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only typical embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
[0013] FIG. 1 is a cross-sectional view illustrating a downhole tool with a first flapper valve and a second flapper valve.
[0014] FIG. 2 is a cross-sectional view illustrating a flapper latch assembly for use with the first flapper valve.
[0015] FIG. 3 is a cross-sectional view illustrating the flapper latch assembly in an unlocked position and the first flapper valve in a closed position.
[0016] FIG. 4 is a cross-sectional view illustrating the flapper latch assembly in a locked position.
[0017] FIG. 5 is a cross-sectional view illustrating the flapper latch assembly in an unlocked position.
[0018] FIG. 6 is a cross-sectional view illustrating the first flapper valve and the second flapper valve in an open position and the flapper latch assembly in the unlocked position.
[0019] FIGS. 7 and 8 are cross-sectional views illustrating the actuation of a release mechanism in the flapper latch assembly.
DETAILED DESCRIPTION
[0020] FIG. 1 is a cross-sectional view illustrating a downhole tool 100 . The tool 100 includes an upper sub 105 , a housing 160 , and a lower sub 110 . The upper sub 105 is configured to be connected to an upper completion assembly (not shown), such as a packer arrangement. The lower sub 110 is configured to be connected to a lower completion assembly (not shown). Generally, the tool 100 is used to selectively isolate the upper completion assembly from the lower completion assembly.
[0021] The tool 100 includes a first flapper valve 125 and a second flapper valve 150 . The valves 125 , 150 are movable between an open position and a closed position multiple times. As shown in FIG. 1 , the valves 125 , 150 are in the open position when the tool 100 is run into the wellbore. Generally, the valves 125 , 150 are used to open and close a bore 135 of the tool 100 in order to selectively isolate a portion of the wellbore above the tool 100 from a portion of the wellbore below the tool 100 .
[0022] The valves 125 , 150 may move between the open position and the closed position in a predetermined sequence. For instance, in a closing sequence, the first flapper valve 125 is moved to the closed position and then the second flapper valve 150 is moved to the closed position as will be described in relation to FIGS. 2-4 . In an opening sequence, the second flapper valve 150 is moved to the open position and then the first flapper valve 125 is moved to the open position as will be described in relation to FIGS. 5-6 . The particular sequence facilitates proper functioning of the tool 100 . For example, in the opening sequence, the second flapper valve 150 is moved to the open position first in order to allow the second flapper valve 150 to open in a substantially clean environment defined between the flapper valves 125 , 150 , since the first flapper valve 125 is configured to substantially block debris from contacting the second flapper valve 150 when the first flapper valve 125 is in the closed position. In the closing sequence, the first flapper valve 125 is moved to the closed position first in order to substantially protect the second flapper valve 150 from debris that may be dropped from the surface of the wellbore. It must be noted that the valves 125 , 150 may be operated according to other suitable sequences.
[0023] As illustrated in FIG. 1 , the first flapper valve 125 is held in the open position by an upper flow tube 140 , and the second flapper valve 150 is held in the open position by a lower flow tube 155 . It should be noted that the flapper valves 125 , 150 may be a curved flapper valve, a flat flapper valve, or any other suitable valve without departing from principles of the present invention. Further, the opening and closing orientation of the valves 125 , 150 may be rearranged into any configuration without departing from principles of the present invention. Additionally, the second flapper valve 150 may be positioned at a location above the first flapper valve 125 without departing from principles of the present invention.
[0024] The tool 100 also includes a shifting sleeve 115 with a profile 165 proximate one end and a profile 190 proximate another end. The tool 100 further includes a spring 120 and a shift and lock mechanism 130 . As discussed herein, the shift and lock mechanism 130 interacts with the spring 120 , the shifting sleeve 115 , and the upper tubes 140 , 155 in order to move the flapper valves 125 , 150 between the open position and the closed position.
[0025] As shown in FIG. 1 , the shift and lock mechanism 130 is a key and dog arrangement, whereby a plurality of dogs move in and out of a plurality of keys formed in the sleeves as the sleeves are shifted in the tool 100 . The movement of the dogs and the sleeves causes the flapper valves 125 , 150 to move between the open position and the closed position. It should be understood, however, that the shift and lock mechanism 130 may be any type of arrangement capable of causing the flapper valves 125 , 150 to move between the open and the closed position without departing from principles of the present invention. For instance, the shift and lock mechanism 130 may be a motor that is actuated by a hydraulic control line or an electric control line. The shift and lock mechanism 130 may be an arrangement that is controlled by fiber optics, a signal from the surface, an electric line, or a hydraulic line. Further, the shift and lock mechanism 130 may be an arrangement that is controlled by a pressure differential between an annulus and a tubing pressure or a pressure differential between a location above and below the tool 100 .
[0026] FIG. 2 is a cross-sectional view illustrating a flapper latch assembly 300 for use with the first flapper valve 125 . As will be described in relation to FIGS. 3-8 , the flapper latch assembly 300 is generally configured to lock the first flapper valve 125 in the closed position. The flapper latch assembly 300 includes a body 305 , a release mechanism 310 , a biasing member 315 , and a pin member 325 . As shown, the flapper latch assembly 300 is in an unlocked position.
[0027] FIG. 3 is a cross-sectional view illustrating the flapper latch assembly 300 in the unlocked position and the first flapper valve 125 in a closed position. In the closing sequence, the first flapper valve 125 is moved to the closed position first in order to protect the second flapper valve 150 from debris that may be dropped from the surface of the wellbore. Referring back to FIG. 1 , in one embodiment, a shifting tool (not shown) having a plurality of fingers that mates with the profile 165 of the shifting sleeve 115 is used to move the first flapper valve 125 to the closed position. The shifting tool may be a mechanical tool that is initially disposed below the tool 100 and then urged through the bore 135 of the tool 100 until it mates with the upper profile 165 . The shifting tool may also be a hydraulic shifting tool that includes fingers that selectively extend radially outward due to fluid pressure and mate with the profile 165 . In either case, the shifting tool mates with the profile 165 in order to pull the shifting sleeve 115 toward the upper sub 105 .
[0028] As the shifting sleeve 115 begins to move toward the upper sub 105 , the shift and lock mechanism 130 starts the closing sequence of the flapper valves 125 , 150 . During the closing sequence, the shift and lock mechanism 130 moves the upper flow tube 140 away from the first flapper valve 125 in a direction as indicated by an arrow 230 . A biasing member (not shown) attached to a flapper member 185 in the first flapper valve 125 rotates the flapper member 185 around a pin 175 until the flapper member 185 contacts and creates a sealing relationship with a valve seat 170 . As illustrated, the flapper member 185 closes away from the lower sub 110 . As such, the first flapper valve 125 is configured to seal from below. In other words, the first flapper valve 125 is capable of substantially preventing fluid flow from moving upward through the tool 100 . In addition, as the shifting sleeve 115 moves toward the upper sub 105 , the spring 120 is also compressed.
[0029] As illustrated in FIG. 3 , the flapper latch assembly 300 is in the unlocked position and the first flapper valve 125 is in the closed position. As the shifting tool urges the sleeve further toward the upper sub, the flapper latch assembly 300 is activated to secure the first flapper valve 125 in the closed position. The flapper latch assembly 300 may be configured to allow the first flapper valve 125 to burp or crack open if necessary. This situation may occur when debris from the surface of the wellbore falls and lands on the first flapper valve 125 . It should be noted that the flapper latch assembly 300 is not configured to allow the first flapper valve 125 to move to the full open position, unless a release mechanism is activated, as shown in FIGS. 7-8 , but rather the flapper latch assembly 300 will only allow the first flapper valve 125 to crack open slightly. As such, the first flapper valve 125 in the closed position acts a barrier member to the second flapper valve 150 by substantially preventing large particles (i.e. a dropped drill string) from contacting and damaging the second flapper valve 150 .
[0030] FIG. 4 is a cross-sectional view illustrating the flapper latch assembly 300 in a locked position. After the first flapper valve 125 is in the closed position and secured in place, the shifting tool continues to urge the sleeve toward the upper sub, thereby causing the flapper valves 125 , 150 and the flapper latch assembly 300 to move together as a subsystem relative to the housing 160 in a direction as indicated by an arrow 235 . The flapper latch assembly 300 moves in the housing 160 until the flapper latch assembly 300 is positioned proximate a recess 340 formed in the housing 160 , thereby allowing the flapper latch assembly 300 to move from the unlocked position to the locked position. At that point, the biasing member 315 causes the body 305 to rotate around the pin member 325 to allow the flapper latch assembly 300 to engage an end portion 145 of the first flapper valve 125 . At the same time, the second flapper valve 150 is moved in the housing 160 away from the lower flow tube 155 , thereby allowing a flapper member in the second flapper valve 150 to rotate around a pivot point until the flapper member contacts and creates a sealing relationship with a valve seat 180 . The flapper member closes away from the upper sub. As such, the second flapper valve 150 is configured to seal from above. In other words, the second flapper valve 150 is capable of substantially preventing fluid flow from moving downward through the tool 100 . Thereafter, the shifting sleeve 115 is urged closer to the upper sub 105 and the flapper valves 125 , 150 are held in the closed position by the shift and lock mechanism 130 . Also, the spring 120 is in a full compressed state.
[0031] To open the valves 125 , 150 according to one opening sequence, the second flapper valve 150 is moved to the open position first in order to allow the second flapper valve 150 to open in a clean environment by manipulating the shift and lock mechanism 130 . As discussed herein, in one embodiment, the shift and lock mechanism 130 is a key and dog arrangement, whereby the plurality of dogs move in and out of the plurality of keys formed in the sleeves as the sleeves are shifted in the tool 100 . The movement of the dogs and the sleeves causes the flapper valves 125 , 150 to move between the open and the closed position. It should be understood, that the shift and lock mechanism 130 is not limited to this embodiment. Rather, the shift and lock mechanism 130 may be any type of arrangement capable of causing the flapper valves 125 , 150 to move between the open and the closed position.
[0032] Prior to moving the second flapper valve 150 to the open position, the pressure around the second flapper valve 150 may be equalized by aligning a port (not shown) with a slot (not shown) formed in the flow tube 155 as the shifting sleeve 115 is moved toward the lower sub 110 . Thereafter, the further movement of the shifting sleeve 115 toward the lower sub 110 causes the flapper valves 125 , 150 and the flapper latch assembly 300 to move together as a subassembly relative to the housing 160 in a direction as indicated by an arrow 240 . The flapper latch assembly 300 moves in the housing 160 until an edge 320 of the flapper body 305 contacts a slanted edge 330 in the housing 160 . At that point, the flapper latch assembly 300 moves to the unlocked position as the contact between the edge 320 and the slanted edge 330 causes the flapper body 305 to rotate around the pin member 325 , thereby causing the flapper latch assembly 300 to disengage from the end portion 145 of the flapper member 185 . At the same time, the second flapper valve 150 moves in the housing 160 toward the lower flow tube 155 . Contact of the second flapper valve 150 with the lower flow tube 155 overcomes a biasing member in the second flapper valve 150 such that the second flapper valve 150 moves from the closed position to the open position as shown in FIG. 5 . As previously discussed, the movement of the shifting sleeve 115 toward the lower sub 110 may be accomplished by a variety of means. For instance, the shifting sleeve 115 may be urged toward the lower sub 110 by a hydraulic or mechanical shifting tool (not shown) that interacts with the profile 190 formed on the shifting sleeve 115 . In turn, the shifting sleeve 115 manipulates the mechanism 130 in order to open the flapper valves 125 , 150 .
[0033] FIG. 6 is a cross-sectional view illustrating the first flapper valve 125 and the second flapper valve 150 in the open position and the flapper latch assembly 300 in the unlocked position. After the second flapper valve 150 is opened, the upper flow tube 140 moves toward the first flapper valve 125 as indicated by an arrow 245 as the shift and lock mechanism 130 is manipulated. Prior to the upper flow tube 140 contacting the flapper member 185 in the first flapper valve 125 , a slot (not shown) formed in the upper flow tube 140 aligns with a port (not shown) to equalize the pressure around the first flapper valve 125 . Thereafter, the upper flow tube 140 contacts the flapper member 185 in the first flapper valve 125 and causes the first flapper valve 125 to move from the closed position to the open position. Subsequently, the flapper valves 125 , 150 are held in place by further manipulation of the shift and lock mechanism 130 . The process of moving the flapper valves 125 , 150 between the open position and the closed position may be repeated any number of times.
[0034] FIGS. 7 and 8 are cross-sectional views illustrating the actuation of a release mechanism in the flapper latch assembly. While the flapper latch assembly 300 is in the locked position, the release mechanism 310 may be activated to allow the first flapper valve 125 to move from the closed position to the open position. The release mechanism 310 is generally activated by applying a force to the first flapper valve 125 in the direction as indicated by the arrow in FIG. 7 . In turn, the force on the first flapper valve 125 causes a portion of the force to act upon the release mechanism 310 . At a predetermined force, the release mechanism 310 is activated, thereby allowing the first flapper valve 125 to move from the closed position to the open position as shown in FIG. 8 . In one embodiment, the release mechanism 310 is a shearable member, such as a shear pin. In this embodiment, the shearable member is designed to fail at the predetermined force. It should be noted the predetermined force to activate the release mechanism 310 is generally less than a force that causes the pin 175 in the flapper latch 125 to fail. In this manner, the activation of the release mechanism 310 allows the first flapper valve 125 to move from the closed position to the open position.
[0035] In one embodiment, a hydraulic chamber arrangement is used to move the flapper valves. For instance, the flapper valves in the downhole tool are moved to the open position by actuating the shift and lock mechanism. In this embodiment, the shift and lock mechanism is actuated when a pressure differential between an ambient chamber and tubing pressure in the bore of the tool reaches a predetermined pressure. The chamber is formed at the surface between two seals. As the tool is lowered into the wellbore, a hydrostatic pressure is developed which causes a pressure differential between the pressure in the chamber and the bore of the tool. At a predetermined differential pressure, a shear pin (not shown) is sheared, thereby causing the spring to uncompress and shift the shifting sleeve toward the lower sub in order to release the flapper valves and start the opening sequence. The shear pin may be selected based upon the depth location in the wellbore that the shift and lock mechanism is to be actuated.
[0036] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. | The present invention generally relates to a method and an apparatus for selectively isolating a portion of a wellbore. In one aspect, an apparatus for isolating a zone in a wellbore is provided. The apparatus includes a body having a bore. The apparatus further includes a first flapper member and a second flapper member, each flapper member selectively rotatable between an open position and a closed position. Additionally, the apparatus includes a flapper latch assembly disposed in the bore, the flapper latch assembly movable between an unlocked position and a locked position, wherein the flapper latch assembly is configured to hold the first flapper member in the closed position when the flapper latch assembly is in the locked position. In another aspect, a method for selectively isolating a zone in a wellbore is provided. In yet a further aspect, a flapper latch assembly for use with a flapper valve is provided. | 4 |
RELATED APPLICATIONS
Not Applicable
BACKGROUND OF THE INVENTION
Field of the Invention
This invention relates to tubular heat exchangers, and in particular to turbulence-inducing devices positioned in the tubes of the tubular heat exchanger that minimize or prevent fouling caused by the heat transfer fluids and enhance or maintain the overall heat transfer coefficient over the operational life of the tubular members.
Description of Related Art
Heat exchangers are found in many industrial and commercial applications. In the design of heat transfer equipment, an important factor includes the footprint of the exchanger relative to the capacity of fluid that is to be heated or cooled (the “receiving fluid”), as well as the requisite flow of the heating or cooling fluid (the “transferring fluid”). The heat transfer coefficient between the transferring fluid and the receiving fluid should be maximized to achieve the smallest allowable footprint of the heat exchanger.
Another factor that must be considered in designing heat exchangers is the tendency of heating or cooling fluids to foul in the tubes through which they pass. One detrimental effect of fouling is a lowering of the heat transfer coefficient. The thermal conductivity of the fouling layer is less than that of the tube material, which increases the heat transfer resistance, reduces the efficacy of the heat exchanger, and increases the tube skin temperature. Another negative effect of fouling is that the formation of depositions on the interior surface of the tubes reduces their cross-sectional area, causing increased resistance to the fluid flow and an increase in the pressure drop across the unit.
In refinery and petrochemical plants, problems caused by tube fouling are very expensive to remedy. Capital expenditures are higher due to the increased size of the heat exchanger (e.g., selecting heat exchangers with 10-50% greater surface area to accommodate conventional fouling expectations), the associated increase in requisite area within the plant, the higher strength and size foundations, and the extra transport and installation costs. Furthermore, the cost of operating the unit is increased due to additional fuel, electricity or process steam requirements. In addition, production losses occur during planned and emergency plant shutdowns due to fouling and associated system failures.
Various attempts to minimize or prevent fouling problems have been advanced. One common prevention technique is to use a fouling factor in the design phase of a heat transfer unit that includes increasing the heat transfer surface area, either by increasing the number of tubes or the tube length. Such a fouling factor is considered a necessary aspect of heat exchanger design, based on acceptance of the fact that fouling is inevitable. In addition to the aforementioned costs associated with selecting a larger heat exchanger, an additional concern is that the excess surface area calculated with a fouling factor can result in start-up complications and actually encourage more fouling. That is, it is common that at start-up, sludge and dirt migrate into dead zones and low velocity locations. The effect of increasing the number of tubes is to decrease the fluid flow velocity, thereby increasing the likelihood of fouling. Similarly, increasing the tube length results in lower fluid pressure, also increasing the likelihood of fouling.
Other known attempts to mitigate fouling problems involve the use of in-line mechanical cleaning devices to remove fouling build-up inside the tubes. These devices, which generally require direct physical contact with the inner tube surface, have not been especially successful in preventing fouling.
Deflection insertions are also another general category of fouling prevention or mitigation devices. For instance, U.S. Pat. No. 1,015,831 to Pielock et al. discloses a device that is inserted in a pipe to deflect the central and peripheral flow of liquid. Fluid along the side walls is directed toward the center of the pipe, and fluid moving along the longitudinal center line is directed towards the side walls. The device is constructed as a ring installed on the pipe's inner surface having a diametrically disposed web or a plurality of webs that form an apex pointed against the direction of fluid flow. However, the device described in Pielock et al. is mainly intended to diffuse central flow in multiphase fluid for equal distribution. Furthermore, in the context of a heat exchanger's transferring tube, fouling will predictably occur at the interface of the Pielock device and the tube's inner surface.
U.S. Pat. No. 3,995,663 to Perry describes a ferrule for insertion at the inlet of a vertical shell-and-tube heat exchanger, including a flange and shoulder to seat upon the tube sheet, a bore and a cylindrical portion as an extension of the bore to facilitate formation of a solid column of liquid entering the tube. The ferrule also includes an outwardly extending connecting wall that distributes fluid towards the apex of a conical member. Fluid entering the bore is directed to the side walls due to the shape of the conical member. Apparently, the purpose of the device is to distribute liquid to the walls of the ferrule rather than to the tube walls to provide liquid in the form of a falling film on the inner surfaces of the vertical tubes for evaporation. Therefore, application of this structure is necessarily limited to vertical shell-and-tube heat exchangers.
U.S. Pat. No. 5,311,929 to Verret and U.S. Pat. No. 4,794,980 to Raisanaen both disclose air-to-air heat exchangers that include cone-shaped elements disposed in each tube along a central rod. The cones serve as deflectors to create turbulence in the gases flowing through the tube. The elements disclosed in Verret are attached using a twisted strip of material bent inside the tubes to provide contact with the tube's internal surface. The conical elements described in Raisanaen are open on the downstream end, thus allowing fouling and sludge accumulation inside the cone.
The above-described references each have drawbacks that render them unsuitable for minimizing or preventing fouling. Additional known attempts to prevent fouling rely upon inserts fixed to the inner wall of the tube. However, fouling will eventually accumulate at, and proximate to the attachment points, which hinders removal of the inserts and thus complicates cleaning the inner surface of the tube.
Therefore, it is an object of the present invention to provide an apparatus for use in the tubes of heat exchangers that eliminates or minimizes fouling of the interior surfaces of the tubes.
It is another object of the present invention to provide an apparatus for use in tubes of heat exchangers that maintains the heat transfer coefficient over the operational life of the tubes.
It is still another object of the present invention to provide an apparatus for use in the tubes of heat exchangers that permits the designer to utilize the minimum theoretical heat exchanger size or capacity for a given application.
SUMMARY OF THE INVENTION
The above objects and further advantages are provided by the apparatus of the present invention for promoting turbulence in the tubes of a heat exchanger conveying the heat transfer fluid that in one embodiment comprehends a turbulence-inducing element formed with a conical upstream portion, from the base of which a second portion extends downstream. In one embodiment, the second portion is convex or hemi-spheroid in shape. In another embodiment, the second portion is conical in shape. In yet another embodiment, the second portion is shaped as a conical frustum. In yet another embodiment, the second portion is shaped as a truncated convex shape with a rounded edge surface. In another aspect of the present invention, longitudinal grooves and/or protrusions are formed on the exterior surfaces of the turbulence-inducing elements. The solid or closed downstream ends of the elements prevent accumulation of deposits.
A plurality of these turbulence-inducing elements are secured to a structural support member that is centrally positioned along the longitudinal axis of the tube. In a preferred embodiment, a plurality of the turbulence-inducing elements extend along substantially the entire length of the tube. The centrally-positioned support member can be a rigid member, such as a rod, or a flexible material, such as a solid or stranded wire or cable. Alternatively, a plurality of centrally-positioned links can be used to join the turbulence-inducing elements.
In a further aspect of the invention, springs can be provided at both ends of the centrally-positioned support member, to maintain the system in tension and absorb sudden load variations.
In the practice of the method of the invention, the apparatus including a plurality of turbulence-inducing elements mounted on the supporting member is inserted into one or more of the tubes of tube-type heat exchangers to induce turbulent fluid flow inside the tube, particularly at the inner wall of the tube. The supporting member is attached to the ends of the tube. The supported elements are dimensioned and configured so that they do not touch the adjacent inner wall of the tube in which they are mounted. During operation, the fluid in the tube flows across the symmetrically-shaped surfaces of the turbulence-inducing elements, which in turn applies tension to the supporting member and which thereby maintains the elements along the center of the tube.
Preventing formation of a quiescent boundary layer enhances the heat transfer coefficient and breaks down or prevents formation of the stagnant film on the inner surface of the tubes associated with the boundary layer. The apparatus and method of the invention also result in a thorough mixing of the heat transfer fluid as it passes through the tube, thereby enhancing its efficiency.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be described in further detail below and with reference to the attached drawings in which the same or similar elements are referred to by the same reference numerals, and in which:
FIG. 1 is a longitudinal cross-sectional view of a typical shell-and-tube heat exchanger of the prior art;
FIG. 2 is a longitudinal cross-sectional view of a prior art tube carrying heat transfer fluid in a tubular-type heat exchangers schematically illustrating the boundary layer phenomenon;
FIG. 3A is a longitudinal cross-sectional view of a tube carrying heat transfer fluid in which the turbulence-inducing elements of the present invention are mounted;
FIG. 3B is an end view of the tube shown in FIG. 3A ;
FIG. 3C is side perspective view of one embodiment in which each linking wire can be routed across a number of tube ends;
FIG. 3D is side perspective view of one embodiment in which a tube sleeve can be inserted into the tubes;
FIGS. 3E and 3F show a side perspective view and end view, respectively, of one embodiment showing a first linking wire routed across a row of tube ends and a second linking wire routed across a column of tube ends;
FIG. 3G is a diagram used to describe relative dimensions according to one example;
FIG. 4 is a longitudinal cross-sectional view of a tube carrying heat transfer fluid according to the present invention schematically depicting the turbulent fluid flow within the tube;
FIGS. 5A, 5B, and 5C are a series of front, side, and rear views, respectively, of one embodiment of a turbulence-inducing element of the present invention with a downstream portion in the form of a convex portion extending from the base of a conical portion;
FIG. 6 is a side perspective view of another embodiment of a turbulence-inducing element of the present invention with a downstream portion in the form of a truncated convex shape with a rounded edge surface;
FIG. 7 is a side perspective view of a further embodiment of a turbulence-inducing element of the present invention with a downstream portion having a shape that is conical with an apex;
FIG. 8 is a side perspective view of an additional embodiment of a turbulence-inducing element of the present invention with a downstream portion having a shape that is conical with a rounded apex;
FIG. 9 is a side perspective view of a still further embodiment of a turbulence-inducing element of the present invention with a frustoconical downstream portion;
FIG. 10 is a side perspective view of an embodiment of a turbulence-inducing element of the present invention having a generally conical upstream portion with a concave lateral outer surface;
FIG. 11 is a side perspective view of a further embodiment of a turbulence-inducing element of the present invention having an upstream portion having a pyramidal structure;
FIG. 12 is a side perspective view of another embodiment of a turbulence-inducing element of the present invention having an upstream portion with a star-shaped pyramidal structure;
FIGS. 13A, 13B, and 13C are a downstream end view, side perspective view, and upstream end view, respectively, of another embodiment of a turbulence-inducing element of the present invention having surface grooves extending in the direction of fluid flow;
FIGS. 14A, 14B, and 14C are a downstream end view, side perspective view, and upstream end view, respectively, of another embodiment of a turbulence-inducing element of the present invention in which the upstream conical surface portion is provided with a plurality of protruding stud elements;
FIGS. 15A, 15B, and 15C are a downstream end view, side perspective view, and upstream end view, respectively, of an additional embodiment of a turbulence-inducing element of the present invention that has both grooves in the direction of fluid flow and protruding stud elements;
FIGS. 16-18 are longitudinal cross-sectional views of various embodiments of arrangements of turbulence-inducing elements according to the present invention including structures for accommodating expansion and contraction of the supporting member in the tube; and
FIGS. 19A and 19B are a side perspective view and a downstream end view, respectively, of another embodiment of a turbulence-inducing element of the present invention;
FIG. 20 is a diagram used to describe relative dimensions according to the embodiment illustrated in FIGS. 19A and 19B .
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIG. 1 , there is shown a longitudinal cross-sectional view schematically depicting the arrangement of elements in a typical shell-and-tube heat exchanger 20 of the prior art. A bundled tube heat exchanger is a well known configuration of a type of heat transfer equipment in which a plurality of tubes convey a heat transfer fluid. By means of the thermal conductivity of the tubes, heat is transferred to a receiving fluid that contacts the exterior surface of the tubes.
Exchanger 20 includes a shell 22 and a tube set 24 having a plurality of tubes 26 . The tubes 26 are supported at their ends by tube sheets 28 , also known as end plates. In the typical construction of a bundled tube heat exchanger, a series of baffles 30 are provided through which the plurality of parallel tubes 26 pass.
In operation, heat transfer fluid is introduced via a tube set inlet 38 proximate to the first end 34 of the shell-and-tube heat exchanger 20 , passes through the tubes 26 , and is discharged from a tube set outlet 40 proximate to the opposite end 36 of the heat exchanger 20 . While heat transfer fluid is passing through tubes 24 , receiving fluid is introduced into the shell inlet 42 proximate the end portion 36 . Receiving fluid contacts the outer surfaces of the tubes 26 as it passes over them and around the baffles 30 , thereby undergoing a temperature change. Heated or cooled fluid from the shell 22 is discharged via the shell outlet 44 proximate to the first end 34 .
As noted above, a common problem encountered in the tubes of shell-and-tube and other tubular heat exchangers is fouling of the inner walls and plugging of the tubes carrying the heat transfer fluid. This fouling leads to decreased cross-sectional area of the tubes, thus increasing the pressure drop across the tubes, and also causing decreased thermal conductivity. This phenomenon is schematically illustrated in FIG. 2 , showing a boundary layer 46 formed on the inner surface of the tube 26 . As a result, the flow velocity of the boundary layer 46 is very low, reducing the heat transfer coefficient and promoting adhesion of impurities to the inner surface of the tube wall.
Heat transfer fluids can be gases or liquids, including high viscosity lube oil. The selection of the number, size and shape of turbulent-inducing elements depends on the allowable pressure; type of need; enhancement of heat transfer; and need for fouling mitigation. For example, if the pressure drop of a specific heat exchanger is small and more turbulence is required, a preferred embodiment would be to use a large number of turbulent-inducing elements, of relatively small size.
As will be apparent to one of ordinary skill in the art, although a shell-and-tube heat exchanger is depicted in FIG. 1 , the turbulence-inducing elements of the present invention and their arrangement is applicable to other tubular heat exchangers including, but not limited to, double pipe heat exchangers and air-cooled heat exchangers.
FIGS. 3A and 3B show a heat exchanger tube 126 according to the present invention including an apparatus 148 having a plurality of turbulence-inducing elements 150 positioned centrally and spaced apart along the length of tube 126 positioned along a structural support element 152 . There are a variety of ways to assemble the present invention, including casting them in place and/or “stringing” the turbulence-inducing elements 150 on the rod, by welding, by use of suitable adhesives, and the like. Note that while the figures show a plurality of identical turbulence-inducing elements 150 , turbulence-inducing elements of different shapes and types can be positioned on the structural support element 152 . Various embodiments of alternative shapes and types of turbulence-inducing elements are described below with respect to FIGS. 5-15 . In addition, the total number of turbulence-inducing elements, the spacing between adjacent turbulence-inducing elements, the dimensions of the turbulence-inducing elements, including length and diameter relative to the tube diameter and other structural parameters, and/or the shape of turbulence-inducing elements, are determined by factors including, but not limited to, the heat transfer fluid flow rate and viscosity, increased back pressure that can result from a large diameter turbulence-inducing element blocking too much of the flow path, the maximum allowable pressure drop, and the target heat transfer coefficient.
The dimensions and spacing of the turbulence-inducing elements 150 relative to the size of the tube 126 are described according to the following formulas and with reference to FIG. 3G , according to one example.
A minimum gap (g) is maintained between the inside diameter (ID) of the tube and the outer diameter (d) of the turbulence-inducing element, according to the following formula:
g≧ 0.25*ID (1)
The diameter of the turbulence-inducing element (d) is determined relative to the inside diameter (ID) of the tube, according to the following formula:
d=ID− 2 g (2)
The length (L) of the turbulence-inducing element is determined relative to the inside diameter (ID) of the tube, according to the following formula:
1.25( ID )<= L <=1.5( ID ) (3)
The space (S) between adjacent turbulence-inducing elements is determined relative to the diameter (d) of the turbulence-inducing element and the gap (g) (described above), according to the following formula:
S= 3.5* d/g (4)
The depth (h) of the second portion extending towards the downstream end of the tube is determined relative to the diameter (d) of the turbulence-inducing element, according to the following formula:
0≦h≦0.25d (5)
The above formulas used for calculating the dimensions and spacing of the turbulence-inducing elements are provided by way of example. In general, the relative dimensions and spacing of the turbulence-inducing elements can be modified in order to strike a balance between preventing or minimizing the formation of a boundary layer and the potential for erosion of the inner surface of the tube due to increased fluid flow rate against the inner surface walls.
Materials of construction suitable for the turbulence-inducing elements and the structural support element include: plastics, including PTFE (Teflon) and nylon; natural or synthetic rubbers; wood or wood-based composites; or relatively soft metals such as aluminum, titanium, and copper.
The ends 184 and 186 of the structural support element 152 are attached at the upstream end 154 and the downstream end 156 , respectively. The ends 184 , 186 can include, for example, ball stops that are attached to a linking wire 155 at the upstream end 154 and a linking wire 157 at the downstream end 156 of the tube.
In one embodiment, as shown in FIG. 3C , each linking wire 155 and 157 can be routed across a number of tube ends.
In a another embodiment shown in FIG. 3D , a tube sleeve 190 can be inserted into the tubes, with a linking wire 192 attached, such as by welds 194 , to points on the inner wall of the tube sleeve that are 180 degrees apart. The end 185 of structural support element 152 is then connected to the center of linking wire 192 , such as with a ball stop.
In a further embodiment shown in FIGS. 3E and 3F , linking wire 200 is routed across a row of tube ends, and linking wire 202 is routed across a column of tube ends. The end of structural support element 152 terminates in a threaded rod 208 . Structural element 152 can be a wire, in which case the threaded rod 208 can be attached such as by welding, by crimping or by ball stop. Alternatively, structural element 152 can be a rod, with threaded rod 208 merely being the end of structural element 152 , to which a thread has been applied, as with a chuck. The linking wires 200 and 202 cross at perpendicular angles at the centers of each tube 126 . A pair of internal guides 204 are provided for each tube 126 that linking wires 200 and 202 are routed across. Threaded rod 208 is then attached to the intersection of linking wires 200 and 202 , for example using internal nut 210 , internal washer 212 , external washer 214 and external nut 216 . Alternatively, linking wires 200 and 202 can be formed as a mesh, with washers at their intersecting points at the center of each tube. Threaded rod 208 can then be inserted through the central washer and secured with an external nut.
The turbulence-inducing elements 150 are configured and dimensioned to direct the flowing heat transfer fluid towards the inner surface of the tube wall. For example, FIG. 4 schematically illustrates the turbulent flow that is created inside the inner tube 126 and, in particular, the flow that is created around the turbulence-inducing elements 150 . According to the present invention, fluid flow is directed toward the tube's inner wall surfaces to thereby disrupt the boundary layer that would otherwise form along the surface of tubes not having the turbulence-inducing elements 150 , with the result being that a region of turbulence is created downstream of the maximum diameter of the device. The likelihood of accumulation of impurities on the inner surface of the tubes is thereby eliminated or minimized because of the turbulent flow created by the apparatus of the present invention.
In addition, FIG. 4 shows that as the fluid flow moves along the tube length, and additional downstream turbulence-inducing elements are encountered, the deflection of fluid by the turbulence-inducing elements is cumulative. For example, a first turbulence-inducing element generally receives a generally laminar flow of fluid from the upstream end of the tube, while a second turbulence-inducing element receives fluid with a flow path that has been deflected by the first turbulence-inducing element, and then a third turbulence-inducing element receives fluid with a flow path that has been deflected by both the first and second turbulence-inducing elements.
FIGS. 5A, 5B, and 5C show a series of front, side, and rear views of one embodiment of a turbulence-inducing element 250 . Turbulence-inducing element 250 includes a first portion 260 which is positioned towards the upstream end of the tube and a second portion 270 towards the downstream end of the tube. The distal end 262 of the first portion 260 has a cross-sectional area smaller than the maximum cross-sectional area of the second end portion 270 . In general, the cross-sectional area of the first portion increases in the direction of fluid flow as arranged in the tube, and the cross-sectional area of the second portion decreases in the direction of fluid flow. Note, however, that the cross-sectional area of the distal end 262 of the first portion 260 should not be larger than the diameter of structural support element 252 , to prevent a perpendicular impingement of fluid particles on the distal end 262 .
Furthermore, in preferred embodiments of the present invention, the turbulence-inducing elements are symmetrical about their longitudinal axes, i.e., from the upstream portion to the downstream portion. Such an arrangement permits a balanced distribution of the transferring fluid within the tube and along the inner wall of the cylindrical tube as shown in FIG. 4 . The thorough mixing of the heat transfer fluid increases the overall efficiency of the unit by disrupting the generally laminar flow of the liquid.
The first portion 260 of the turbulence-inducing element 250 is configured generally in the shape of a conical frustum, with the distal end 262 formed as a truncated apex or a truncated curved or rounded apex. In certain embodiments, the truncation can be minimized such that the distal end approaches an apex or rounded apex, depending on the diameter of the structural support element 252 . In a preferred embodiment, the distal end 262 is configured so as to minimize any energy loss associated with localized pockets of turbulence, which would otherwise deleteriously increase the pressure drop along the tube.
The turbulence-inducing element 250 can be attached to the structural support element 252 by any of a number of means. In a preferred embodiment, the turbulence-inducing element 250 can be cast on the wire or rod of the structural support element 252 . Alternatively, the turbulence-inducing element can be hollow or have a light-weight core between the distal end and the center of the convex second portion so that the rod can be inserted through and welded in place. Other examples include attaching the turbulence-inducing element 250 to structural support element 252 by crimping or pinning.
In one preferred embodiment, the shape of the second portion 270 facing the downstream end of the tube is generally convex. The edges 266 of the interface 264 between the imaginary transverse plane of the base of the first portion 260 , e.g., a plane characterized by a plurality of circumferential lines of a cone-shaped structure, and the imaginary base of the second portion 270 (shown in broken lines) are preferably rounded or partially rounded.
The configuration of the second portion can be any suitable shape that minimizes or eliminates edges, as this will minimize or eliminate the accumulation of material that can promote surface fouling of the second portion.
In preferred embodiments, the configuration of the second portion includes a closed outer surface to prevent heat transfer fluid from accumulating within the turbulence-inducing elements.
As shown in FIG. 5 , the shape of the second portion can be a convex shape or a hemi-spheroid or other curvilinear shapes. FIGS. 6-9 show various additional examples of suitable shapes for the second portion. In one embodiment, as shown in FIG. 6 , a turbulence-inducing element 350 includes a first portion 360 in the configuration of a conical frustum and a second portion in the configuration of a truncated convex shape or a hemi-spheroid shape. In another embodiment, as shown in FIG. 7 , a turbulence-inducing element 450 includes a first portion 460 in the configuration of a conical frustum and a second portion 470 comprising a small surface area truncated apex, e.g., with the area of the truncated portion approaching the cross-sectional area of the supporting member. In a further embodiment, as shown in FIG. 8 , a turbulence-inducing element 550 includes a first portion 560 in the configuration of a conical frustum and a second portion 570 comprising a surface having a rounded apex. In still another embodiment, as shown in FIG. 9 , a turbulence-inducing element 650 includes a first portion 660 in the configuration of a conical frustum and a second portion 670 comprising surface having a relatively large area truncated apex, e.g., with the area of the truncated portion many times larger than the cross-sectional area of the rod, as shown in FIG. 9 .
One of ordinary skill in the art will appreciate that other configurations can be applied to the second portion of the turbulence-inducing elements according to the present invention, including a cross-sectional area that generally decreases in the direction of fluid flow.
The first portion of the turbulence-inducing elements can also be one of many shapes that have a cross-sectional area that generally increases along the direction of fluid flow, with the exception of embodiments shown in FIGS. 14-15 in which protruding elements are provided on the lateral surface of the first portion to induce additional turbulence and, in one embodiment, to assist in maintaining the turbulence-inducing elements aligned with the longitudinal axis of the tube. For instance, as shown in FIGS. 5-9 , the first portion can be a conical frustum. In another embodiment, and referring to FIG. 10 , a turbulence-inducing element 750 includes a first portion 760 in the shape of a conical frustum having a concave lateral surface 768 . In a further embodiment, and referring to FIG. 11 , a turbulence-inducing element 850 includes a first portion 860 in the shape of a pyramidal frustum. Embodiments of the first portion 860 preferably have bases with at least five sides to minimize pocket areas along the lateral surface of the pyramid, and more preferably have bases with an even number of sides to provide a symmetrical turbulence-inducing element. In an additional embodiment, and referring to FIG. 12 , a turbulence-inducing element 950 includes a first portion 960 in the shape of a star pyramid frustum. In certain embodiments, including those described with respect to FIGS. 5-12 , the first portion is configured so that energy loss is minimized along the direction of fluid flow.
One of ordinary skill in the art will appreciate that other configurations can be applied to the first portion of the turbulence-inducing elements according to the present invention that have a cross-sectional area that generally increases in the direction of fluid flow.
In further embodiments, and referring to FIGS. 13-15 , one or more of the turbulence-inducing elements used in a tube can include additional features or extensions. In particular, with reference to FIGS. 13A, 13B, and 13C , a turbulence-inducing element 1050 includes grooves 1072 distributed about the circumference of the element 1050 . The grooves generally begin at the halfway point of the first portion 1060 (which in the embodiment shown is in the configuration of a conical frustum), and extend downstream along its lateral surface to the base of the first portion 1060 . The grooves 1072 begin at a shallow depth, with the depth increasing as the grooves extend downstream, and the grooves end at the intersection between the base of the first portion and the second portion; upon encountering the solid second portion, the streams are directed out toward the tube wall. The grooves are preferably distributed evenly around the conical frustum to maintain the device at the tube center, i.e., to prevent fluid flow from creating asymmetrical forces that could displace the turbulence-inducing elements 150 towards the inner wall of the tube. In a preferred embodiments, the grooves 1072 are straight to avoid rotation-inducing forces on the turbulence-inducing elements, which could cause them to separate from the structural support element. In an alternate embodiment, the symmetrical grooves are curved, with mirrored curved grooves at complementary locations that prevent rotation of the turbulence-inducing elements.
In another embodiment, with reference to FIGS. 14A, 14B, and 14C , a turbulence-inducing element 1150 includes a first portion 1160 having conical studs or spikes 1174 distributed on its lateral surface. These studs 1174 increase turbulence within the tube, thus providing a further enhancement to the anti-fouling and thermal mixing benefits of the turbulence-inducing element of the present invention. The studs can be conical, frustoconical, pyramidal, cylindrical, hemi-cylindrical, or of other suitable shapes. In one embodiment, these projections from the first portion 1160 can extend to the inner tube walls, maintaining the device at the tube center to avoid fouling accumulation. The studs may be cast or molded with the body of the turbulence-inducing element, or can be welded to the body, or can be inserted into holes designed for that purpose and pinned into place.
In a further embodiment, as shown in FIGS. 15A, 15B, and 15C , a turbulence-inducing element 1250 includes grooves 1272 distributed evenly about the circumference of the element 1250 (as described with reference to FIG. 13 ), and a first portion 1260 having conical studs 1274 distributed on its lateral surface (as described with reference to FIG. 14 .)
The arrangement of the turbulence-inducing elements within a tube can follow the general configuration shown and described above with respect to FIGS. 3A and 3B . In further embodiments, referring generally to FIGS. 16, 17 and 18 , additional elements are included at certain locations on the structural support element to provide suitable tension and expansion capabilities to the apparatus of the present invention. In particular, FIG. 16 is a schematic illustration of an apparatus 1348 including a plurality of turbulence-inducing elements 1350 arranged along the structural support element 1352 , similar to that described with respect to FIGS. 3A and 3B . In addition, a portion of the structural support element 1352 proximate each end is provided with springs 1380 . The distal ends of the structural support element 1352 are attached to the linking wires at the tube ends in a manner similar to that described with respect to FIGS. 3A and 3B .
The spring 1380 is preferably formed as helical extension spring having coils that are suitably dimensioned and spaced apart so as to minimize or prevent the likelihood of fouling inside the spring and/or on the tube's inner wall surface proximate the spring. In particular, the outer coil diameter is smaller than the inside tube diameter, with sufficient clearance to prevent scraping of the inner tube wall. Further, the coil spacing, known as the “pitch” of a spring, is sufficiently large to allow fluid to flow through the spring without substantial resistance to minimize or prevent the likelihood of fouling inside the spring. For example, each spring element 1380 can have an outer diameter one-half of the tube's inside diameter, and the spacing between coils of the spring can be between the tube's inside diameter and the tube's outer diameter. It will be appreciated that the spacing between coils depends upon the tension and the coil factor, in addition to any stop ball that may be in place.
Advantageously, including one or more spring elements on the turbulence-inducing apparatus of the present invention facilitates installation of the apparatus, allows for stresses to be absorbed thereby reducing the stress load on the structural support element and the end connections, and maintains tension in the apparatus 1348 even under conditions of transferring fluid flow surge. In addition, spring elements can minimize the tendency of the structural support element 152 to expand longitudinally during operation due to high temperatures, and also to minimize the tendency of the turbulence inducing devices 150 to sag toward the bottom surface of the tube due to gravity. The use of the spring elements can such sag and maintain the turbulence-inducing elements the longitudinal centerline of the tube.
Referring now to FIG. 17 , an apparatus 1448 includes a plurality of turbulence-inducing elements 1450 arranged along the structural support element 1452 , with spring elements 1481 near each end. In particular, spring elements 1481 each include a first terminal end 1482 that extends through the coils of the spring elements to the turbulence-inducing element 1450 , and a second terminal end 1483 that also extends through the coils, in the opposite direction as terminal end 1482 , to each of the ends 1484 , 1486 of the structural support element 1452 . Accordingly, in the event of forces that cause displacement of the turbulence-inducing elements within the tube, the coils of the spring elements 1481 compress and the overall length of the structural support element 1452 increases by the compression length of the spring elements 1481 . Such an arrangement allows for extension of the overall length of the structural support element 1452 while preventing overstretching of the spring elements 1481 .
Referring now to FIG. 18 , a further embodiment of an apparatus for use in a heat exchanger tube for promoting turbulence of transferring fluid and minimizing fouling and other detrimental effects associated with boundary layer accumulation is shown. In particular, apparatus 1548 includes a plurality of turbulence-inducing elements 1550 arranged along a structural support element 1552 . A joint element 1590 is provided between a portion of the structural support element 1552 and a separate spring element 1580 . At each end, the structural support element 1552 extends from the separate spring element 1580 to end 1584 , 1586 . An additional safety wire 1554 is connected at one end to the joint element 1590 and is connected at its other free end to a safety stop 1558 , which is shown in FIG. 18 as a ball stop. The additional safety wire 1554 is inserted through the separate spring element 1580 and a sliding opening 1592 fixed to the structural support element 1552 . (For purposes of illustration only, in FIG. 18 the additional safety wire 1554 is not inserted through the separate spring element 1580 and sliding opening 1592 and, therefore, is not shown in its operational position.) In FIG. 18 , the sliding opening 1592 is shown as a ring. The benefit of the additional safety wire 1554 is that the safety stop 1558 can act as a brake or safety guard for preventing damage to the separate spring element 1580 , by preventing the spring from stretching beyond a predetermined distance.
Referring now to FIGS. 19A and 19B , a further embodiment of an apparatus for use in a heat exchanger tube for promoting turbulence of transferring fluid and minimizing fouling and other detrimental effects associated with boundary layer accumulation is shown. FIG. 19A illustrates a side view of the embodiment in a heat exchanger tube 1610 , and FIG. 19B illustrates a downstream end view of the embodiment. In particular, apparatus 1600 includes turbulence-inducing elements that are formed from an assembly of two cones, namely, an outer cone 1620 and an inner cone 1630 nested inside. The two cones are arranged such that an annular gap 1650 is formed between the outer cone 1620 and the inner cone 1630 .
The outer cone 1620 is hollow. At the upstream end, the wall of the outer cone 1620 is relatively thin. At the downstream end, the wall of the outer cone 1620 is relatively thick. The inner cone 1630 includes a substantially closed outer surface and is affixed to the central wire in the same manner as described in the earlier embodiments.
The inner cone 1630 is connected to the outer cone 1620 via a plurality of longitudinal strips 1640 that are plate welded. It is preferable to use an even number of longitudinal strips to provide a symmetrical load which helps to maintain the cone assembly at the tube center. In a preferred embodiment, four longitudinal strips are utilized.
This embodiment will provide for more turbulence during fluid flow for more fluid mixing. In addition, because this configuration allows a portion of the transferring fluid to flow through the annulus gap between the two cones, it creates less erosion to the pipe's inner surface compared with the previously described embodiments. This embodiment is useful in situations where a large cone diameter is required for generating additional turbulence, which would otherwise cause erosion to the pipe's inner surface if some fluid was not permitted to flow through the inside of the cone assembly as described above.
Referring to FIG. 20 , the dimensions and spacing of the turbulence-inducing elements illustrated in FIGS. 19A and 19B relative to the tube size are described according to the below formulas, according to one example.
A gap (g 1 ) is maintained between the inside tube diameter (ID) and the outer diameter of the outer cone 1620 , according to the following formula:
g 1=0.1 *ID (6)
A gap (g 2 ) is maintained between the outer cone 1620 and the inner cone 1630 , according to the following formula:
g 2=0.1 *ID (7)
The thickness (t) of the base of the outer cone 1620 is determined according to the following formula:
t= 0.15 *ID (8)
The diameter (d) of the base of the inner cone 1630 is determined according to the following formula:
d=ID− 2* g 1−2 *g 2−2* t (9)
The length (L 1 ) of the outer cone 1620 is the same as the length (L 2 ) of the inner cone 1630 and is determined by the following formula:
L =1.5 *ID (10)
The spacing (S) between adjacent cone assemblies is determined by the following formula:
S =3.5* d /( g 1 +g 2) (11)
The cone assembly of this embodiment does not include a second portion extending towards the downstream end of the tube as was described with some of the above embodiments.
Advantageously, the apparatus of the present invention can be integrated in new or existing heat transfer devices. Unlike prior art systems that attempt to impart turbulence to fluid flowing in a heat transfer device, the apparatus of the present invention can be installed in clean or fouled existing tubes of a heat transfer device.
In addition, the turbulence-inducing devices of the present invention are not designed to contact the tube's inner surface during operation, unlike prior art systems that attempt to impart turbulence to fluid flowing in a heat transfer device.
In an alternative embodiment one or more radial supporting devices are installed on, and extend radially from the longitudinal support element to contact the adjacent wall of the tube. The supporting device can be constructed from one or more pieces of wire tubing or other rigid material to provide three or four points of contact with the inner surface of the tube to thereby maintain the structural support element aligned with the longitudinal axis of the tube. The arms can be spaced from each other at intervals of 120° or 90°. The radial supporting devices can also be fabricated by casting metal or plastic materials with radial arms extending from a central hub.
Referring again to FIG. 14 , in yet another alternative embodiment, one or more radially-extending supporting devices are installed on, and extend radially from the surface of, the turbulence-inducing devices to contact the adjacent wall of the tube. In this embodiment, it is preferred that the radially-extending supports are positioned in groups at one or more circumferential locations along the longitudinal axis of the turbulence-inducing element, wherein adjacent circumferential groups are spaced from each other along the central axis of the turbulence-inducing element. In one example, a single circumferential group includes four radial supports, being spaced at substantially 90 degrees from each other. Preferably, each circumferential group includes radial supports in multiples of four. The length of each radial support depends on the shape of the turbulence-inducing element and the location of the radial support on the surface of the turbulence-inducing element. For example, referring to the turbulence-inducing element shown in FIG. 14 , radial supports in a first circumferential group have lengths that differ from radial supports in an adjacent circumferential group, such that all of the radial supports extend a substantially uniform distance from the longitudinal axis of the element.
The special geometry and studs serve to center the device in the tube during operation, preventing or reducing build-up of deposits inside the tubes. Existing turbulent devices that are held in position by contacting the tube inner surface lead to fouling at the contact points with the tube surface. This complicates maintenance because of the difficulty of first removing the turbulent devices without damaging them and then cleaning the tubes.
The method and apparatus of the present invention have been described above and in the attached drawings; however, modifications will be apparent to those of ordinary skill in the art and the scope of protection for the invention is to be defined by the claims that follow. | A heat exchanger tube for conveying a heat transfer fluid, into which one or more turbulence-inducing elements are fixedly positioned on a supporting member extending in spaced relation along the central axis of the tube. The turbulence-inducing elements have a first portion facing upstream and a second portion facing downstream. The entire exterior surface of the first portion forms a continuous solid surface that blocks and deflects the path of the flowing fluid. | 5 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
This application is a Divisional of U.S. application Ser. No. 12/591,487, filed Nov. 20, 2009, now U.S. Pat. No. 8,201,979 incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The Invention relates to collapsible structures, in particular a collapsible structure having an operational unit that can be transported.
2. Background of the Invention
Flashlights have been used extensively in areas where lighting is not available. In many circumstances, however, flashlights are inadequate because they fail to provide adequate lighting to accommodate the needs of workers, campers, or persons engaged in other activities. Portable lights which stand alone provide necessary levels of light while leaving workers and other individuals free hands to perform tasks and conduct other activities. Portable lights, however, tend to be bulky and large and inconvenient to carry. The invention disclosed herein provides a collapsible light in a form factor which is portable and easy to carry to provide light for many applications.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a collapsible structure according to the invention in a collapsed position for transport;
FIG. 2 illustrates a collapsible structure in a collapsed position as it might be carried on a back of a person;
FIG. 3 shows a collapsible structure according to the invention in a fully deployed position;
FIG. 4 shows a strut in an assembly for use in a collapsible structure according to the invention;
FIG. 5 shows a portion of a collar assembly in a collapsible structure according to the invention;
FIG. 6 shows an exploded view of the elements of a collapsible structure according to the invention;
FIG. 7 shows a transparent view of a collapsible structure according to the invention in the collapsed position to illustrate its internal configuration;
FIG. 8 shows a bottom perspective view of a collapsible structure according to the invention in a collapsed position;
FIG. 9 shows the collar, base and legs of an assembly according to the invention;
FIG. 10 is a side view of a collapsible structure according to the invention in a collapsed position;
FIG. 11 illustrates the position of a multifunction power switch in a collapsible structure according to the invention;
FIG. 12 illustrates an operational unit in a collapsible structure according to the invention from a front perspective position; and
FIG. 13 illustrates an operational unit in a collapsible structure according to the invention from a rear perspective position.
FIG. 14 illustrates a latching mechanism for use in a collapsible structure according to the invention.
FIG. 15 is an electrical schematic of a collapsible structure according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a collapsible structure 101 , such as a collapsible light, according to the invention in a substantially cylindrical form factor, resembling a bazooka, for easy transport. Collapsible structure 101 has attached to it a carrying strap, 103 , to facilitate carrying the bazooka-shaped collapsible structure 101 on one's back, as illustrated in FIG. 2 . FIG. 1 further shows securing strap 105 . Securing strap 105 can be used as one way to secure the legs, as discussed further herein, to form an exterior portion of the cylindrical shape in the collapsed position. Other means for securing the legs in the collapsed position can also be used. FIG. 1 further illustrates operational unit 150 , such as lamp head 107 , which has sockets therein for illuminating elements. As shown in FIG. 1 , lamp head 107 is tucked into a collar 109 to protect the lamp head 107 when the collapsible structure 101 is in the collapsed position.
FIG. 3 illustrates an embodiment of the collapsible structure 101 according to the invention in the deployed position. As shown in FIG. 3 , the structure of the collapsible structure 101 according to the invention includes a main body 301 which mounts on top of a lower body serving as a battery compartment 303 to form a substantially cylindrical shape. The main body 301 and battery compartment 303 can be formed separately or as an integrated unit. Other shapes, such as triangular, square, oval and rectangular, may also be employed without departing from the scope of the invention.
The invention also is not limited to any particular battery type. For example, the battery can be rechargeable or non-rechargeable. Battery charging circuitry and a suitable plug to an external power source may be incorporated into the lower body battery compartment 303 , or elsewhere in the collapsible structure 101 , as may be convenient. It is within the scope of the invention to provide illumination using an AC power source and/or one or more transformers.
The interior of main body 301 can house electrical cables, such as a coiled electrical cable (not shown), to deliver electrical power to one or more illuminating elements, such as light emitting diodes, in the lamp head 107 . Other types of illuminating elements, such as incandescent, halogen or fluorescent light elements, may be used in lamp head 107 , without departing from the scope and spirit of the invention. As discussed further herein, the main body 301 also accommodates one or more telescoping members 608 , which allow the operational unit 150 of the collapsible structure 101 according to the invention to be set at different heights to provide light over different size areas.
The main body 301 is surrounded by collar 109 . In the exemplary configuration shown in FIG. 3 , collar 109 is a two part hollow cylindrical member, including upper collar portion 305 and lower collar portion 307 . The upper and lower collar portions, 305 and 307 , may be formed separately and connected together or may be formed as an integrated unit. Upper collar portion 305 has a wider outer diameter than lower collar portion 307 .
One or more legs 309 are pivotally attached or hinged to lower collar portion 307 at pivot points 311 . The legs 309 preferably have a curved shape, such that when the portable light according to the invention is in the collapsed position, the legs 309 form a cylindrical exterior surface which approximates the exterior surface of the upper collar portion 305 .
Optional metal prongs 312 on the interior surface of legs 309 exert a spring force biasing legs 309 outward from the lower collar portion 307 into the deployed position. Struts 310 control the outward extension of legs 309 . Struts 310 are pivotally connected to the lower portion of the central section of the collapsible structure 101 , for example to battery compartment 303 , and pivotally connected to the interior portion of legs 309 . Struts 310 act to control the legs 309 as they deploy away from the outer surface of the lower collar portion 307 , limit the distance the legs 309 deploy and provide stability when the legs 309 are fully deployed. Those of ordinary skill will recognize that struts 310 could be connected at different locations on the interior surface of the legs 309 and on the central section of the collapsible structure 101 to achieve different relationships between the legs 309 and the central section of the collapsible structure 101 as desired. For example, the struts 310 could be positioned and sized such that the base 313 touches the ground or other surface beneath the base 313 when the collapsible structure 101 is deployed. Alternatively, struts 310 could be positioned and sized to insure that the base 313 does not touch the ground or other surface beneath the base when the collapsible structure 101 according to the invention is deployed.
FIG. 4 illustrates one possible configuration of strut 310 . The strut 310 has a central member 401 extending between a first strut leg 403 which pivotally engages a leg 309 and a second strut leg which pivotally engages the battery compartment 303 . Other strut configuration may be used without departing from the scope of the invention.
When the legs 309 are collapsed, the exterior surface of each leg 309 is substantially aligned with the exterior surface of lower collar portion 307 , thereby forming a substantially cylindrical shape covering the main body 301 and battery compartment 303 . Base 313 encloses battery compartment 303 forming a battery compartment lid at its bottom portion. As shown in FIG. 3 , base 303 has an outer diameter which approximates the outer diameter of the upper collar portion 305 . In one exemplary configuration, a lip 315 formed by the exterior of the battery compartment 303 and base 313 can be entirely recessed or recessed in one or more locations so that 7 when legs 309 are collapsed, they can be held in place by the recesses. As noted above, however, an alternative is to hold legs 309 closed with a strap 105 .
In operation, collar 109 and main body 301 move relative to each other, so that the collapsible structure 101 can be deployed or placed in the collapsed position. Collar 109 has hand grips 320 , which are openings in the upper collar portion 305 . These openings serve as hand grips for use in collapsing the collapsible structure 101 . When the collapsible structure 101 is deployed and the collar 109 is lifted using hand grips 320 , legs 309 lift from the surface on which they sit and move toward the battery compartment 303 . This movement of the legs 309 toward the battery compartment 303 drives the collar 109 upward relative to the main body 301 . When the collapsible structure 101 is deployed from the closed position, collar 109 moves downward relative to the main body 301 , as the legs 309 move away from the battery compartment 303 .
In order to facilitate and control the movement between the main body 301 and the collar 109 , main body 301 has slots 317 on its exterior surface 319 . Slots 317 can be formed either as indentations in the exterior surface 319 of the main body 301 or parallel protrusions from the exterior surface 319 .
As shown in FIG. 5 , at least one part of collar 109 , such as lower collar portion 307 , has on its interior one or more guides 501 . Guides 501 engage slots 317 in main body 301 and slide therein. FIG. 5 also shows lower collar portion 307 having one or more other interior members 503 on its inner surface. Interior members 503 provide added strength to the collar portion. In addition, because interior members 503 extend inward toward the main body 301 , interior members 503 help to control lateral movement or wobbling between the main body 301 and the collar 109 .
FIG. 6 is an exploded view of the elements of the exemplary embodiment of the collapsible structure 101 according to the invention as discussed herein. FIG. 6 illustrates how the various elements previously discussed fit together. In addition, FIG. 6 illustrates a battery pack 601 for insertion into battery compartment 303 . FIG. 6 also shows top cap 603 which mounts into the upper portion of main housing 301 . Top cap 603 includes power switch 605 . Power switch 605 can be a on-off switch or can be configured to cause operational unit 150 , such as lamp head 107 to emit multiple levels of illumination, for example, dim, medium and bright. Switch 605 can also be configured to turn on illuminating elements in the lamp head 107 in a desired sequence. Switch 605 can also be continuously variable, so that the lamp head 107 can be dimmed. The switch 605 can be any type suitable for turning on operational unit 150 , for example a rotary switch, without departing form the scope of the invention.
Preferably, top cap 603 and base 313 along with main body 301 and battery compartment 303 form a watertight enclosure, which protects elements within the main body 301 , particularly during transport. The elements within this watertight enclosure include the battery pack 601 , electrical circuits and switches, cables supplying electrical power to the operational unit 150 , and telescoping member 608 , which adjusts the height of the operational unit 150 . Such a watertight enclosure also helps facilitate flotation of the collapsible structure 101 according to the invention, should it fall into a liquid.
Top cap 603 has opening 607 which accommodates one or more telescoping tubes. FIG. 6 shows a telescoping member 608 that includes fixed tube 609 with cam lock 610 and a telescoping tube 611 which fits within fixed tube 609 . The cam lock 610 can be used to set the height of telescoping tube 611 to any desired position within the range of the length of the tubes. More than one telescoping tube and cam lock can be used without departing from the scope and spirit of the invention. Electrical power to the operational unit 150 is typically delivered through a coiled cable (not shown) which fits within the tubes and extends to a length appropriate to size and number of telescoping tubes.
FIG. 7 is a transparent view of the collapsible structure 101 according to the invention, which illustrates the components of the collapsible structure 101 in the collapsed position for transport. FIG. 7 also illustrates an optional protective feature which can be provided by collar 109 . As shown in FIG. 7 , collar 109 and operational unit 150 , such as lamp head 107 , are sized such that when the collapsible structure 101 is collapsed and the telescoping tubes 611 of the telescoping member 608 are retracted into each other, operational unit 150 fits within collar 109 . Thus, when sized this way collar 109 protects operational unit 150 from damage during transport. As noted, however, this feature is optional and operational unit 150 can be of any desired size. FIG. 7 illustrates still another feature of the collapsible structure 101 according to the invention. As shown in FIG. 7 , the collapsible structure 101 according to the invention can be scalloped in at least one area 701 to facilitate carrying the unit on one's back, for example using should strap 103 as previously disclosed herein.
FIG. 8 illustrates a perspective view of the collapsible structure 101 according to the invention in a closed position. FIG. 8 illustrates base 313 , which forms a battery compartment lid, with a rim 801 to protect the battery compartment 303 . The battery compartment lid provides access to change the batteries, which power the operational unit 150 . Connections between the battery and the cable to the operational unit 150 are internal to the battery compartment. The battery compartment 303 can also have a charging socket 803 , as shown in FIG. 8 . Charging circuitry is internal to the battery compartment 303 and is not shown.
FIG. 9 is a more detailed illustration of the pivot connection between lower collar portion 307 and legs 309 . As noted previously, a metal prong can be used to bias the legs 309 outward toward the deployed position. FIG. 9 shows another arrangement in which latch 901 is used to lock legs 309 into the deployed position.
The side view in FIG. 10 illustrates another approach to locking in the closed position. In FIG. 10 latch 1001 is used to latch the collar 109 to the legs 309 to maintain the collapsed position. FIG. 10 also illustrates the cylindrical shape, resembling that of a bazooka, of the collapsible structure 101 according to the invention when in the collapsed position.
FIG. 11 is a more detailed illustration of switch 605 as located in main body top cap 603 . Switch 605 can be equipped with a backlight, such as an LED, or other indicator to provide an indication of the current charge level.
FIG. 12 shows the lamp head 107 from the front, or illuminating side, as connected to an end of the telescoping tube 611 . As illustrated in FIG. 12 , lamp head 107 is connected to the telescoping tube 611 using a connector 1201 which can pivot and/or rotate within the telescoping tube 611 to provide a wide range of motion. FIG. 12 also shows light emitting diodes 1203 in the lamp head 107 , which illuminate to provide light. One or more other types of illuminating members could also be used. For example, the light emitting diodes could be replaced with or used in conjunction with halogen bulb, fluorescent bulb and/or incandescent bulbs. Any desired combination of such illuminating elements could be controlled by switch 605 to illuminate in any desired sequence, without departing from the scope of the invention.
FIG. 13 shows lamp head 107 connected to telescoping tube 611 from the rear of the lamp head 107 . As shown in FIG. 13 , when pivoting connector 1201 is an offset hinge. Offset hinge 1202 includes a member 1301 , which connects at a first end to the telescoping tube 611 . Member 1301 can be arranged to rotate within tube 611 , thereby allowing lamp head 107 to be placed anywhere in a 360 range to direct light as desired. A second end of member 1301 pivotally connects to member 1302 , which is connected to lamp head 107 . By pivoting second member 1302 about point 1303 , light from lamp head 107 can be directed vertically as desired. As shown, offset hinge 1201 permits about 135 degrees of movement of lamp head 107 . Other arrangements which permit a wider or smaller range of motion may also be used. When the collapsible structure 101 according to the invention is to be placed in the collapsed position, lamp head 107 is pulled toward the telescoping tube 611 , such that member 1302 pivots about point 1303 to collapse member 1302 toward member 1301 . When member 1302 is collapsed on member 1301 , lamp head 107 is positioned so that the illuminating elements therein face upward vertically. In this way, when the telescoping tube 611 is lowered into the main body 301 , the lamp head 107 can be recessed into collar 109 , so that collar 109 protects the lamp head 107 . As illustrated in FIG. 12 , when deployed, the connection between the lamp head 107 and the main body 301 provides a wide range of motion, allowing the lamp head 107 to be rotated to direct the light in a preferred direction and to be pointed upward or downward at an angle limited only by the physical dimensions of the lamp head 107 and the pivoting connector 1201 . It will also be recognized that more than one pivoting connector 1201 can be used to direct light in any desired direction.
FIG. 14 shows a detail of a latch mechanism that can be used in a collapsible structure according to the invention. FIG. 14 shows main body 301 and leg 309 in the collapsed position. To deploy, one lifts the flexible latch 1401 located on battery compartment 303 . Leg 309 deploys outward from the main body 301 until member 1402 aligns with groove 1403 . Lifting latch 1401 to disengage member 1402 from groove 1403 allows the collapsible structure 101 to return to the collapsed position. In this position, hoop 1405 on the inside of the leg 309 engages with a corresponding fork 1406 , thereby eliminating the need for a leg strap to hold the legs 309 in collapsed position.
FIG. 15 is an electrical schematic of the collapsible structure 101 according to the invention. Those of ordinary skill will recognize that the circuits implement the features previously discussed herein. Microcontroller 1501 , such as MSP430F2002IPW, provides general control and operation to control LED drivers 1503 , 1505 , 1507 , and 1509 , for example, CAT 4101. These regulate the current to (drive) LEDs 1510 and 1512 , 1514 , and 1516 . LEDS 1510 , 1512 , 1514 , and 1516 receive power from fuse/resistor circuits 1502 , 1504 , 1506 , and 1508 . Voltage regulator 1511 provides voltage regulation from battery 1513 . Battery 1513 may be recharged through charging connector 1515 and charging circuit 1519 . Microcontroller 1501 is programmed to perform its functions through programming connector 1517 .
The above description for a collapsible structure, such as a portable light, is illustrative, as the structure of the invention may be used in conjunction with other devices. It will be recognized that the lamp head 107 may be replaced by other operational units 150 performing other functions. For example, the lamp head 107 may be replaced by a speaker to broadcast sound, a device which provides heat, a fan, a sensor to measure contaminants or air quality or any other number of devices. Indeed, the operational unit 150 connected to the telescoping member 608 need not be powered. For example, the operational unit 150 in the description above may be replaced by a reflector or a solar powered device, which generates its own power. In the case of an operational unit 150 , which does not require power, the battery compartment 303 can remain empty. In still another application, the operational unit 150 connected to the end of the telescoping member 608 may be one which generates electrical power, such as a windmill or solar collector. In that case, the battery compartment 303 discussed above may be used to house energy storage devices. | A collapsible device has a main body surrounded by a collar whose position is adjustable along the longitudinal axis of the main body. Pivotally connected or hinged legs are attached to the collar and to the main body with struts. When the collar is on one position, the legs deploy outward from the main body to the extent permitted by the struts, thereby allowing the legs to support the collapsible device upright. An operational unit is attached to a member that telescopes from the main body. When the collar is another position, the legs are drawn in toward the main body to form a cylindrical shape for facilitating transportation. The operational unit can be positioned so that when the telescoping member is retracted into the main body, the collar surrounds the exterior of the operational unit, thus protecting the operational unit for transport. | 8 |
BACKGROUND OF THE INVENTION
A lamp base for an incandescent lamp comprises a metallic threaded shell, a central eyelet and insulating glass which serves to insulate the eyelet from the base shell as well as secure the eyelet centrally in the open bottom of the base shell. In the automated manufacture of incandescent lamp bases, the eyelet and the shell are placed in a nest on an indexing turrent of the base making machine and a gob of molten glass of predetermined size and viscosity is then delivered to the nest. A glass plunger assembly then forms the glass and spreads the eyelet flanges embedding them into the glass as the glass hardens to form the interconnection between the eyelet and the base shell while providing the required insulation between the two parts. Prior art turrets with a single nest at each of the indexing stations on the base turret could be fed from a single stream of glass by severing the glass stream and while forming a ball with the next glass stream the prior gob of glass was delivered directly into the nest.
In order to speed up the manufacture of bases on a single base making machine, a second ring of nests were provided on the turret in order that each index would produce two bases instead of one. U.S. Pat. No. 2,957,276 to A. L. Spaller illustrates the use of two separate glass streams to deliver glass gobs to the side-by-side nests at each index location of the turret. Since the viscosity of the glass gob when it reaches the nest is critical and is effected by time and delivery distances from the furnace orifices from which the glass stream flows, having two separate glass streams doubles the problem of maintaining the glass between its critical parameters. By employing a single glass stream and severing that glass stream in order to delivery glass gobs simultaneously to two different nests on the indexing turret cuts these problems in half.
SUMMARY OF THE INVENTION
In accordance with the present invention an apparatus is provided for forming and delivering insulating glass to an indexing turret on a lamp base making machine by providing a dial support having a horizontally disposed wear plate forming the upper surface thereof and an elongated vertically disposed aperture extending through the dial support and wear plate and having a drive shaft mounted for rotation within the vertical aperture carrying a circular dial mounted to the upper end thereof and positioned for rotation with its bottom side in contact with the wear plate. The circular dial has a plurality of chambers therein with each of the chambers having an opening in the top and bottom surfaces thereof. The openings in the top surface of the dial are located on the first circular locus radially equidistant from the center of the dial while the openings in the bottom surface are alternately located on the first circular locus and on a second circular locus which is radially equidistant from the center of the dial but being a greater distance from the center of the dial then the first circular locus. A glass stream receiving means is positioned over the first locus on the dial for receiving and directing a continuous stream of glass into the openings in the top surface of the dial. The wear plate is constructed and arranged to close off the openings in the bottom surface of the dial for a portion of the rotation of the dial thereby containing the glass within the chambers for a portion of the rotation. A gob guide chute is mounted to the dial support and includes gob guide apertures therethrough which are constructed and arranged to underlie the openings in the bottom of the circular dial whereby glass gobs released from the chambers in the circular dial through the bottom openings will be directed by the gob guide apertures to preselected locations on the indexing turret. In operation, the apparatus of this invention repetitively severs a continuous stream of molten glass into gobs of uniform weight and size with a continuously rotating dial. While the gobs of glass are in the dial chambers, these gobs of uniform weight and size are formed into a ball-like shape while being conveyed sequentially to a pair of radially different discharge locations. The ball-like gobs are then discharged from the rotating dial into nests on the indexing turret of the base making machine.
BRIEF DESCRIPTION OF THE DRAWING
Many of the attendent advantages of the present invention will become more readily apparent and better understood as the following detailed description is considered in connection with the accompanying drawing, in which:
FIG. 1 is a top plan view of a base making machine employing the dual gob feeder of this invention;
FIG. 2 is a side elevation view, partly in section of the dual gob feed mechanism of this invention;
FIG. 3 is a top plan view thereof;
FIG. 4 is a top plan view of the gob feed dial with a portion of the top plate broken away;
FIG. 5 is a sectional view taken along the line V--V of FIG. 4;
FIG. 6 is a schematic view illustrating the delivery of glass through the dial; and
FIG. 7 is a sectional view of a nest containing the lamp base after receiving a gob of glass.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now in detail to the drawing wherein like reference characters represent like parts throughout the several view, there is illustrated in FIG. 1 a top plan view of a glass base making machine incorporating the novel dual glass gob feeder of this invention. The general arrangement of the base machine is conventional and includes a base 10, a drive motor 12 which provides the power for the various operative equipments of the glass base machine through various gear reduction mechanisms and includes the drive for the main turret 14 which carries 72 base forming nests 16 therein. The general arrangement of the operative equipment associated with the nests 16 on the glass base machine turret 14 are the vibratory bowl 18 for deliverying eyelets to a pair of eyelet feed tracks 20 and 22 which delivery eyelets to the eyelet placer assemblies 24 and 26. The vibratory bowl and dual tracks delivery eyelets to the eyelet placer assemblies which place a single eyelet into each of the nests 16. The operation of the eyelet feed mechanism is disclosed in detail in copending application Ser. No. 095,819 filed Nov. 19, 1979 by James Petro and owned by the assignee of this invention.
As the nests proceed with a single eyelet in each nest a base shell is fed from the base shell storage hoppers 28 through shell feed tracks 30 to the shell placement assembly 32 which places a shell about the eyelet in each of the nests. The nests containing the eyelet and shell then proceed to the gob feeder assembly 34 which feeds a gob of molten glass to each of the nests, which molten glass proceeds to the bottem of the nest surrounding the eyelet and interior lower portion of the base shell. This gob feeder assembly, generally designated 34, forms the subject matter of this invention.
The nests containing the eyelet, base shell and gob of glass proceed to the glass plunger assembly 36 where the eyelet flanges are spread and embedded into the glass as the glass hardens to form the finished base shell and eyelet assembly. The base assemblies are then ejected from the nests at 38.
The dual gob feed mechanism of this invention generally designated 34 in FIG. 1 includes a furnace (not shown) including a molten glass metering device of the type disclosed in U.S. Pat. No. 4,162,152 issued July 24, 1979 to James Petro and owned by the assignee of this invention, for deliverying a continuous stream of molten glass 39 to the rotary gob feed mechanism. The rotary gob feed mechanism is best illustrated in FIGS. 2 and 3 and includes a base support member 40 mounted to the base 10 of the base making machine. The base support 40 has at the upper end thereof a wear plate 42 and an aperture 44 extending through both the base member 40 and the wear plate 42. Coolant, preferably water, enters the base support 40 through conduit 41, traverses the base support through a series of conduits (not shown) and exits from the base support through conduit 43. This coolant maintains the wear plate 42 in a cooled condition. A dial drive shaft 46 extends through the aperture 44 and is connected at its lower end to the main machine drive through a reduction coupling (not shown) and has mounted at its upper end the water cooled dial 48 which embodies the principal delivery mechanism of this invention. The dial 48 includes a cover plate 50 and is mounted for intimate engagement with the wear plate 42 when it is rotated by means of the dial drive shaft 46.
As best illustrated in FIGS. 4 and 5 the dial cover plate 50 is secured to the water cooled dial 48 by a plurality of bolts 52. The cover plate 50 includes twelve identical elongated apertures 54 therein with the openings in the apertures 54 in the top plate being located on a first circular locus radially equidistant from the center of the dial and equidistantly spaced one from the other on that locus. The apertures 54 communicate with chambers 56 and 58 in the water cooled dial 48. The chambers 56 and 58 are differently shaped and include at their bottom end an aperture 60-62 in the bottom surface of the water cooled dial 48. The apertures 62 associated with the chambers 58 are located essentially on the same circular locus as the openings or apertures in the top surface of a dial cover plate 50 with the apertures 60 associated with the chambers 56 being located on a second circular locus which locus is radially equidistant from the center of the dial but being a greater distance from the center of the dial then the first circular locus. As will be apparent as the description proceeds, gobs of glass are delivered from the chambers 56 to the inner circle of nests on the turret and to nests of the outer circle of the turret from the chambers 58. The rotary dial includes alternately therein six of the chambers 56 and six of the chambers 58.
The dial 50 also includes a plurality of circular channels 64 which surround each of the chambers 56 and 58. These channels carry continuously flowing coolant in form of water which enters the series of circular channels at 66 and exits therefrom at 68 after traversing each of the ring channels 64 which surround the chambers 56 and 58. Water is delivered to the channels 64 and returned therefrom by means of horizontal conduits 65 and 67, respectively, in the dial cover plate 50 which interconnect with a conventional rotary valve 69. Cooling water enters the rotary valve through conduit 71, proceeds through conduit 65 and channels 64 to return line 67 and then exits through conduit 73. The operation of the rotary valve will be readily apparent to one of ordinary skill in the art. Cooling the rotary dial maintains a uniform dial temperature and prevents sticking of glass to dial.
The glass stream 39 enters the gob feed mechanism through a fill bushing 70 which is pivotally mounted to the support 40 at 72 by a fill bushing support member 74 which permits the fill bushing to ride on the top plate 50 while being located on the same circular locus as the apertures 54 in the top plate 50. Water inlet line 76, conduit 77 in the fill bushing support 74 and water outlet line 78 permit cooling of the fill bushing 70, again to prevent the glass from sticking to the fill bushing.
A gob delivery chute block 80 is mounted by means of the delivery chute block support strap 82 to the support member 40. The gob delivery chute block 80 includes a first curved delivery chute or aperture 84 and a second curve delivery chute or aperture 86 each extending therethrough which serve as guides for the gobs of glass as they leave the bottom openings 60 and 62 respectively in the rotary dial 48. A gob leaving the bottom opening 60 in the chamber 56 will be delivered through the chute or aperture 84 into a nest on the inner circle of nests 16 while a gob leaving the bottom opening 62 in a chamber 58 will be delivered through delivery chute or aperture 86 into the outer circle of nests 16. The chutes 84 and 86 are essentially guides for the freely falling gobs of glass and closely approximate the free fall trajectory of a gob released from the rotating dial at a speed of approximately 30 revolutions per minute. The gob delivery chute block 80 may also be water cooled if desired.
An air blow system is provided and may be utilized when it is necessary to add some impetus to the removal of the glass gob from the bottom openings 60 and 62 of the dial. This is accomplished through an air delivery system which includes the air blow pipe 88 mounted to the post 90 through the pivot 92 which permits air to be blown through the orifices 94 and 96 which overlie the openings 54 in the top plate 50. As the bottom openings of their associated chambers reach their respective discharge openings.
In operation, the turret 14 is indexed at a rate of 180 indexes per minute which permits the manufacture of 360 bases per minute because of the pairs or sets of nests 16 at each index position. In order to deliver 360 gobs of glass per minute the water cooled dial must therefore rotate at 30 revolutions per minute. As glass is delivered from the glass furnace in the form of glass stream 39 into the fill bushing 70, the gob begins to build up on the top plate 50 until an orifice or opening 54 intersects the fill bushing at which point the built up glass as well as the continuing stream falls through the opening 54 in top plate 50 into the chamber 56 or 58 associated with that opening in the top plate. The glass moves downwardly and rewardly as in the case of the chamber 58 or laterally outwardly as in the case of the chamber 56 as well as rewardly. As illustrated in the schematic FIG. 5, the glass gob falls to the bottom of the chambers 56 and 58 through approximately 90° of rotation of the dial 48 until the bottom openings 60 and 62 come to the portion of the edge of wear plate 42 designated 98 and 100 where there is no longer a wear plate closing the bottom openings 60 and 62 in the chambers 56 and 58 at which point the ball-like gob of glass is permitted to exit from the chambers 56 and 58 into the gob guide chute block containing guide chutes 84 and 86 for delivery from the guide chute 86 into an outer nest 16 or from the guide chute 84 into an inner nest 16. As will be apparent from FIGS. 2 and 3, the guide chute 84 delivers its gob of glass to the inner nest of the index station immediately preceeding the index station at which guide chute 86 delivers its gob of glass to the outer nest.
As will be apparent from the foregoing, a single stream of molten glass is severed into gobs of predetermined size and delivered to a pair of laterally spaced nests on the lamp base making machine indexing turret by means of the gob feed dial of this invention. The gobs of glass are fed alternately to the two different laterally spaced locations while the dial is rotating due to the configuration of the alternate chambers in the dial body. More specifically, every other chamber, the chambers 56 and 58, respectively, are designed to move the gob radially outwardly from the center of the disc as the disc rotates from the glass receiving position to the gob discharge position while the alternate gob travels on the same circular locus on which it is received to its subsequent discharge location. With the base making machine turret 14 indexing at 180 indexes per minute and the dial 48 rotating at 30 revolutions per minute, a gob of glass will be delivered to each of the 72 nests during six revolutions of the gob feed dial. Of course, these speeds are preferable, but it should be understood that increased rates of speed are possible without departing from the scope of this invention. | A method and apparatus for forming and delivering insulating glass in gob form to a lamp base making machine from a continuous stream of molten glass. A rotating dial severs the glass stream into uniform gobs and during rotation forms the gobs into a ball like form and delivers the gobs to a pair of radially spaced drop points for delivery to the base shells on an indexing base making machine. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates to multimedia communications, and, in particular, relates to a particular technique for handling multimedia calls with clients having legacy phones and services.
BACKGROUND OF THE INVENTION
[0002] The world of telecommunications is evolving at a rapid pace. Consumers are perceived to demand new features, especially in the area of multimedia services. Sharing files, video conferencing, sharing a virtual white board, and similar activities are helpful in the business context as geographically dispersed personnel try to coordinate efforts on projects. While the business world may be the driving force behind the need for such multimedia services, the residential consumer may also desire to take advantage of these services.
[0003] A few approaches have been proposed to provide integrated multimedia services. The first approach is to replace the customer premises equipment and network equipment with equipment that supports this functionality seamlessly. This approach is less than optimal for a number of reasons. First, it forces a large cost on the network providers and the consumers who have to replace costly, functioning equipment that, in many cases, is still well within its nominal life expectancy. Second, the older equipment has evolved over time until approximately three hundred different services are offered on this legacy equipment. After transitioning to the newer equipment, there will be a lag between deployment and reintegration of these services as new software must be written to implement the services on the new equipment. Many consumers of these services would not be happy with the loss of these services in the interim. Other drawbacks such as determining a standard or protocol and retraining users in the new hardware and software are also present.
[0004] A second approach has been proposed by the assignee of the present invention and embodied in U.S. patent application Ser. No. 09/960,554, filed Sep. 21, 2001, which is hereby incorporated by reference in its entirety. That application provides a way to integrate multimedia capabilities with circuit switched calls. In the circuit based domain, this solution is functional. However, there remains a need for integrating multimedia capabilities in packet switched calls while preserving presently deployed network hardware.
SUMMARY OF THE INVENTION
[0005] The present invention provides a solution in the packet domain for integrating voice calls with multimedia sessions as a blended call. A blended call is a call which blends voice and multimedia functions into a single communication session. In an exemplary embodiment, a multimedia server is associated with a telephony server. The multimedia server has software incorporated therein that manages blended calls, using the functions of the multimedia server where appropriate and the telephony server where appropriate. To the multimedia server, there is a single session, but the session may have a voice component and a multimedia component. This software is sometimes referred to herein as a blender. In an alternate embodiment, the blender may be a function of sequential logic devices or other hardware that performs the same functions.
[0006] Specifically, the present invention takes an incoming call from a remote caller that is received at a telephony server and accesses a database to determine if the intended recipient of the phone call has blended capabilities. If the answer is negative, the call is handled according to conventional protocols. If the answer is affirmative, the intended recipient supports blended calling, then the telephony server directs the call to a multimedia server, and particularly to a multimedia server with blender software associated therewith. The blender software receives the call request and initiates a single session with two call components: 1) a voice call component and 2) a multimedia call component. The voice call component is handled through the telephony server, and the multimedia call component is handled through the multimedia server. As used herein, the multimedia component includes all the non-voice parts of the call. As part of the two call components, two signaling paths are routed to the blender software, which may integrate the signaling paths into a single signal path as part of the single session, which is used by the multimedia server to control the bearer paths associated with the call. Further, when passing the voice call component back to the telephony server, the blender may include an indication that the component is being passed from the blender and that the telephony server is not to redirect or “loop” the signal back to avoid infinite loops between the blender and the telephony server. The indication to prevent the redirection or looping back may be a “loopback signal” such as a flag, information in a header, or other signaling technique. Additionally, the indication may not be a signal per se, but could be a persistent attribute such as call delivery via a specific trunk on the telephony server reserved for signals that have been processed by the blender. As used herein, the terms “loopback signal” and “loopback indication” cover such signals and indications. It should be appreciated that a loopback signal falls within the definition of a loopback indication as used herein.
[0007] An outgoing call from a user that has blended capabilities may be processed at the telephony server and a destination address extracted to verify that the user is making a call. The telephony server, upon reference to a database to determine that the caller in this instance has blended capabilities, refers the call to a blender function on the multimedia server. The blender then initiates two call components: 1) a voice call component and 2) a multimedia call component. The multimedia server may handle both components as a single session, or may redirect or loop the voice call component back to the telephony server with an indication that the voice call component has been redirected back from blender processing. As noted above, the indication may be a loopback signal or loopback indication.
[0008] While many systems may be used, the present invention is well suited for use with a Session Initiation Protocol for Telephones (SIP-T) configuration as the information included in the SIP-T messages contains the information helpful in setting up and tearing down the parallel call components.
[0009] In another aspect of the present invention, an Intelligent Network (IN) signal may be used to determine if a blended call is being handled. If the call is a blended call, then the call is referred to the blender. If the call is not blended, the telephony server handles the call as normal. This embodiment effectively integrates the circuit based system described in the previously incorporated '554 application with the packet based approach of the present invention.
[0010] Those skilled in the art will appreciate the scope of the present invention and realize additional aspects thereof after reading the following detailed description of the preferred embodiments in association with the accompanying drawing figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The accompanying drawing figures incorporated in and forming a part of this specification illustrate several aspects of the invention, and together with the description serve to explain the principles of the invention.
[0012] [0012]FIG. 1 illustrates a communication environment according to one embodiment of the present invention;
[0013] [0013]FIG. 2 illustrates the methodology of an exemplary embodiment of an incoming voice call used in the present invention;
[0014] [0014]FIG. 3 illustrates the methodology of an exemplary embodiment of an incoming multimedia call used in the present invention;
[0015] [0015]FIG. 4 illustrates the methodology of an exemplary embodiment of an outgoing voice call used in the present invention; and
[0016] [0016]FIG. 5 illustrates the methodology of an exemplary embodiment of an outgoing multimedia call used in the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0017] The embodiments set forth below represent the necessary information to enable those skilled in the art to practice the invention and illustrate the best mode of practicing the invention. Upon reading the following description in light of the accompanying drawing figures, those skilled in the art will understand the concepts of the invention and will recognize applications of these concepts not particularly addressed herein. It should be understood that these concepts and applications fall within the scope of the disclosure and the accompanying claims.
[0018] The present invention is designed to prolong the viability of existing network devices by allowing existing customer premises equipment and existing network elements to be used to support multimedia capabilities. As used herein, a blended call is a call that supports voice and multimedia exchanges of information. To create the blended call, a telephony server or a multimedia server sends calls to blender software. The blender software initiates parallel voice and multimedia components with the customer premises equipment. The voice session may pass through the telephony server with an indication that blended processing has occurred. The blender further keeps control of the signaling paths of the parallel components so that the bearer path may be controlled to accommodate multimedia requests at any stage during the call.
[0019] Because of the desire to be backwards compatible, the present invention may be used on any number of network systems using a number of different protocols. An exhaustive list of suitable networks and protocols is beyond the scope of the present discussion, but those of ordinary skill in the art will appreciate variations on the subject matter herein disclosed after a review of an exemplary embodiment, which is based on a session initiation protocol (SIP) environment.
[0020] A communication environment 10 capable of carrying out the concepts of the present invention is illustrated in FIG. 1. The communication environment 10 depicted includes a communication network 12 , which may preferably include a packet switched network with SIP enabled devices. Thus, the network may include any type of packet switched network having devices using SIP to facilitate communications between two or more devices, also referred to herein as a SIP enabled network.
[0021] Two clients 14 , 16 are connected to the communication network 12 . Each client 14 , 16 may have customer premises equipment (CPE) 18 associated therewith, denoted 18 A for client 14 and 18 B for client 16 . Specifically, client 14 may have a telephone type device 20 and a computer type device 22 . Client 16 may have a telephone type device 24 and a computer type device 26 .
[0022] In general, the telephone type devices 20 , 24 are directed to voice communications with limited data options such as displaying a number called, a calling number, time elapsed and other common telephony functions. In contrast, the computer type devices 22 , 26 may have a monitor, a keyboard, user input devices, and other conventional computer features such that a user may provide inputs and receive outputs and particularly generate and view multimedia content on the computer type device 22 , 26 . It is possible that a telephone type device 20 , 24 could be integrated with its corresponding computer type device 22 , 26 into a single piece of customer premises equipment 18 with the functionalities of both devices.
[0023] Telephone type devices 20 , 24 and computer type devices 22 , 26 may contain data processing devices such as microprocessors which implement software that may be stored on any appropriate computer readable medium such as memory, floppy disks, and compact discs. Alternatively, the functionality of the present invention may be stored in sequential logic as is well understood. The telephone type devices 20 , 24 may, if desired, be “dumb” SIP terminals, H.323 terminals, or other devices delivering primarily voice based service. Each piece of customer premises equipment 18 may be a user agent within the SIP enabled network. As the telephone type devices 20 , 24 and the computer type devices 22 , 26 do not have a full range of features, they may be referred to as feature limited user agents.
[0024] Clients 14 , 16 are connected to the communication network 12 by one or more connections 28 . These connections 28 may be wireless or wirebased. In the event that they are wirebased, copper line, fiber optic line, or other comparable communication medium may be used. It is preferred that the connection 28 be a wideband connection, suitable for exchanging large amounts of information quickly. Note further that while multiple connections are shown, a single connection may in fact provide all the communication links to the customer premises equipment 18 .
[0025] At some point in the communication network 12 , the connection 28 from the telephone type device 20 , 24 terminates on a telephony server, such as telephony servers 30 , 32 . The telephony servers 30 , 32 may be the CS2000 or DMS100 sold by Nortel Networks Limited of 2351 Boulevard Alfred-Nobel, St. Laurent, Quebec, Canada, H4S 2A9. Other class five telecommunication switches or comparable devices including a PBX or a KEY system could also be used as needed or desired and may support both circuit switched voice calls and voice over packet calls. The telephony servers 30 , 32 may communicate with one another and other components in the communication network 12 via a Session Initiation Protocol for Telephones (SIP-T). SIP-T is fully compatible with other SIP enabled devices. Still other communication protocols could be used if needed or desired.
[0026] Each telephony server 30 , 32 may be connected to or integrated with a database (DB) server 34 , 36 . The database servers 34 , 36 may track which clients support which services. For example, a client 14 may support blended services, call forwarding, and the like, each of which is noted in the database server 34 . The database server 34 may index the entries by a trunk line, a directory number, or other unique identifier as is well understood.
[0027] Other components of the present invention are multimedia servers (MS) 38 , 40 which may be positioned throughout the communication network 12 as needed to provide the appropriate quality of service for the present invention. Multimedia servers 38 , 40 are sometimes referred to in the industry as media portals and may be the Interactive Multimedia Server (IMS) sold by Nortel Networks Limited. The IMS is based on JAVA technology and is a SIP enabled device capable of serving SIP clients by providing call conferencing, call transfers, call handling, web access, whiteboarding, video, unified messaging, distributed call centers with integrated web access and other multimedia services. Other media portals or multimedia servers may also be used if needed or desired.
[0028] Operating off of the data processing devices of the multimedia servers 38 , 40 is software that embodies blenders 42 , 44 respectively. An exemplary blender 42 , 44 is further explicated in commonly owned U.S. patent application Ser. No. 10/028,510, filed Dec. 20, 2001, which is hereby incorporated by reference in its entirety. The '510 application refers to the blender as a combined user agent. The present invention builds on the functionality described in the '510 application by showing how the telephony server and the multimedia server interact in response to commands from the blender. As an alternative to software, the blenders 42 , 44 may be instructions embedded in sequential logic or other hardware as is well understood.
[0029] The present invention takes incoming and outgoing calls associated with a client, such as client 14 , and routes the call to the blender 42 associated with the telephony server 30 . The routing to the blender 42 may be done by standard telephony interfaces such as an ISUP trunk, a Primary Rate Interface (PRI) link, a Public Telephone Service (PTS) trunk, or more preferably a SIP or SIP-T connection. The blender 42 then initiates two parallel components for the call. The first component is a voice component and the second component is a multimedia component. Each component may be established with the corresponding piece of customer premises equipment 18 A, and the signaling paths pass through and are controlled by the blender 42 . A more detailed exploration of this is presented below.
[0030] It should be appreciated that the various components within the communication network 12 may communicate with one another even though specific connections are not illustrated. This reflects that in a packet network, the connections are frequently virtual and may change over time or between packets depending on load, router availability, and similar network traffic conditions. Further, the SIP enabled network may have gateways to the Public Switched Telephone Network (PSTN), the Public Land Mobile Network (PLMN), and the like. As the particular network and protocol are not central to the present invention, a further discussion of these well known elements is foregone. Also, the particular connections to the client 14 may be varied. For example, a single Digital Subscriber Line (DSL) into a location may serve both the telephone type device 20 and the computer type device 22 . Alternatively, the telephone type device 20 may be served by a phone line and the computer type device 22 served by a cable modem or the like as is well understood.
[0031] Before turning to the details of the present invention, an overview of SIP may be helpful, as the following discussion is couched in terms of the commands used by SIP. The specification for SIP is provided in the Internet Engineering Task Force's Request for Comments (RFC) 3261: Session Initiation Protocol Internet Draft, which is hereby incorporated by reference in its entirety. A SIP endpoint is generally capable of running an application, which is generally referred to as a user agent (UA), and is capable of facilitating media sessions using SIP. User agents register their ability to establish sessions with a SIP proxy by sending “REGISTER” messages to the SIP proxy. The REGISTER message informs the SIP proxy of the SIP universal resource locator (URL) that identifies the user agent to the SIP network. The REGISTER message also contains information about how to reach specific user agents over the SIP network by providing the Internet Protocol (IP) address and port that the user agent will use for SIP sessions.
[0032] A “SUBSCRIBE” message may be used to subscribe to an application or service provided by a SIP endpoint. Further, “NOTIFY” messages may be used to provide information between SIP endpoints in response to various actions or messages, including REGISTER and SUBSCRIBE messages.
[0033] When a user agent wants to establish a session with another user agent, the user agent initiating the session will send an “INVITE” message to the SIP proxy and specify the targeted user agent in the “TO:” header of the INVITE message. Identification of the user agent takes the form of a SIP URL. In its simplest form, the URL is represented by a number of “<username>@<domain>”, such as “janedoe@nortelnetworks.com.” The SIP proxy will use the SIP URL in the TO: header of the message to determine if the targeted user agent is registered with the SIP proxy. Generally, the user name is unique within the name space of the specified domain.
[0034] If the targeted user agent has registered with the SIP proxy, the SIP proxy will forward the INVITE message directly to the targeted user agent. The targeted user agent will respond with a “200 OK” message, and a session between the respective user agents will be established as per the message exchange required in the SIP specification. Media capabilities are passed between the two user agents of the respective endpoints as parameters embedded within the session setup messages, such as the INVITE, 200 OK, and acknowledgment (ACK) messages. The media capabilities are typically described using the Session Description Protocol (SDP). Once respective endpoints are in an active session with each other and have determined each other's capabilities, the specified media content may be exchanged during an appropriate media session.
[0035] Against this protocol backdrop, FIG. 2 illustrates a flow chart of the methodology of an incoming call to a blended client 14 . In particular, a client 16 dials a number for the client 14 on the telephone type device 24 (block 100 ). The telephony server 32 receives the dialed number (block 102 ) as is conventional. The telephony server 32 references the database server 36 to learn that telephony server 30 serves the dialed number (block 104 ). The telephony server 32 contacts the telephony server 30 with the call request (block 106 ). So far, the call processing is performed according to any conventional protocol and over any conventional network hardware.
[0036] When the telephony server 30 receives the call request, the telephony server 30 references the database server 34 about the number dialed (block 108 ) to determine if the number dialed supports blended services (block 110 ). If the answer to block 110 is “no”, blended services are not supported, the telephony server 30 rings the client 14 conventionally (block 112 ).
[0037] If, however, the answer to block 110 is “yes”, the dialed number does support blended services, then the telephony server 30 passes the call request to the blender 42 in the multimedia server 38 (block 114 ). The blender 42 issues an INVITE message (hereinafter “invite”) to the multimedia server 38 (block 116 ). The multimedia server 38 performs call disposition handling including offering the call to client 14 (block 118 ). Call disposition handling may include for example a “find-me, follow-me” function, call blocking, routing to voice mail based on call screening criteria, updating a user's presence-state information, and the like.
[0038] The multimedia server 38 sends an “invite” to the client 14 via the blender 42 (block 120 ). The blender 42 separates the “invite” into a call request and a multimedia request (block 122 ). The requests may be INVITE messages according to the SIP standard. The blender 42 sends the call request back to the telephony server 30 which rings the telephone type device 20 (block 124 ). The blender 42 may, as part of sending the call request back to the telephony server 30 , include indicia or otherwise provide an indication that designates that the call request is coming from the blender such that the telephony server 30 does not redirect or otherwise loop the call request back to the blender 42 as would be normal for an incoming call. These indicia may take any appropriate form such as a flag, information in the header, a persistent condition, or other technique, and prevent an infinite loop from forming between the telephony server 30 and the blender 42 .
[0039] The blender 42 sends the multimedia request to the computer type device 22 (block 126 ). The multimedia server 38 maintains control over the signaling paths associated with the blended session. In an exemplary embodiment, the blender 42 merges the signaling paths of the voice component and the multimedia component into a single signaling path and passes the merged signaling path to the multimedia server 38 as a single session. By having access to the signaling path of the session, the multimedia server 38 may control the bearer paths of the components without having to parse the information in the bearer path.
[0040] Note that because SIP is being used, the multimedia server 38 has access to the Uniform Resource Locators (URLs) of the endpoints of the call (the respective clients 14 , 16 ), the capabilities of the clients 14 , 16 , and other information relevant to the call disposition handling. Other protocols may provide the same information, but SIP is particularly well suited for this task.
[0041] [0041]FIG. 3 illustrates an incoming multimedia call methodology. The client 16 desires to instant message (IM) the client 14 . To achieve this, the client 16 IM's the client 14 with computer type device 26 (block 150 ). The IM request may include an address for the client 14 , an indication that the client 16 supports blended capabilities and other SIP information. The multimedia server 40 receives the IM request (block 152 ) and references a database (not shown explicitly) to learn that multimedia server 38 serves the address (block 154 ).
[0042] The multimedia server 40 contacts the multimedia server 38 with the IM request (block 156 ). The multimedia server 38 sends an “invite” to client 14 via the blender 42 (block 158 ). The blender 42 separates the “invite” into a call request and a multimedia request (block 160 ). The call request is passed to the telephony server 30 with indicia that the call request is coming from the blender 42 (block 162 ) to prevent the creation of an infinite loop. The telephony server 30 sends an “invite” to the telephone type device 20 (block 164 ). At this point the telephone type device 20 may not ring, but it may answer the “invite” to set up the signaling path associated with the provision of call services. The blender 42 also sends an “invite” to the computer type device 22 (block 166 ). The answers from the telephone type device 20 and the computer type device 22 arrive at the blender 42 (block 168 ), which merges them into a single signaling path and delivers the signaling path to the multimedia server 38 . The multimedia server 38 then manages the call (block 170 ) by maintaining control over the signaling path and allowing the bearer path to be routed through the communication network 12 as needed. If at any point one of the clients 14 , 16 wishes to establish a voice connection, the signaling path for the voice session is already in existence through the blender 42 and may be activated. Alternatively, the invitation for the voice component may only be generated upon request by the users. Thus, the IM session may continue as normal until a user decides to speak with the other party. Upon issuing the appropriate command to the computer type device 22 , the blender 42 receives the request to activate the voice component.
[0043] [0043]FIG. 4 illustrates the methodology of an outgoing voice call from a client 14 . The client 14 dials a number with the telephone type device 20 (block 200 ). The telephony server 30 receives the dialed number (block 202 ). The destination address is extracted by the telephony server 30 (block 204 ) to determine that the client 14 is actually making a call rather than activating a call handling feature such as call forwarding, programming a speed call number, or similar features. The call can be a speed call activation, a normally dialed number, or other technique such that an indication is made that there is a call and not a call handling feature. The telephony server 30 references the database 34 (block 206 ) and determines if the client 14 supports blended services (block 208 ).
[0044] If the answer to block 208 is “no”, the client 14 does not support blended services, the call is processed conventionally (block 210 ). If however, the answer to block 208 is “yes”, the client 14 does support blended services, the telephony server 30 passes the call to the blender 42 (block 212 ). The blender 42 sends an “invite” to the computer type device 22 (block 214 ). The computer type device 22 accepts (block 216 ). Note that a bearer path may not exist yet to the computer type device 22 , but the signaling path associated with the provision of the multimedia session may be created such that if the client 14 desires to begin using multimedia services, they are readily available. The blender 42 passes the combined signal to the multimedia server 38 (block 218 ). The multimedia server 38 performs call disposition handling and sends an “invite” to client 16 (block 220 ). The multimedia server 38 may route the voice portion of the call back through the telephony server 30 if needed or desired, or may handle that portion itself. Other arrangements could also be made. Note also that the invitation to the computer type device 22 may not be issued until a function is invoked that necessitates the provision of multimedia services.
[0045] [0045]FIG. 5 illustrates an exemplary method of an outgoing multimedia call from the client 14 . The client 14 desires to instant message the client 16 and sends an IM to client 16 with the computer type device 22 (block 250 ). The multimedia server 38 receives the multimedia request (block 252 ). The multimedia server 38 may reference a database (not shown explicitly) to determine which multimedia server serves the destination address of the IM request (block 254 ). The multimedia server 38 sends an invitation to the client 14 via the blender 42 (block 256 ).
[0046] Concurrently with the invitation to the client 14 , the multimedia server 38 sends an “invite” to the multimedia server 40 (block 258 ). The multimedia server 40 then invites the client 16 to join the call (block 260 ). The blender 42 is meanwhile separating the “invite” to the client 14 into a call request and a multimedia request (block 262 ). The blender 42 invites the telephone type device 20 and the computer type device 22 (block 264 ) to join the call. Note that the original request from the computer type device 22 may cause the multimedia request to subsume into the original request. Further, the “invite” to the telephone type device 20 may be routed through the telephony server 30 and have a loopback signal or a loopback indication that prevents the formation of an infinite loop between the telephony server 30 and the blender 42 .
[0047] The blender 42 passes the combined signaling path from the telephone type device 20 and the computer type device 22 to the multimedia server 38 (block 266 ) and the multimedia server 38 connects the signal from the blender 42 with the signal from the multimedia server 40 and performs call disposition handling (block 268 ). Again, it is possible that the telephony server 30 may not pass the invitation to the telephone type device 20 until that function is invoked by the participants.
[0048] As another embodiment, instead of relying on SIP for all of the trigger commands, the present invention may be integrated with an Intelligent Network (IN) such that for basic call disposition handling, the IN triggers and commands are used. For mid-call activation of multimedia features, the fact that the multimedia server 38 has access to the signaling path allows the multimedia server 38 to provide the requested multimedia services. For more information on the use of the IN as a trigger point, see the previously incorporated '554 application.
[0049] Note that while the processes above have been described in a generally linear fashion, it is within the scope of the present invention to rearrange the order of some of the steps such that they occur concurrently or in different orders where needed or desired.
[0050] Those skilled in the art will recognize improvements and modifications to the preferred embodiments of the present invention. All such improvements and modifications are considered within the scope of the concepts disclosed herein and the claims that follow. | A communications system that supports multimedia components is easily adapted to existing network elements. Voice components arriving at or coming from a user having multimedia capabilities are referred from a telephony server serving the user to a multimedia server. A determination is made as to whether the other party supports multimedia capabilities. If that determination is negative, the component is passed back to the telephony server with an indication that the session is coming from the multimedia server to avoid an infinite loop. If the determination is positive, a parallel multimedia component is established between the parties while the multimedia server remains aware of the bearer path. | 7 |
BACKGROUND OF THE INVENTION
This invention relates to an automatic sample injector for injecting a liquid sample into the vaporization chamber of a gas chromatograph.
A syringe is commonly used for injecting a liquid sample to be vaporized for analysis into a gas chromatograph. Such a syringe comprises a barrel, a plunger adapted to slide inside the barrel in a liquid-tight relationship therewith, and a needle at the tip of the barrel having a liquid passage therethrough. After a liquid sample is introduced into the barrel, the needle is caused to penetrate a septum (a rubber membrane) and is inserted into the vaporization chamber such that the liquid sample can be dispersed. The liquid sample is made into particles as it is sprayed, vaporized by the heat in the vaporization chamber and transported into the chromatograph column by a carrier gas which is introduced into the vaporization chamber.
An automatic sample injector is for carrying out these processes automatically, comprising a syringe-driving mechanism for moving the syringe with respect to the vaporizer and inserting the needle into the vaporization chamber and a plunger-driving mechanism for moving the plunger with respect to the barrel so as to suck in a liquid sample into the barrel or to inject it out of the barrel. There may also be provided means for moving the syringe between a sample bottle and the vaporizer and for cleaning the barrel and the needle.
One of the problems with automatic sample injectors is that the plunger sometimes gets stuck inside the barrel and cannot be moved. A pulse motor is usually used for driving the plunger but since it is controlled in an open loop, it may appear to the motor (or the control unit therefor) as if the injector is operating normally even when the plunger is stuck inside the barrel and the injector is not operating normally at all. After a specified number of pulses is transmitted to the motor, for example, the control unit of the driving mechanism takes it for granted that the plunger has already moved and starts the next operation. If the plunger is stuck, the needle may be pulled out of the vaporization chamber before the liquid sample is completely injected thereinto, and subsequent processes will be carried out as if there was no abnormality. Since the automatic injector is used for analyzing many samples continuously, many analyses will thus be wasted in the case of such an accident. If the motor has a stronger torque than the force holding the plunger, there may be a damage to the plunger which is usually made of a metallic material such as stainless steel and is very thin (about φ1 mm×several cm).
In order to prevent such occurrences, it has been known to provide an automatic sample injector with a sensor for detecting the plunger at a specified home position (such as the position of the plunger when it is inserted most deeply) and to check whether the plunger has come back to the home position after a specified number of pulses has been transmitted from the control unit to the motor or whether the plunger has left the home position.
Although a prior art detector of this kind can detect an abnormal condition when the plunger does not return to the home position or leave the home position, this relates to a situation when the plunger is completely stuck to the barrel and cannot move at all. When the plunger is stuck but not completely and it can still move a little although the resistance is very strong, however, a prior art detector will not identify it as an abnormality, and there remains the possibility that the suction and injection of the sample may not be carried out as intended before the system moves onto the next process. If the motor has a strong torque, furthermore, the plunger is again likely to be damaged.
SUMMARY OF THE INVENTION
It is therefore an object of this invention to provide an improved automatic sample injector for a gas chromatograph capable of detecting any abnormal condition of the plunger preliminarily and thereby preventing incorrect operations of the gas chromatograph and damage to the device components.
An automatic sample injector embodying this invention, with which the above and other objects can be accomplished, may be characterized as comprising a plunger motor with variable torque for moving the plunger inside the barrel of the syringe, a plunger position sensor for detecting the plunger at a specified position, and an abnormality detecting means for detecting an abnormal condition of the plunger by first operating the plunger motor at a smaller torque than the normal torque for actual operation and by using the plunger position sensor.
The abnormality detecting means serves to drive the plunger motor at a smaller torque (referred to as "the test torque") than the torque (referred to as "the actual torque") at the time of actual operation before this automatic sample injector is actually used for the injection of a sample for real analysis. In order to preliminarily determine the magnitude of the test torque, the operator first determines a minimum torque, which is required for pushing the plunger into or out of the barrel to suck in or push out a solvent when the syringe is under normal condition. Next, the plunger is pulled fully outward from the barrel without pulling it out of the barrel and is then stopped such that it will not move. Next, the plunger is pushed in and the maximum torque at which the motor can be driven without damaging the plunger is determined, and the test torque is set somewhere between this minimum torque and the maximum torque. Since the minimum torque and the maximum torque thus defined depend on the individual injector, the test torque should be set separately for each injector.
As the injector is run at the test torque, as described above, the plunger position sensor is used to check whether the plunger is functioning correctly or not. If the plunger is somewhere other than the home position at the beginning of a test run, for example, it is determined whether the plunger comes back to the home position within a specified time determined from this initial position of the plunger. If the plunger is at the home position at the beginning, on the other hand, it may be checked whether the plunger leaves the home position within a specified period of time. In this manner, it is possible to check not only whether the plunger is completely stuck inside the barrel or not, but also whether or not an abnormally large force is being required to push in or pull out the plunger although the plunger is not completely stuck.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated in and form a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the principles of the invention. In the drawings:
FIG. 1 is a schematic structural diagram of an automatic sample injector embodying this invention;
FIG. 2 is a sectional view of the syringe of FIG. 1; and
FIG. 3 is a schematic simplified diagram for showing the structure of the stepping motor of FIG. 1 and its control unit.
DETAILED DESCRIPTION OF THE INVENTION
The invention is further described by way of an example with reference to drawings. FIG. 1 shows an automatic sample injector 10 embodying this invention for a gas chromatograph with its vaporization chamber shown at 19, comprising a syringe driving mechanism 15 for moving a syringe 11 up and down and a plunger driving mechanism 16 for moving a plunger 13 of the syringe 11 up and down. The syringe driving mechanism 15 comprises a (syringe-driving) motor 151 and a pair of pulleys 152 affixed with respect to the sample vaporization chamber 19, a belt 153 which is stretched between these pulleys 152 and a syringe clamper 154 attached to the belt 153. The plunger driving mechanism 16 comprises a (plunger-driving) motor 161 set on the syringe clamper 154, a pair of pulleys 162 affixed with respect to the syringe clamper 154, a belt 163 stretched between these pulleys 162 and a plunger clamper 164 attached to the belt 163. The plunger driving mechanism 16 further includes a home position sensor 165 comprised of light emitting and receiving units set on a side of the syringe clamper 154 and a reflective mirror affixed to the plunger clamper 164 such that the presence of the plunger 13 at its home position is detected because the light from the light emitting element is reflected by the mirror to the light receiving element when the plunger 13 is pushed into the barrel 12 of the syringe 11 as deeply as possible. FIG. 2 shows the structure of the syringe 11 more in detail. Same symbols are used both in FIGS. 1 and 2 to indicate the same components for convenience.
The plunger-driving motor 161 of the plunger driving mechanism 16 is a stepping motor having many magnetic poles 22 and ON-OFF switches 24 each associated with corresponding one of the magnetic poles 22, as shown schematically in FIG. 3. Each of the ON-OFF switches 24 comprises a FET, and the entire assembly is controlled as a FET array 23 by a control unit 18 which serves to open individual switches 24 of the array 23 for a specified period time to excite the corresponding magnetic poles of the stepping motor 161 to thereby cause its rotor 21 to rotate by a desired angle. In other words, the angle of rotation by the rotor 21 is controlled by the number of pulses outputted from the control unit 18. Each pulse for causing the rotor 21 to rotate by a specified angle comprises a large number of fine pulses such that the control unit 18 can vary the rotary torque of the stepping motor 161 by changing the duty ratio of these fine pulses.
Operations of the control unit 18 when an actual analysis is carried out by the gas chromatograph will be explained next. First, the syringe driving mechanism 15 lifts the syringe 11 to its raised position and a container (not shown) containing a sample is placed in the space between the sample vaporization chamber 19 and the needle 14 of the syringe 11. After the syringe driving mechanism 15 lowers the syringe 11 such that the needle 14 goes into the sample inside the sample container, the plunger driving mechanism 16 is activated to pull up the plunger 13 to cause a specified amount of the sample to be introduced into the barrel 12 of the syringe 11. The syringe 11 is then lifted, and after the needle 14 is taken out of the sample container, the sample container is removed from the space. The placing and removal of the sample container may be carried out by means of an auto-sampler of a known kind.
In order to inject the sample now contained inside the syringe 11 into the sample vaporization chamber 19, the syringe driving mechanism 15 causes the syringe 11 to move downward such that the needle 14 of the syringe 11 will enter the sample vaporization chamber 19 by penetrating a septum at the top thereof. The syringe driving mechanism 15 is provided with a stopper (not shown) which serves to stop the downward motion of the syringe 11 when the tip of the needle 14 reaches a specified position inside the sample vaporization chamber 19. Immediately thereafter, the plunger driving mechanism 16 pushes the plunger 13 downward until its lower end comes into contact with the bottom of the barrel 12, causing the specified amount of the sample to be sprayed inside the sample vaporization chamber 19. According to the embodiment described above, this position of the plunger 13 serves as its home position.
Prior to the actual operation for a real analysis as described above, the automatic sample injector 10 according to this invention is run as follows to check whether the plunger 13 is operable normally. First, the presence of the plunger 13 at the home position is ascertained. Thereafter, the control unit 18 controls the FET array 23 and transmits a specified number of pulses to the plunger-driving motor 161 for the same torque (duty ratio) as for the actual run. The number of pulses in this situation is set such that the plunger 13 under a normal condition will be sent to the position protruding from the barrel 12 as far out as possible without falling off therefrom. After all these pulses are transmitted, the home position sensor 165 checks whether the plunger 13 has left the home position. If the plunger 13 has not left the home position, it means that the plunger 13 is stuck at the home position, and the control unit 18 concludes that the syringe 11 is in an abnormal condition.
If the home position sensor 165 discovers that the plunger 13 is not found at the home position, the same number of pulses as above is transmitted to rotate the plunger motor 161 but at a test torque, which is smaller than the torque at the time of actual analysis. The magnitude of the test torque is preliminarily determined, as explained above, so as to be larger than the minimum torque required for the plunger 13 to move inside the barrel 12 but smaller than the torque at the time of actual analysis such that the plunger will not be bent and damaged. As explained above, the exact magnitude of the test torque should preferably be determined preliminarily for each device. With the magnitude of the test torque thus set, the plunger 13 should return to its home position after a specified number of pulses have been transmitted if the syringe 11 is in normal condition. Thus, it can be determined by checking the output of the home position sensor 165 after these pulses are transmitted whether the plunger 13 is experiencing any difficulty in moving inside the barrel 12. After the condition of the plunger 13 is thus tested successfully, the actual operation for real analysis as described above is carried out.
Although the invention was described above by way of an example wherein the plunger 13 is normally at its home position, this is not intended to limit the scope of the invention. The device may be operated such that the plunger 13 is preliminarily moved to the home position with a test torque before the testing process described above is carried out. In such a case, the number of pulses corresponding to the total stroke of the plunger may be transmitted and an abnormal condition can be detected if the plunger 13 is thereafter found not to have reached the home position.
In summary, an automatic sample injector according to this invention is adapted to carry out a test run at a low torque before it is used for a real analysis such that it is possible to detect not only the kind of abnormal condition wherein the plunger is completely stuck inside the barrel of the syringe but also situations where the plunger can be moved but the force required to do so is abnormally great. Thus, incorrect injection of sample at the time of actual analysis can be prevented and damage to the plunger can also be avoided. | An automatic sample injector for a gas chromatograph includes not only a syringe with a barrel and a plunger which is adapted to move inside the barrel but also a plunger-driving motor for pushing and pulling the plunger inward and outward inside the barrel, a position sensor for the plunger and an abnormality detector for detecting an abnormal operating condition of the plunger. The plunger-driving motor has a variable torque, and it is operated at a preliminarily determined reduced torque smaller than the normal torque at which it is operated under normal conditions. The subsequent motion of the plunger, or lack thereof, is monitored by the position sensor to determine whether the plunger is totally or partially stuck inside the barrel. | 8 |
BACKGROUND AND SUMMARY OF THE INVENTION
This invention relates to a punch retainer for use on stamping presses and, more particularly, to a punch retainer generally of the type disclosed in my U.S. Pat. No. 4,174,648, dated Nov. 20, 1979. In my aforesaid patent there is disclosed a punch retainer provided with a latch having cylindrically shaped opposite sides which are adapted to tangentially engage in wedging relationship an inclined face on the punch and an inclined face of a socket within the punch retainer. The latch is urged into said tangential wedging engagement with the punch and the inclined wall of the socket by means of a spring. While the arrangement shown in said patent is admirably suited for use with punches having a circular punching end, experience has shown that where the punch is provided with a non-circular punching end the dimensional tolerances of the cooperating surfaces on the punch, the latch and the retainer are critical and must be closely controlled if the punched hole has to be within very close tolerances. Unless such tolerances are closely controlled, the punch might be firmly seated within the socket but the punching end thereof may be rotated at least slightly from its desired accurately oriented position.
The primary object of the present invention is to provide a simple mechanism for firmly retaining a punch within a retainer so that the non-circular punching end of the punch is accurately oriented in a circumferential sense relative to the retainer.
A more specific object of the invention resides in the provision of a spring housed within the retainer for engaging a flat surface on the punch which is accurately machined relative to the non-circular punching end of the punch.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, features and advantages of the present invention will become apparent from the following description and accompanying drawings, in which:
FIG. 1 is a vertical sectional view through a punch and retainer according to the present invention;
FIG. 2 is a sectional view along the line 2--2 in FIG. 1;
FIG. 3 is a fragmentary sectional view along the line 3--3 in FIG. 2;
FIG. 4 is a fragmentary view illustrating generally the manner in which the latch engages the punch;
FIG. 5 is an elevational view of the tool employed for displacing the latch to the punch release position;
FIG. 6 is a view similar to FIG. 1 and showing a modified form of the invention;
FIG. 7 is a sectional view on an enlarged scale along the line 7--7 in FIG. 6;
FIG. 8 is a fragmentary sectional view of a portion of the arrangement shown in FIG. 6 illustrating the manner in which the latch is displaced to the punch releasing position; and
FIG. 9 is a fragmentary sectional view along the line 9--9 in FIG. 7.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In FIG. 1 there is shown a punch retainer block 10 mounted on an upper reciprocating die shoe 12 and having a punch 14 retained in block 10. Punch 14 has a generally cylindrical shank 16, the side wall of which is ground with a flat 18 adjacent the upper end of the punch. The lower end of the punch is provided with a non-circular punching portion 19. A recess 20 is formed in the side wall of the punch directly below the flat 18. Recess 20 preferably comprises a flat inwardly inclined face 22, the lower end of which is tangent to an outwardly curved face 24.
Retainer block 10 comprises a lower body portion 26 and an upper cap plate 28 which are secured together by screws 30 (FIG. 3). Retainer block 10 is accurately located on die shoe 12 by dowel pins 32 and firmly secured thereto by screws 34.
Body 26 of retainer block 10 is formed with an accurately cylindrical bore 36 adapted to snugly receive the shank 16 of punch 14. At one side of bore 36 body 26 is formed with a socket 38 extending downwardly from the top face thereof. The portion of socket 38 which intersects bore 36 is defined by two parallel, vertically extending, side walls 40. The laterally outer end portion of socket 38 is enlarged as at 42 and connected to the portion defined by side walls 40 by a narrow slot 44. The laterally outer side wall 46 of socket 38 which is intersected by slot 44 is inclined so that it converges slightly with respect to the inclined face 22 on punch 14. For example, face 22 may be inclined to the vertical at an angle of about 15° and the face 46 may be inclined to the vertical at an angle of about 221/2° so that the included angle therebetween is about 71/2°.
The means for retaining punch 14 seated in block 10 comprises a cylindrical roller 48 supported within socket 38 by a yoke 50. As shown in FIG. 1, yoke 50 extends around a central groove in cylinder 48, laterally outwardly through slot 44 and into the enlarged cylindrical portion 42. The portion of yoke 50 within the enlarged portion 42 is generally U-shaped and formed with an upstanding leg 52 which serves as a retainer for a compression spring 54. The lower end of spring 54 is seated on the return bend portion 55 of yoke 50 and the upper end of spring 54 abuts against the under side of cap plate 28. Spring 54, acting through yoke 50, normally biases roller 48 downwardly in socket 38. In its uppermost position, wherein roller 48 abuts against the bottom face of cap plate 28 (the broken line position shown in FIG. 1), roller 48 projects into bore 36 and just clears the flat 18 at the upper end of the punch when the punch is circumferentially oriented so that the flat 18 is parallel to the axis of roller 48.
When the punch is seated in bore 36 in the position shown in FIG. 1 it may be removed therefrom by advancing a tool 58 upwardly through a bore 60 in body 26 to displace roller 48 upwardly out of recess 20 against the bias of spring 54 to the broken line position. As a matter of convenience tool 58 is threaded as at 62 and bore 60 is threaded so that the roller 48 can be advanced to the broken line position by threading tool 58 upwardly and retained in its raised position by the threaded connection between tool 58 and bore 60. In this position roller 48 just clears the flat 18 on the punch and enables the punch to be withdrawn from bore 36. When tool 58 is threaded out of bore 60 roller 48 will assume the approximate position shown in FIG. 1 under the bias of spring 54.
When it is desired to insert the punch in the retainer, the punch is pushed upwardly into bore 36 with the flat 18 aligned generally parallel with the axis of roller 48. The upper edge of flat 18 engages roller 48 and displaces it upwardly and inwardly of socket 38, which movement is permitted by spring 54. As the shank of the punch is moved progressively upwardly in socket 36 and after roller 48 clears flat 18, spring 54 displaces roller 48 downwardly progressively until the upper end of the punch is seated against the cap plate 28. At this time, one side of roller 48 tangentially engages the flat inclined face 22 on the punch with line contact. The opposite side of roller 48 is in tangential line contact with the flat wall 46 of socket 38. Roller 48 is thus engaged in wedging relation between punch 14 and the inclined face 46 of the socket 38 in the retainer body.
The present invention is directed specifically to the means for automatically rotating the punch 14 slightly, if necessary, so that, when it is fully seated in retainer 10, the flat 18 is parallel to a high degree of accuracy to the line of intersection between a horizontal plane and the inclined face 46 of socket 38. These means are in the form of a spring 64. As shown in FIGS. 1 and 2, spring 64 includes a body portion 66 having a lateral extension 68 extending through slot 44 and hooked over one of the coils of spring 54. At its opposite end spring 64 has a downwardly bent leg 70 adapted to engage the flat 18 and adjacent the extension 68 the spring is provided with a pair of downwardly bent legs 72 having straight lower edges 74 which engage the inclined face 46 of socket 38 on the opposite sides of slot 44. Leg 70 is bent downwardly from the body portion of spring 64 at a much sharper angle than legs 72. Thus, legs 72 are substantially more flexible than leg 70. The lower edges of legs 72 are accurately parallel to the leg 70 of spring 64 and remain accurately parallel thereto when the legs 72 are flexed.
In the free condition of spring 64 the lateral spacing between legs 72 and leg 70 is such that the leg 70 extends into bore 36 a slight distance beyond flat 18. However, the upper end of punch 14 is chamfered as at 76 so that when the punch is inserted upwardly in bore 36 chamfer 76 engages the lower end of leg 70 which aligns the flat 18 on the punch accurately parallel to the edge 74 of spring 64. Thereafter, when the punch is advanced upwardly to its fully seated position shown in FIG. 1, the spring legs 72 are flexed inwardly toward the punch axis by the inclined surface 46 so that the non-circular punch end 19 is oriented circumferentially in a predetermined position relative to the retainer to a high degree of accuracy. In the absence of a mechanism such as spring 64, punch 14 could be fully seated within the retainer with roller 48 in a slightly cocked condition, in which event the punching end 19 would not be oriented to a high degree of accuracy in the desired position relative to the retainer.
The arrangement shown in FIGS. 6 through 9 is the same as in the previously described embodiment with the exception of the means for retaining the punch in the predetermined accurately oriented position relative to the retainer. In this embodiment these means comprise a circumferentially resilient roll pin 80 which is seated in a slot 82 at the upper end of socket 38. The laterally outer face 84 of slot 82 is accurately parallel to the line of intersection between a horizontal plane and the inclined face 46. Roll pin 80 is in the form of a tubular member formed of spring material having spaced apart edges 86. Slot 82 and pin 80 are dimensioned and located such that, when the pin 80 is seated in slot 82, the laterally inner side thereof projects inwardly of bore 36 slightly beyond the square notch 88 at the upper end of the punch. Thus, in a manner similar to that described with reference to the previous embodiment, when the punch is fully inserted into bore 36, pin 80 properly aligns the punch and is compressed between the outer wall 84 of slot 82 and notch 88 so as to maintain the punch in the desired position with respect to the orientation of the punch end 19 relative to the retainer.
It will therefore be seen that the spring retainers 64,80 assure the proper orientation of the punch to a high degree of accuracy. These retainers eliminate the necessity for a very high degree of dimensional accuracy of the interengaging surfaces between the punch, roller 48 and the inclined face 46 of socket 38. At the same time, it will be appreciated that the manufacture of spring 64 or pin 80 to a high degree of accuracy and inexpensively does not pose any serious manufacturing problems. | A punch and retainer assembly wherein the punch has a non-circular punching end, a flattened surface at the upper end of the side wall thereof and a radially inwardly extending recess directly below the flattened side wall portion. The punch retainer includes a vertically movable latch adapted to engage within the recess on the shank of the punch and retain the punch within the retainer. Means are provided for limiting vertical movement of the latch so that the punch can be inserted into the retainer only when the flattened surface thereof is aligned parallel with the pivot axis of the punch. Spring means are also provided for maintaining the non-circular punching end of the punch in a predetermined circumferential angular relationship relative to the latch. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
The present application claims priority from provisional U.S. Pat. App. Nos. 61/347,254 filed on May 21, 2010 and 61/373,713 filed on Aug. 13, 2010, both of which are incorporated by reference herein in their entireties.
FIELD OF INVENTION
The present invention relates to containers and lids therefore, and more specifically, to the prevention of spills during cooking or other transitions.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
No federal funds were used to develop or create the invention disclosed and described in the patent application.
REFERENCE TO SEQUENCE LISTING, A TABLE, OR A COMPUTER PROGRAM LISTING COMPACT DISK APPENDIX
Not Applicable
BRIEF DESCRIPTION OF THE FIGURES
In order that the advantages of the invention will be readily understood, a more particular description of the invention briefly described above will be rendered by reference to specific embodiments illustrated in the appended drawings. Understanding that these drawings depict only typical embodiments of the invention and are not therefore to be considered limited of its scope, the invention will be described and explained with additional specificity and detail through the use of the accompanying drawings.
FIG. 1 provides a perspective view of a first embodiment of the container protector engaged with a container.
FIG. 1A provides a cross-sectional view of the first and second embodiment of the container protector engaged with a container adjacent a container end wall.
FIG. 1B provides a cross-sectional view of an embodiment of the container protector having a ridge formed therein.
FIG. 2 provides a perspective view of a second embodiment of the container protector engaged with a container.
FIG. 3 provides a perspective view of a third embodiment of the container protector engaged with a container.
FIG. 4 provides a perspective view of another embodiment of the container protector.
DETAILED DESCRIPTION
Listing of Elements
ELEMENT DESCRIPTION
ELEMENT #
Container protector
10
Container
20
Container side wall
22
Container end wall
24
Container handle
24a
Interior lip
30
Side skirt
32
End skirt
34
Handle extension
34a
Ridge
36
Container protector with bottom
40
Before the various embodiments of the present invention are explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangements of components set forth in the following description or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or of being carried out in various ways. Also, it is to be understood that phraseology and terminology used herein with reference to device or element orientation (such as, for example, terms like “front”, “back”, “up”, “down”, “top”, “bottom”, and the like) are only used to simplify description of the present invention, and do not alone indicate or imply that the device or element referred to must have a particular orientation. In addition, terms such as “first”, “second”, and “third” are used herein and in the appended claims for purposes of description and are not intended to indicate or imply relative importance or significance. As used herein, the term “rectangle” is meant to include any quadrilateral having four right angles.
Referring now to the drawings, wherein like reference numerals designate identical or corresponding parts throughout the several views, FIG. 1 provide a perspective view of a first embodiment of the container protector 10 engaged with a container 20 . The embodiment of the container protector 10 shown in FIG. 1 is configured to engage a container 20 that is rectangular in shape. Such containers 20 typically include two opposing container side walls 22 connected to two opposing container end walls 24 in one integral structure. Container handles 24 a may be fashioned in the container end walls 24 to facilitate repositioning of the container 20 during use or otherwise moving the container 20 .
The first embodiment of the container protector 10 includes two opposing side skirts 32 configured to seal against the container side walls 22 . Two opposing end skirts 34 are configured to seal against the container end walls 34 . The side skirts 32 are affixed to the end skirts 34 so that the shape of the container protector 10 is substantially the same as the shape of the container 20 . Handle extensions 34 a may be included in the end skirts 34 to seal against the container handle 24 a in containers 20 that are configured with container handles 24 a . However, container protectors 10 configured for use with containers 20 not having container handles 24 a may be constructed without handle extensions 34 a.
It is contemplated that the container protector 10 will be constructed of a pliable and/or semi-pliable material and configured so that the container protector 10 stretches by a certain amount when engaged with the container 20 , thereby creating a hermetic seal between the container 20 and the container protector 10 . That is, the elastic or semi-elastic nature of the container protector 10 allows it to expand so that it is secured to the container 20 . Accordingly, in many applications the periphery of the container protector 10 will be less than the periphery of the container 20 for which it is designed. During use, attachment of the container protector 10 to the container 20 will require the user to stretch the container protector 10 over the container 20 , thereby ensuring the container protector 10 is adequately secured to the container 20 and that an adequate seal is created between the container protector 10 and container 20 .
An interior lip 30 may be connected to both the opposing side skirts 32 and the opposing end skirts 34 . The interior lip 30 is configured to extend inward from the periphery of the container 20 , which is best shown in FIGS. 1A and 1B , which provide different cross-sectional views of the container protector 10 engaged with a container 20 .
A cross-sectional view of a portion of the container protector 10 and container 20 adjacent a container handle 24 a and a handle extension 34 a is shown in FIG. 1A . A cross-sectional view of a portion of the container protector 10 and container 20 along a container side wall 22 and side skirt 32 is shown in FIG. 1B . As shown in these various figures, the interior lip 30 extends upward beyond the periphery of the container 20 and inward therefrom. This extension of the interior lip 30 combined with the sealing engagement between the end skirts 34 and container end walls 24 , the handle extensions 34 a and container handles 24 a , and the side skirts 32 and container side walls 22 serves to functionally increase the volume of the container 20 . Accordingly, if material is positioned in the container 20 and the container 20 is subsequently heated, which may expand the material in the container 20 , the container protector 10 may prevent the material from flowing out of the container 20 . One example of such a situation is during cooking, especially baking scenarios. It is contemplated that the first embodiment of the container protector 10 will be sized to seal a nine-inch-by-thirteen-inch, seven-inch-by-eleven-inch, or other rectangular-shaped container 20 . The container 20 may or may not include container handles 24 a , and the container protector 10 may be formed accordingly (i.e., with or without handle extensions 34 a ).
A second embodiment of the container protector 10 is shown in FIG. 2 , wherein the container protector 10 is configured to seal against a square-shaped container 20 . The container protector 10 in the second embodiment functions identically to that of the first embodiment. However, in the second embodiment of the container protector 10 the container protector 10 is sized to seal an eight-inch-by-eight-inch, nine-inch-by-nine-inch, or other square-shaped container 20 . As with the first embodiment, in the second embodiment the container 20 may or may not include container handles 24 a , and the container protector 10 may be formed accordingly (i.e., with or without handle extensions 34 a ).
A third embodiment of the container protector 10 is shown in FIG. 3 , wherein the container protector 10 is configured to seal against a circular-shaped container 20 . The container protector 10 in the third embodiment functions identically to that of the first and second embodiments. However, in the third embodiment of the container protector 10 the container protector 10 is sized to seal circular-shaped container 20 . As with the first and second embodiments, in the third embodiment the container 20 may or may not include container handles 24 a , and the container protector 10 may be formed accordingly (i.e., with or without handle extensions 34 a ).
A container protector with bottom 40 is shown in FIG. 4 . The container protector with bottom 40 functions identically to the other embodiments of the container protector 10 disclosed herein. However, the container protector with bottom 40 includes a bottom portion 38 connecting the side skirts 32 and end skirts 34 so that the container protector with bottom 40 forms a type of vessel with substantially the same shape as the container 20 for which the container protector 10 is designed. The bottom portion 38 may be configured to either allow for or inhibit accumulation of baked-on materials between the container protector with bottom 40 and the container 20 , thereby enhancing removal of food particles after use.
As is apparent in light of the present disclosure, when the container protector 10 is fully engaged with a container 20 for which the container protector 10 was designed, a seal is formed along the entire periphery of the container 20 . This seal allows the interior lip 30 of the container protector 10 to act as an extension of the container 10 , thereby effectively increasing the volume of the container 20 . Accordingly, if the material positioned within the container 10 expands during cooking, baking, or during any other transitory condition put upon the material and/or container 20 , the container protector 10 prevents the material from exiting the container 20 .
The optimal dimensions of the height of the side skirt 32 , and skirt 34 , and interior lip 30 will depend on several factors, including but not limited to the specific application for the container protector 10 and the height of the container side and end walls 22 , 24 . However, it is contemplated that for most applications the height of the side skirt and end skirt 34 will be between 0.25 and 2.5 inches, and the height of the interior lip 30 will be between 0.1 and 2.5 inches. The thickness of the interior lip 30 , side skirt 32 , end skirt 34 , and handle extension 34 a will vary from one embodiment of the container protector 10 to the next, but for many applications a thickness between 0.1 and 0.7 inches will suffice. The length of the side skirts 32 and end skirts will vary depending on the size and configuration of the container 20 for which the container protector 10 is designed.
The various elements of the container protector 10 may be integrally formed as one unit, or the various elements may be separately formed and later affixed to one another. The container protector 10 may be formed of any material known to those of ordinary skill in the art that is suitable for the application for which the container protector 10 is used. Such materials include but are not limited to rubber, silicon, other polymers, or combinations thereof. It is contemplated that for some applications the container protector may be constructed of a silicone rubber material that is heat resistant up to 480 F, but the temperature that the material of construction will withstand in no way limits the scope of the container protector 10 . The silicon rubber material is typically used in the construction of other types of bakeware due to its superior durability.
Other methods of using the container protector 10 and embodiments thereof will become apparent to those skilled in the art in light of the present disclosure. Accordingly, the methods and embodiments pictured and described herein are for illustrative purposes only.
It should be noted that the container protector 10 is not limited to the specific embodiments pictured and described herein, but is intended to apply to all similar apparatuses and methods for preventing a material positioned in a container from overflowing the container. Modifications and alterations from the described embodiments will occur to those skilled in the art without departure from the spirit and scope of the container protector 10 . | In one embodiment of a container protector the container protector comprises two opposing side skirts, two opposing end skirts, and a interior lip connected to both side skirts and end skirts. The container protector may also include one or more handle extension to facilitate use with a container having one or more handles. The container protector is designed to sealing fit around the top periphery of a container with the interior lip extending upward to prevent material within the container from flowing outward therefrom during transitions. Such transitions may be caused by heating, transportation, or other disturbances. The precise dimensions of the container protector will vary from one embodiment to the next, and the container protector may take any shape depending on the container for which it is designed. | 0 |
The invention described herein may be manufactured, used and licensed by or for the Government for Governmental purposes without the payment of any royalties thereon.
BACKGROUND OF THE INVENTION
This invention relates to the determination of the optimum isothermal heat treatment procedure for alloys such as steel and austempered ductile iron. For years, workers have followed various procedures to determine the transformation characterstics and proper heat treatment procedures to obtain the optimum properties for a given alloy.
There are many problems associated with the various methods employed for these purposes in the past. The original method, which is still used, was a trial and error method. Another method presently used includes the steps of preparing a number of specimens, austenitizing them at appropriate temperatures and then cooling them rapidly by immersion in a liquid maintained at a lower temperature where the transformation of austenite into the desired microstructure (e.g. bainite, martensite) occurs. The specimens are then removed and examined to determine the microstructure.
An improved method uses metallurgical "quench" dilatometers which use a hollow specimen that can be quickly cooled from austenitizing temperatures under controlled conditions by a controlled combination of R.F. heating and gas cooling. The progress of the transformation in this type of system is monitored dilatometrically (i.e. by measuring length changes that accompany the phase transformation).
The metallurgical dilatometer is an excellent tool however it has the disadvantage of using relatively complex instrumentation with associated maintenance difficulties. In addition, false results are often obtained.
SUMMARY OF THE INVENTION
Briefly, the present invention utilizes magnetic properties of alloys and takes advantage of the dramatic difference in magnetic states of austenite, which is paramagnetic, and austenite decomposition products which are ferromagnetic. With the apparatus of the invention, a specimen is austenitized in a high temperature furnace and then it is rapidly cooled in a low temperature furnace where the austenite decomposition occurs. The change in phase within the specimen is monitored magnetically by means of coils which surround the low temperature furnace.
The present invention permits the monitoring of a transformation as it occurs and permits the same specimen to be used many times so that all of the main transformation characteristics can be obtained from a single specimen. In this way, the costly, time consuming specimen preparation processes of prior art methods are eliminated.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic representation of apparatus embodying the invention and
FIG. 2 is an enlarged sectional view of a portion of the apparatus shown in FIG. 1.
DESCRIPTION OF THE INVENTION
The present invention has been utilized primarily with austempered ductile iron (ADI) however it has broad applicability to other alloys that are subjected to similar austenitizing and cooling transformation in their thermal processing.
Referring to the drawings, thermomagnetic processing apparatus 10 embodying the invention includes an upper quartz tube 20 oriented vertically with an austenitizing furnace 30 enclosing the tube adjacent its upper end. The furnace is a standard furnace which is capable of maintaining temperatures up to about 1200 degrees C.
The lower end of the quartz tube 20 is secured to a coupling 32, for example of brass, by threading or other suitable means. A lower metal tube of, for example stainless steel, 22 has its upper end threadedly coupled to the coupling 32 and it extends downwardly therefrom.
A quench block 40 is mounted within the coupling 32. The quench block is in the form of a hollow tubular block of metal or ceramic having an axial through hole 42 to allow a specimen to be inserted to be quenched. A hole 44 is drilled radially into the the quench block to join the axial hole 42 and to allow a thermocouple to be inserted. The quench block 40 is made of a metal or ceramic of sufficient mass to absorb heat from the specimen as required.
A lower furnace 50 used for isothermal transformations is disposed about the lower metal tube 22. This furnace, in one embodiment has a diameter of one inch and is vacuum jacketed and fabricated of non-magnetic materials and is capable of maintaining isothermal temperatures up to 600 degrees C.
A specimen 60 to be treated and analyzed is secured to a fine wire 70 by which the specimen can be raised and lowered within the quartz tube 20 and metal tube 22. According to the invention, the fine wire 70 forms one part of a thermocouple and has a diamter of about 0.005 inch to provide minimal friction and drag on the specimen as it is released from the quench block as described below. The wire is spot welded directly to the specimen to form one leg of a thermocouple. The other leg of the thermocouple is a sharpened 0.020 inch wire 72 which serves as the pinning assembly that is enclosed in a sheath of insulating material such as alumina, and inserted through the hole 44 in the side of the quench block and into the center of the block.
A purge gas inlet pipe 80 is also coupled into the quench block and is used for introducing a purge gas which is used to protect the specimen from oxidation at high temperatures. The sheathed wire 74 is introduced into the quench block through the pipe 80.
The specimen 60 is copper coated and the suspension wire 70 can be copper while the pinning wire 72 may be constantan thermocouple wire so that the system operates as a copper constantan thermocouple. Other thermocouple pairs such as chromel-alumel will also operate satisfactorily.
The wires 70 and 72 are connected to a voltmeter 76.
When the pinning wire 72 contacts the specimen, the thermocouple circuit is completed and the arrangement provides dynamic, accurate, instantaneous measurement of the specimen temperature.
The progress of the isothermal transformation from non-ferromagnetic austenite to the various ferromagnetic decomposition products, such as bainite, is monitored magnetically in the apparatus of the invention by means of a set of electrical coils that surround the specimen and lower furnace. The coil set includes a primary coil 84 which magnetizes the specimen with an alternating field and a secondary coil 86 which detects the extent of magnetization of the specimen. A pickup or sensing coil 88 is embedded in the driver coil 84 and thus is also mounted on the tube and it is coupled to display and computer instrumentation for data recording and control of operations.
The sensing coil output is analyzed in a standard manner to provide a digital output to a computer of the real and imaginary parts of the coil/specimen impedance. It is the imaginary component that is approximately linearly related to the volume of transformed austenite.
In one embodiment of the invention, a commercial coil system used was made by Forster instruments and is known as Magnatest-S. The driving coil provides sufficient magnetic driving force to magnetize a sample in the approximately linear range and provide a detectable response for the sensing coil which, as noted, is embedded within the driver coil.
The high sensitivity of the coil system permits measurements at low frequency, e.g. 16 Hz, which allows the signal to penetrate the entire volume of the ferromagnetic sample. The output of the pickup coil is registered digitally as real and imaginary components of the secondary coil impedance. The dominant contribution is the imaginary component from the coil impedance.
In the apparatus 10, the quartz tube 20 has a diameter of about one inch and the austempering furnace has a diameter of about 0.75 inch. The furnace is vacuum jacketed for maximum thermal isolation to avoid undue heating of the close fitting coil arrangement. The furnace windings are specially wound bifilarly to preclude spurious magnetic fields in the pickup coil. It is desirable that the magnetic response (coil/specimen impedance) be approximately proportional to the volume transformed and for this, it is important that the specimen be fabricated in rod form with a proper length to diameter ratio. One suitable specimen was 1/8 by 3/4 inches.
Because the specimens are thin it is essential that their surfaces be protected from degradation by oxidation and decarburization at high temperatures. This is accomplished by electroplating the specimens with copper and providing a continuous flow of protective atmosphere such as 90 percent helium and 10 percent hydrogen during thermal treatment through pipe 80.
The method of the invention is as follows. First the alloy specimen to be analyzed is prepared in rod form with typical dimensions being approximately 1/8 inch diameter by 3/4 inch length. The alloy may be, for example, ASTMA723 steel.
Next the specimen is electroplated with a thin layer of copper of a minimum of 0.002". The layer may also be thicker.
Next the specimen is attached to the fine wire 70 of for example 0.005 inch chromel thermocouple wire.
The specimen is lowered by way of the wire 70 into the quartz tube 20 and into the austenitizing furnace and maintained therein at temperature and for a desired time. The time in this furnace is not critical and may be about 15 minutes at about 850 degrees C.
Next, the specimen is lowered into the quench block and pinned there by the wire 72 which is inserted through hole 44 into the axial opening in the quench block as shown in FIG. 2. The specimen is held in the quench block until the thermocouple voltage indicates that the desired target temperature has been reached. This time is usually about 10 seconds.
Next, pinning pressure by wire 72 is released and so that the specimen 60 is dropped into the low temperature furnace maintained at desired temperature and immediately begin monitoring magnetization output to register the progress of the transformation. Magnetization changes and time are recorded by a computer. Total times to completion typically range from one to 24 hours.
Finally, the data is analyzed to determine needed details of transformation for the specimen material. The apparatus is designed to measure the amount of material transformed as a function of time from non-magnetic austenite to ferromagnetic decomposition products such as bainite or pearlite at a given temperature. The increase in magnetic response as a function of time measures the amount transformed as a function of time. The specific measure used in this embodiment of the invention is the imaginary component of the complex impedance. These measurements are made over a range of temperatures. The resulting data represent the transformation characteristics of the alloy under study which can then be used by materials engineers to obtain the desired microstructure and material properties. | The disclosure is of apparatus for determining the transformation characteristics of a metal alloy by treating the alloy to render it austenitic and then monitoring the isothermal decomposition of the austenite by measuring the magnetic change in the alloy. | 6 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of priority Provisional Application No. 60/672,676, filed Apr. 19, 2005. the disclosures of which are incorporated herein by reference.
TECHNICAL FIELD
The present invention generally relates to a method and apparatus for making uniform nanofiber webs, and more specifically relates to a method of making uniform nanofiber webs, wherein a source of process air is utilized to affect the spray pattern and quality of fibrillated material as it is expressed from a die assembly including a multi-fluid opening.
BACKGROUND OF THE INVENTION
Meltspun technologies, which are known in the art to include the spunbond and meltblown processes, manage the flow of process gases, such as air, and polymeric material simultaneously through a die body to effect the formation of the polymeric material into continuous or discontinuous fiber. In most known configurations of meltblowing nozzles, hot air is provided through a passageway formed on each side of a die tip. The hot air heats the die and thus prevents the die from freezing as the molten polymer exits and cools. In this way the die is prevented from becoming clogged with solidifying polymer. In addition to heating the die body, the hot air, which is sometimes referred to as primary air, acts to draw, or attenuate the melt into elongated micro-sized filaments. In some cases, a secondary air source is further employed that impinges upon the drawn filaments so as to fragment and cool the filaments prior to being deposited on a collection surface. Typical meltblown fibers are known to consist of fiber diameters less than 10 microns.
More recently, methods of forming fibers with fiber diameters less than 1.0 micron, or 1000 nanometers, have been developed. These fibers are often referred to as ultra-fine fibers, sub-micron fibers, or nanofibers. Methods of producing nanofibers are known in the art and often make use of a plurality of multi-fluid nozzles, whereby an air source is supplied to an inner fluid passageway and a molten polymeric material is supplied to an outer annular passageway concentrically positioned about the inner passageway. While the physical properties of nanofiber webs are advantageous to a variety of nonwoven markets, commercial products have only reached limited markets due to associated cost.
U.S. Pat. No. 5,260,003 and No. 5,114,631 to Nyssen, et al., both hereby incorporated by reference, describe a meltblowing process and device for manufacturing ultra-fine fibers and ultra-fine fiber mats from thermoplastic polymers with mean fiber diameters of 0.2-15 microns. Laval nozzles are utilized to accelerate the process gas to supersonic speed; however, the process as disclosed has been realized to be prohibitively expensive both in operating and equipment costs.
U.S. Pat. No. 6,382,526 and No. 6,520,425 to Reneker, et al., also both hereby incorporated by reference, disclose a method of making nanofiber by forcing fiber forming material concentrically around an inner annular passageway of pressurized gas. The gas impinges upon the fiber forming material in a gas jet space to shear the material into ultra-fine fibers. U.S. Pat. No. 4,536,361 to Torobin, incorporated herein by reference, teaches a similar nanofiber formation method wherein a coaxial blowing nozzle has an inner passageway to convey a blowing gas at a positive pressure to the inner surface of a liquid film material, and an outer passageway to convey the film material. An additional method for the formation of nanofibers is taught in U.S. Pat. No. 6,183,670 to Torobin, et al., which is hereby incorporated by reference.
Spacing of nozzles within the die body may be arranged such that material exiting the nozzle arrangement can be collected in a more uniform manner upon a forming surface. It has been recognized that a linear formation of equally spaced nozzles may result in a striping pattern that is visibly noticeable within the collected web. The stripes are found to reflect the spacing between adjacent nozzles. The striping effect seen in the web can further be described as “hills and valleys” whereby the “hills” exhibit a noticeably higher basis weight than that of the “valleys”. The industry may also refer to such basis weight inconsistencies as gauge bands.
U.S. Pat. Nos. 5,582,907 and 6,074,869, both incorporated herein by reference, address striping observed in meltblown webs by organizing nozzles into two linearly arranged parallel rows each having substantially equally spaced. Additionally, the two rows of nozzles are offset such that the nozzles are staggered in relationship to each other. Further, the staggered nozzles of the two rows are angled inward toward each other. In this fashion, each nozzle is utilizing a respective supply of primary process air, but lacks an ancillary air source to assist with web formation. These patents further assert external disruption of the polymeric material by an alternate gas source detracts from achievement of sufficient web uniformity.
A need remains for a process that can utilize multi-fluid openings for facilitating the distribution of molten polymer and a gas in the formation of nanofibers and further incorporates an ancillary gas source that assists with a uniform fiber collection across the width of the web.
SUMMARY OF THE INVENTION
The present invention is directed to a method and apparatus for making nanofiber webs, wherein a source of process air is utilized to affect the spray pattern and quality of fibrillated material expressed from a die assembly including a multi-fluid opening. Appropriately, the aforementioned process air is defined herein as an alternate or ancillary air source apart from primary process air, which primary air is simultaneously supplied with the molten polymeric material to the fiber forming multi-fluid opening. The ancillary air source of the invention is further distinct from secondary air, which is also known in the art as quenching air. The ancillary air can be described as a continuous fluid curtain of shielding or shaping air. While the use of air is preferred, the invention contemplates the use of alternate suitable gases, such as nitrogen. For the purpose of this disclosure, the ancillary air is referred to herein as a “fluid curtain nozzle” or “continuous air curtain”.
According to the present invention, disclosed herein is a method of forming uniform nanofiber webs, The method includes a multi-fluid opening, wherein the opening includes a passage for directing a gas and a separate passage for directing a polymeric material through the opening. The method further includes at least one fluid curtain nozzle positioned in operative association with the multi-fluid opening. According to the method of the present invention, a molten polymeric material and a gas fluid is simultaneously supplied to separate respective passages of the multi-fluid opening. The gas is directed through the multi-fluid opening to impinge upon the polymeric material to thereby form a spray pattern. A fluid is also directed through the fluid curtain nozzle for controlling the spray pattern of nanofiber expressed from the multi-fluid opening and subsequently, the nanofiber is collected on a surface to form a uniform nanofiber web.
In addition to controlling the spray pattern of the nanofiber expressed from the multi-fluid opening, the fluid curtain is believed to further control the temperature of the multi-fluid opening, wherein the temperature of the multi-fluid opening may be elevated by fluid curtain.
In one embodiment, continuous air curtains are employed to affect the spray pattern and quality of fibrillated material as the material is expressed from a multi-fluid opening including an array of two or more multi-fluid nozzles. The multi-fluid nozzles have an inner passageway for directing a first fluid, such as gas, and an outer annular passageway surrounding the inner passageway for directing a second fluid or molten polymeric fiber forming material. In addition, at least one continuous air curtain is positioned in operative association with the complete plural nozzle array to affect the polymeric spray formation pattern, which can be generally described as conical. The one or more air curtains are observed to “compress” and shape the spray pattern of fibrillated material that is emitted from the nozzles thereby decreasing the distance from which the fibers are spaced across the conic spray formation. Further, as the air curtains impinge upon the polymeric spray to affect the spray pattern, the air curtains can also function to shield the spray formations between adjacent plural nozzle arrays to diminish interaction or comingling of the fibrous material between adjacent nozzle arrays. Reduced comingling of the fibrillated polymeric spray of nanofiber between adjacent nozzle arrays is believed to significantly improve the uniformity of the web as the nanofibers are gathered onto a collection surface.
In one contemplated embodiment, a method for forming the uniform nanofiber web comprises an array of two or more multi-fluid nozzles preferably aligned in a generally linear arrangement, wherein a plurality of the multi-fluid nozzle arrays are positioned parallel to one another across the width of the fiber forming apparatus. In addition, at least one air curtain nozzle is positioned in operative association with each of the plural multi-fluid nozzle arrays, wherein the air curtain nozzle defines a generally elongated slot through which fluid is directed for formation of the fluid (air) curtain.
The present invention also contemplates the use of one or more air curtains with various other multi-fluid opening configurations, such as slot dies. Examples of slot die configurations include a double slot die and a single slot die. It is believed that the use of one or more air curtains in operative association with the double slot multi-fluid opening or single slot multi-fluid opening affects fiber formation and enhances the uniformity of the resultant web.
Other features and advantages of the present invention will become readily apparent from the following detailed description, the accompanying drawings, and the appended claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the effect of the air curtains on the polymeric spray formations of the multi-fluid nozzle configurations;
FIG. 2 is a schematic diagram of an array of annular nozzles embodying the principle of the present invention;
FIG. 3 is a schematic diagram of a slot die assembly embodiment of the present invention;
FIG. 4 is a schematic diagram of an alternate slot die assembly embodiment of the present invention; and
FIG. 5 is a schematic diagram of still another alternate non-annular embodiment of the present invention.
DETAILED DESCRIPTION
While the present invention is susceptible of embodiment in various forms, there is shown in the drawings, and will hereinafter be described, a presently preferred embodiment of the invention, with the understanding that the present disclosure is to be considered as an exemplification of the invention, and is not intended to limit the invention to the specific embodiment illustrated.
The method of making nanofiber webs in accordance with the present invention can be practiced in keeping with the teachings of U.S. Pat. Nos. 4,536,361 and 6,183,670, both previously incorporated herein by reference. The present invention further contemplates a method of forming fibrillated nanofibers and nanofiber webs, wherein one embodiment, shown in FIG. 2 , includes a die assembly 20 including an array of plural multi-fluid nozzles 28 . Each nozzle defines an inner fluid passageway for directing a gas 24 , and an outer passageway, wherein the outer passageway surrounds the inner passageway for directing polymeric material 22 through the nozzle. In addition, at least one fluid curtain nozzle 26 , or “air curtain” nozzle, is positioned in operative association with each array of plural multi-fluid nozzles. While the use of air through the fluid curtain nozzle may be preferred, the invention contemplates the use of alternate suitable gases, such as nitrogen.
FIG. 1 is a schematic view illustrating the influence of the air curtains in relation to individual nozzles. The air curtains shape and shield the spray pattern of the nozzles to reduce comingling between adjacent fibrous spray patterns of fibrillated material. FIG. 2 is a schematic view of the multi-fluid nozzle arrays 28 , wherein at least one air curtain 26 is positioned within operative association with the array 28 . As demonstrated in FIG. 1 , the air curtains shape the spray pattern of fibrillated material emitted from the nozzles within the array and further shields the spray formations of adjacent multi-fluid nozzle arrays.
It is also in the purview of the present invention to provide a die assembly including a slot configuration for delivery of a gas and a polymeric material. In such a configuration, it is contemplated to provide a polymeric material as a continuous film on a film forming surface, wherein non-limiting examples of film forming surfaces may include linear, wave-like, grooved, and the like. FIG. 3 is an illustrative embodiment a slot configuration, wherein the film forming surface 32 is linear. The slot configuration shown in FIG. 3 , is also referred to as a double slot-die assembly 30 , A double slot-die assembly defines a pair of linear film forming surfaces 32 arranged in converging relationship to each other. In accordance with the invention, the double slot-die assembly defines an elongated gas passage 34 for directing pressurized gas against molten polymer on both pair of linear film forming surfaces 32 . Film fibrillation is believed to occur once the path(s) of the film and gas intersect which may begin to occur as the film descends against the film forming surfaces and may continue to occur as the film is deposited into the gaseous stream. In addition, at least one fluid curtain nozzle 36 , or “air curtain” nozzle, is positioned in operative association with each film forming surface. Again, while the use of air through the fluid curtain nozzle may be preferred, the invention contemplates the use of alternate suitable gases, such as nitrogen.
In another illustrative embodiment, as shown in FIG. 4 , another die assembly 40 including a slot configuration, wherein a pair of linear film forming surfaces 42 are defined and arranged in parallel relationship to each other. Further, a pair of gas passages 44 arranged in converging relationship for each directing pressurized gas for impingement against respective film forming surfaces 42 . In addition, this embodiment, further includes at least one fluid curtain nozzle 46 , or “air curtain” nozzle, is positioned in operative association with each film forming surface.
In yet another illustrative embodiment, as shown in FIG. 5 , the slot configuration is also referred to as a single slot-die assembly 50 , which defines at least one gas exit passage 54 and one film forming surface 52 . Pressurized gas from a gas plenum chamber (not shown) is directed through a gas exit passage 54 , which in this illustrated embodiment is disposed at an acute angle to the film forming surface 52 . In addition, at least one fluid curtain nozzle 56 , or “air curtain” nozzle, is positioned in operative association with the film forming surface.
In yet another embodiment, the slot configuration includes a film forming surface, a gas exit passage, and an impingement surface, wherein the gas exiting the die is directed against the formed film on an impingement surface. In such an embodiment, the film forming surface may be a horizontal surface, otherwise referred to as 0°, or positioned at an angle up to about 80°. Preferably, the film forming surface is positioned at about 0° to about 60°. The film forming surface can be described to also have a length. The film forming surface preferably has a length of about 0 to about 0.120 inches. In addition, the impingement surface also has a preferred surface position, wherein the impingement surface may be perpendicular to the film forming surface or otherwise described as having a 90° angle relative to the film forming surface or the impingement surface may be at an angle than 90° relative to the film forming surface. Further, the impingement surface has a preferred length of between about 0-0.150 inches, more preferably between about 0-0.060 inches, and most preferably between about 0-0.001 inches.
According to the invention molten polymeric material suitable for formation of the nanofibers and nanofiber webs of the present invention are those polymers capable of being meltspun including, but are not limited to polyolefin, polyamide, polyester, poly(vinylchloride), polymethylmethacrylate (and other acrylic resins), polystyrene, polyurethane, and copolymers thereof (including ABA type block copolymers), polyvinylalcohol in various degrees of hydrolysis in cross-linked and non-cross-linked forms, as well as elastomeric polymers, plus the derivatives and mixtures thereof. Modacrylics, polyacrylonitriles, aramids, melamines, and other flame-retardant polymers have been contemplated as well. The polymers may be further selected from homopolymers; copolymers, and conjugates and may include those polymers having incorporated melt additives or surface-active agents.
As illustrated in FIG. 1 , the polymeric material is supplied to the outer passageways of the nozzle, a fluid, typically air, is simultaneously supplied through the respective inner passageway of each nozzle to impinge upon the polymeric material directed through the respective outer passageway to thereby form a spray pattern of fibrillated nanofibers from each nozzle. The spray pattern formed from the array of plural multi-fluid nozzles is affected by at least one air curtain nozzle, wherein said air curtain nozzle defines a generally elongated slot, as illustrated in FIG. 2 .
In such an embodiment, the slot may demonstrate a linear configuration, which is positioned in operative association with the entire array of nozzles to control and shape the spray patterns of the array. Preferably, the slot has a length of about at least the length of the plural multi-fluid nozzle array, and most preferably has a length which is approximately equal to the length of the array plus two times the center-to-center spacing of the individual nozzles. Thus, in a current embodiment, wherein a nozzle array includes three individual nozzles spaced approximately 0.42 in, center-to-center an associated air curtain nozzle has a slot length of approx. 1.7 in. Further, the slot preferably is provided with a width of about 0.003 in. to about 0.050 in. Air temperatures suitable for use with the process of the present invention preferably exhibit a range between 10° C. and 400° C., and more preferably exhibit a range between 25° C. and 360° C.
The air curtain has been observed to further shield the spray patterns of adjacent multi-fluid nozzle arrays, thereby reducing the degree of comingling between the multi-fluid nozzle arrays, as well as minimizing excess comingling of fibers of adjacent multi-fluid nozzles within an array. In addition, with respect to the slot configuration embodiments, the air curtain is further believed to affect the shape of the spray pattern of the fibrillated film. Without intending to be bound by theory, it is believed that a controlled spray pattern of fibrillated material results in a more uniform collection of nanofibers on a surface to produce a more uniform web.
Web uniformity usually refers to the degree of consistency across the width of the web and can be determined by several systems of measurement, including, but not limited to, coefficient of variation of pore diameter, air permeability, and opacity. Web uniformity metrics tend to be basis weight dependent. The nonwoven nanofiber fabric of the present invention may exhibit basis weights ranging from very light to very heavy, wherein the range captures fabric less than 5 gsm through fabrics greater than 200 gsm.
One acceptable uniformity metric is disclosed in U.S. Pat. No. 5,173,356, which is hereby incorporated by reference and includes collecting small swatches taken from various locations across the width of the web (sufficiently far enough away from the edges to avoid edge effects) to determine a basis weight uniformity. Additional acceptable methods for evaluating uniformity may be practiced in accordance with original paper, “Nonwoven Uniformity—Measurements Using Image Analysis”, disclosed in the Spring 2003 International Nonwovens Journal Vol. 12, No. 1, also incorporated by reference.
Despite the aforementioned methods of evaluating uniformity, lighter weight webs may nonetheless exhibit non-uniform performance characteristics due to differences in the intrinsic properties of the individual web fibers. As taught in U.S. Pat. No. 6,846,450, incorporated herein by reference, light weight webs may be evaluated for uniformity by measuring properties of the fibers rather than the web. It's been further contemplated to measure web uniformity in an inline process by way of various commercially available scanning devices that monitor web inconsistencies. In addition to improved web uniformity, it's believed the nanofiber web formed on the collection surface exhibits a loftier caliper as the nanofibers are deposited in a more controlled manner through the use of air curtains.
The present invention further contemplates the use of air curtains to improve the quality of the fibrillated material by forming more uniform nanofibers and creating a controlled environment from the time the polymer is first sprayed from the die assembly until the time the formed nanofibers are gathered on a collection surface. Fiber uniformity may be measured by those methods known in the art, such as by a scanning electron microscopic once the fabric is offline or inline by way of ensemble laser diffraction, as disclosed in original paper, “Ensemble Laser Diffraction for Online Measurement of Fiber Diameter Distribution During the Melt Blown Process, of the Summer 2004 International Nonwovens Journal, which is hereby incorporated by reference. Without intending to be bound by theory, when air curtains are used in conjunction with an array or two or more multi-fluid nozzles, it is believed that the air curtains form a controlled gradient-like effect of ancillary air as it diverges from the multi-fluid nozzle tip toward the fiber collection surface. In the region of the nozzle tip, the air currents influence the fiber formation process by acting to control the temperature at the nozzle tip. This control can include elevating the temperature of the fluid nozzles with the fluid (air) current. As the air from the curtains diverges from the nozzle tip, the air curtains of the invention are believed to entrain surrounding environmental air, which acts to isolate the newly formed nanofibers, while minimizing the deleterious effects of “shot” on web formation. Shot is known in the art as a collection of polymer that fails to form fiber during the fiber formation process and deposits onto the fiber collection surface as a polymeric globule deleteriously affecting the web formation.
In accordance with the present invention, the formed nanofibers are generally self bonding when deposited on a collection surface; however, it is in the purview of the present invention that the nanofiber web may be further consolidated by thermal calendaring or other bonding techniques known to those skilled in the art. It is further in the purview of the invention to combine the nonwoven nanofiber web of the present invention with additional fibrous and non-fibrous substrates to form a multilayer construct. Substrates which can be combined with the nanofiber web (N) may be selected from the group consisting of carded webs (C), spunbond webs (S), meltblown webs (M), and films (F) of similar or dissimilar basis weights, fiber composition, fiber diameters, and physical properties. Non-limiting examples of such constructs include S-N, S-N-S, S-M-N-M-S, S-N-N-S, S-N-S/S-N-S, S-M-S/S-N-S, C-N-C, F-N-F, etc., wherein the multilayer constructs may be bonded or consolidated by way of hydraulic needling, through air bonding, adhesive bonding, ultrasonic bonding, thermal point bonding, smooth calendaring, or by any other bonding technique known in the art.
The nonwoven construct comprised of the uniform nanofiber web may be utilized in the manufacture of numerous home cleaning, personal hygiene, medical, and other end use products where a nonwoven fabric can be employed. Disposable nonwoven undergarments and disposable absorbent hygiene articles, such as a sanitary napkins, incontinence pads, diapers, and the like, wherein the term “diaper” refers to an absorbent article generally worn by infants and incontinent persons that is worn about the lower torso of the wearer can benefit from the improved uniformity of a nanofiber nonwoven in the absorbent layer construction.
In addition, the material may be utilized as medical gauze, or similar absorbent surgical materials, for absorbing wound exudates and assisting in the removal of seepage from surgical sites. Other end uses include wet or dry hygienic, anti-microbial, or hard surface wipes for medical, industrial, automotive, home care, food service, and graphic arts markets, which can be readily hand-held for cleaning and the like.
The nanofiber webs of the present invention may be included in constructs suitable for medical and industrial protective apparel, such as gowns, drapes, shirts, bottom weights, lab coats, face masks, and the like, and protective covers, including covers for vehicles such as cars, trucks, boats, airplanes, motorcycles, bicycles, golf carts, as well as covers for equipment often left outdoors like grills, yard and garden equipment, such as mowers and roto-tillers, lawn furniture, floor coverings, table cloths, and picnic area covers.
The nanofiber material may also be used in top of bed applications, including mattress protectors, comforters, quilts, duvet covers, and bedspreads. Additionally, acoustical applications, such as interior and exterior automotive components, carpet backing, insulative and sound dampening appliance and machinery wraps, and wall coverings may also benefit from the nanofiber web of the present invention. The uniform nanofiber web is further advantageous for various filtration applications, including bag house, plus pool and spa filters.
It has also been contemplated that a multilayer structure comprised of the nanofiber web of the present invention may be embossed or imparted with one or more raised portions by advancing the structure onto a forming surface comprised of a series of void spaces. Suitable forming surfaces include wire screens, three-dimensional belts, metal drums, and laser ablated shells, such as a three-dimensional image transfer device. Three-dimensional image transfer devices are disclosed in U.S. Pat. No. 5,098,764, which is hereby incorporated by reference; with the use of such image transfer devices being desirable for providing a fabric with enhanced physical properties as well as an aesthetically pleasing appearance.
Depending on the desired end use application of the uniform nonwoven nanofiber web, specific additives may be included directly into the polymeric melt or applied after formation of the web. Suitable non-limiting examples of such additives include absorbency enhancing or deterring additives, UV stabilizers, fire retardants, dyes and pigments, fragrances, skin protectant, surfactants, aqueous or non-aqueous functional industrial solvents such as, plant oils, animal oils, terpenoids, silicon oils, mineral oils, white mineral oils, paraffinic solvents, polybutylenes, polyisobutylenes, polyalphaolefins, and mixtures thereof, toluenes, sequestering agents, corrosion inhibitors, abrasives, petroleum distillates, degreasers and the combinations thereof. Additional additives include antimicrobial composition, including, but not limited to iodines, alcohols, such as such as ethanol or propanol, biocides, abrasives, metallic materials, such as metal oxide, metal salt, metal complex, metal alloy or mixtures thereof, bacteriostatic complexes, bactericidal complexes, and the combinations thereof.
From the foregoing, it will be observed that numerous modifications and variations can be affected without departing from the true spirit and scope of the novel concept of the present invention. It is to be understood that no limitation with respect to the specific embodiments illustrated herein is intended or should be inferred. The disclosure is intended to cover, by the appended claims, all such modifications as fall within the scope of the claims. | The present invention is directed to a method and apparatus for making nanofiber webs, wherein a source of process air is utilized to affect the spray pattern and quality of fibrillated material expressed from a die assembly including a multi-fluid opening. Appropriately, the aforementioned process air is defined herein as an alternate or ancillary air source apart from primary process air, which primary air is simultaneously supplied with the molten polymeric material to the fiber forming multi-fluid opening. The ancillary air source of the invention is further distinct from secondary air, which is also known in the art as quenching air. The ancillary air can be described as a continuous fluid curtain of shielding or shaping air. | 3 |
BACKGROUND OF INVENTION
1. Field of invention
This invention relates to an improved chemical system for the enhancement and maintenance of cementaceous and composite asphalt building materials.
2. Description of the Prior Art
Cement tile and asphalt shingles have historically dominated the residential roofing market. Despite their success, the unattractive discoloration encountered throughout the United States and Canada particularly in moist temperate climates is becoming increasingly unacceptable. While the approach among respective manufacturers differ, the consensus in the cement tile industry has deferred the problem to the after market roof cleaning industry which has flourished in providing the routine service required to maintain appearance. High pressure water systems incorporating chlorine bleach are typically used. In warm humid climates typical in the Gulf States the service is required annually. Roof painting where permitted can postpone reoccurrence approximately two fold. In contrast, the asphalt shingle industry cautions against the use of high pressure washing systems as the process may remove granules which will shorten roof life. A gentle application of dilute aqueous chlorine bleach and trisodium phosphate from a ladder or walkboards is suggested by the Asphalt Roofing Manufacturers Association to avoid roof damage. The effectiveness of such cleaning is only temporary and there is little evidence of successful practitioners serving the residential asphalt shingle after-market. However, manufacturers offer several types of algae resistant products which have met with limited success.
The state-of-the-art technology for algae resistant asphalt shingles centers on a source of microbicide which can be released as a result of mechanical and/or chemical weathering. Of commercial significance, are shingles incorporating a percentage of zinc metal or zinc oxide coated granules as the inhibitor source. A second generation incorporating copper oxide as an inhibitor source of relatively higher toxicity has recently been introduced. The release of soluble metallic salts from these sources is typically via adsorption of carbon and sulfur dioxides in presence of moisture yielding acidic reactants. The residence time of soluble metal salts released from these products can be quite limited being readily removed by rain. However, slow release of inhibitor from these relatively inert sources is projected to continue over extended periods of time. Clearly, environmental conditions as they effect release and residence time on roof surface are major variables in this mechanism of inhibition. The effectiveness of the technology can only be improved with increased quantities of source material exhibiting higher levels of toxicity to counteract the transient nature of the active chemical inhibitors.
The present industry approach appears well founded on the observed inhibition which develops on the trailing surfaces below metal vents and stand pipes installed with roofing systems. While this potential source of tin, copper and zinc microbicide in the form of soluble metal salts is obvious, the mechanism by which inhibition is established may not be. A priori, released microbicide from any source must have a finite residence time in order to be effective. For this purpose, the exchange and chelation of polyvalent metallic ions with organic and inorganic receptor sites that develop on weathered asphalt and granule surfaces is well documented. Carboxylic acid end groups represent the highest oxidation state of asphalt surface while hydrous oxide surface functionality results from granule weathering. As electron donor sites, both interact with polyvalent metal cations to increase their residence time on weathered roof surfaces. Uncontrolled early release of such inhibitors contributes both to their fugitive nature and the substantial chemical inefficiencies inherent in the present state-of-the-art. Further compromises result from the complexities of asphalt shingle manufacture involving distribution and adhesion by partial embedment as the only means of securing granule inhibitor sources.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide an improved chemical treatment system to inhibit algae discoloration which occurs on cement tile and composite asphalt roofing products.
It is a further object of the present invention to provide a durable transparent chemical system which confers luster with out altering esthetic appearance and retains a level of effectiveness consistent with the life of roof surface.
It is a still further object of the present invention to provide a predetermined controlled level of active chemicals securely bound and uniformly distributed over the entire exposed area of the roof assuring optimum effectiveness against discoloration.
It is another object of the present invention to provide a simple and economical process for the application of the improved chemical treatment system which can be used to enhance after market maintenance procedures and alternatively be incorporated in plant manufacture or field installation of cement tiles or asphalt shingles. These and other objects and advantages of the present invention will become more apparent to those skilled in the art when the instant disclosure is read in conjunction with the accompanying examples.
SUMMARY OF THE INVENTION
The above objects have been achieved in the process of the present invention by utilizing a weatherable water-borne resin in combination with wetting agents which confer positive spreading coefficients for effective uniform thin film coverage over the entire surface area of the roofing product. Incorporation of polyvalent metallic salts can be accomplished by concurrent premixing of compatible aqueous systems for combined application with resin or separate sequential treatment. On setting, the polyvalent metallic cations become bonded by organic ligands with the desired uniform distribution and intimate contact over the entire surface area susceptible to algae growth. The chemical treatment system inhibits algae discoloration of both asphalt shingles and cement tile and needs only to be applied to exposed surfaces given the true autotrophic nature of the predominant species encountered.
The transparent water-borne resins used in the system may suitably be any of the water-borne resins including those engineered for optimum adhesion and weatherability as single-ply membranes for built-up roofing application. Among the commercially more cost effective, vinyl polymers of acrylate esters and their copolymers with styrene, vinyl acetates and urethanes have gained prominence in built-up roofing applications by virtue of excellent weathering, adhesion and elastic properties. Emulsion systems formulated with thermoplastic, cationic exchange and chelating resins can also be used to secure the polyvalent metallic cations. Copolymer polyacrylate resin products of anionic polymerization are particularly suitable; alone or in combination with other organic ligands.
Employed in conjunction with the water-borne resin is sufficient wetting agent, based upon surface tension required, to achieve positive spreading on the substrate surface. A wide variety of ionic and nonionic wetting agents are available for this purpose. The preferred wetting agents are high performance alkyl and alkyl ester sulfonates, which provide excellent system compatibility. The preferred water-borne resins and wetting agents comprise anionic organic ligands which serve to secure the polyvalent metallic cations in the form of unique chelates and salts with general microbicide activity and excellent chemical stability. The preferred microbicides are comprised of water soluble salts of copper, tin and zinc which also confer the desired system compatibility and durability.
DETAILED DESCRIPTION OF THE INVENTION
The method of the present invention is suitable for treating exterior residential roofing products which support the growth of unsightly dark colored algae. Representative products include the popular composite asphalt shingles and cement tiles which typically contain carbonate nutrients for the prevalent gloeocapsa algae. It is beneficial to clean or otherwise restore the esthetic appeal of roof surfaces prior to application of the chemical inhibitor system. As a special feature of the present invention, surface active agents are incorporated to overcome the resistance to wetting and rewetting characteristic of roofing surfaces. The enhanced performance of bleaching and/or cleaning processes through the use of wetting agents is readily apparent in terms of the uniformity of chemical absorption achieved. The incorporation of optimum surface specific wetting agent clearly advances state-of-the-art and is instrumental to chemical effectiveness and efficiency of roof cleaning as well as application of inhibitor system with uniform distribution and ultimate adhesion.
The inhibitor system of the present invention is composed of polyvalent metallic salts and chelates with the organic ligands of wetting agents and water borne-resins. The system is produced on the roofing surface through interaction of inorganic water soluble polyvalent metallic salts and formulated organic water-borne resins and wetting agents. The soluble polyvalent inhibitor salts become encapsulated as the resin sets through interaction in binding dissociation equilibria. Displacement of monovalent resin and surfactant cations by polyvalent metallic inhibitor cations is solubility driven by the precipitation of insoluble polyvalent salts and chelates. The monovalent cation by-product salts are eventually leached from the inhibitor film system during subsequent weather exposure. Uniform deposition accomplished with the use of wetting agent permits the ultimate system stability and versatility. The durability of the inhibitor system derives from the inherent bonding nature of film forming resin and the compatibility of organometalic inhibitor salts and chelates formed upon co-application of the chemical system. Substrate surface as the point of microbial growth can be uniformly protected with effective composition and concentration of inhibitors. The physical and chemical stability to ultraviolet light/weathering as well as the level of toxicity for a range of ion pairs is well documented as basis for selection. Most significantly, the novel polyvalent metallic salts and chelates of organic ligands produced by exchange exhibit greater affinity toward the organisms responsible for discoloration owing to their lipophilic nature.
In addition to uniform application of the inhibitor system, stiochometry is important for optimum chemical efficiency. For this purpose, an excess of anionic organic ligand is incorporated to drive the binding dissociation equilibria toward insoluble polyvalent chelate and salt formation. Precautions must be taken in application to avoid premature coagulation of the water-borne resins by added electrolyte. Sequential or dilute surface addition of components is effective toward circumventing this instability problem. Surface areas of residential roofing products are typically quite low and can be satisfactorily protected with thin film inhibitor coverage toward achieving optimum adhesion and cost effectiveness. The versatility of the system allows for concentration and composition control of both the microbicide and binder ligands for optimum product performance. Most surprising and very unexpected is elimination of adverse surface blushing of polymer films accompanying ligand exchange yielding more hydrophobic structures. Quite significantly, blushing has been the primary impediment in development of transparent single-ply membrane technology of water-borne resins. This is particularly true in residential roofing where the luminous opacity accompanying the surface dew point temperature is esthetically unacceptable in the marketplace. The obviation of blushing in the present systems leaves only a degree of luster imparted by the transparent film without altering the original esthetic appeal.
As mentioned above, substrate surface wetting is instrumental toward achieving optimum chemical efficiencies of the present invention. As a general class of surfactants they can be nonionic, anionic or cationic. Representative types include alkyl- and alkyl arylethoxylates, sulfates, sulfonates and quaternary ammonium salts. Nonionic ethoxylates of synthetic aliphatic alcohols with low HLB are available under the trade name Renex from ICI Americas Inc., Wilmington, Del. Polyoxypropyl polyoxyethyl block copolymers available under the trade name Pluronic from BASF Corp., Parsippany, N.J. are also effective nonionics. Alkyl sulfate sodium salts available under the trade name Witcolate from Witco Chemical Corp., New York City, N.Y. are preferred in bleaching formulations for their stability. Alkyl sodium sulfo succinates, available from various suppliers, are preferred for most difficulty wettable substrates. Generally, wetting agents serve equally well in rewetting and therefor, can be applied independently in preparing the substrate surface or as a formulated component. Each formulations must be evaluated with regard to pot life to circumvent premature interactions which include the exchange of an equivalent amount of organic ligand as an integral part of the inhibitor system. Product selection is dictated by properties of the specific substrate and the necessary reduction of liquid surface tension to facilitate wetting which is readily apparent in droplet behavior upon surface contact.
The toxicity of metal salts over abroad range has been published in numerous technical sources such as "Dangerous Properties of Industrial Materials", 6th edition by N. Irving Sax. While any water soluble salts of polyvalent metals from the third, fourth and fifth horizontal periods of the periodic table can be used, judicious selection would focus on metals responsible for the inhibition observed on existing roof installations which include zinc copper and tin. Examples of salts which can be used in accordance with the present invention include, zinc acetate dihydrate, zinc sulfate heptahydrate, cupric sulfate pentahydrate, cupric nitrate trihydrate and stannic sulfate dihydrate. They are readily dissolved and commercially available. The deposition of these salts from solutions with positive spreading coefficients assures effective molecular coverage of the substrate surface which supports algae growth.
Any suitable exterior water-borne resins and organic ligands may be used in securing the polyvalent metallic inhibitors of the present invention via mechanisms of encapsulation, chelation and salt formation. The elastomeric roof mastics, which have been developed for adhesion, elongation and weatherability, exhibit optimum performance in transparent thin film application on sloped surfaces. As indicated above, anionic water-borne resin systems are preferred to secure polyvalent metallic cations in binding exchange equilibria and it is desirable to have films with good light stability and elasticity. Examples of polymer emulsions which can be used in accordance with the present invention are styrene-acrylic ester copolymers available from Rhone-Poulenc, Kennesaw, Ga. under the trade name Rhodoplas. The preferred acrylic ester copolymers which generally offer superior light stability are available from Rohm & Haas Co., Philadelphia, Pa. under the trade name Rhoplex. The particularly suitable resins are those which exhibit sufficient thermoplastic character to resists dirt pick-up and sufficient light stability to resist yellowing during service life.
The relative amounts of polyvalent metal salt, organic ligands can vary widely within the primary objective to accommodate both the specific substrate surface and service requirements. Of the total composition yielding the microbicide system more than about 85% is organic and the remaining inorganic salt content is ultimately reduced to less than about 5% as a result of leaching the monovalent by-product salts during service life. A preferred composition is 91% organic ligands and 9% metallic salt. Valence state and equivalent weight of the selected metallic salts are determining factors in establishing stiochometry and a substantial excess of organic ligand can be highly beneficial. While surface films uniformly applied can physically encapsulate metallic inhibitors the transfer of polyvalent metallic ions to the solid phase by cation exchange is a preparative feature which relies on receptor sites incorporated in anionic resin systems. The organic ligands exchanged in chelate or salt formation confer film compatibility and added durability of the microbicides. The preferred products exhibit lipophilic properties with enhanced microbicide activity, while the resin film serves to reduce surface erosion and prolong roof life.
The inhibitor system is readily produced by applying the dissolved polyvalent metal salt and resin emulsion in ratios ranging from 1:10 to 1:500 parts by weight respectively. Incorporation of wetting agent at levels comparable to metal salt are typical. The process is carried out by any suitable method such as spraying, rolling or brushing of components preferably on a clean, readily wettable surface. A preferred method is by simultaneous dual spray application of salt solution and resin emulsion. The quantities applied in coverage of exposed roofing surface is in the range of 0.01 to 3.0 pounds per square. The preferred level of application is in the range of 0.1 to 0.3 pounds per square. Versatility of the system in terms of both chemical composition and level of application permit adaptation to specific substrates as well as environmental exposure conditions.
The invention is further illustrated by the following examples in which all parts and percentages are by weight unless otherwise indicated.
EXAMPLE 1
Samples of asphalt shingle and cement tile were treated with various water-borne resins and exposed to atmospheric conditions in Central Florida. Samples consisted of light and dark shingle composites and unpigmented cement tiles. Resin emulsions were brush applied to the rough surfaces producing films approximately 3 to 5 mils thick. The samples were monitored with the following observations; plus signs indicating relative degree.
__________________________________________________________________________Substrate Resin Daily 3 months 6 months 12 months__________________________________________________________________________Light shingle 1 blush++ soil+ soil+ soil+yellow++ 2 blush++ unchanged soil+ soil++ 3 blush++ unchanged unchanged unchangedDark shingle 1 blush+++ soil+ unchanged soil+ 2 blush+++ unchanged unchanged soil+ 3 blush+++ unchanged unchanged unchangedCement tile 1 blush+ unchanged unchanged soil+yellow+ 2 blush+ unchanged unchanged soil+ 3 blush+ unchanged unchanged unchanged__________________________________________________________________________ Resin 1. Rhodoplas GS 125; styrene acrylate copolymer. Resin 2. Rhoplex EC 1791; acrylate copolymer. Resin 3. Rhoplex AC 264; acrylate copolymer.
Given necessary atmospheric conditions, daily blushing was observed from sunrise until surfaces dried. The blushing effect was most objectionable on dark asphalt shingle and least noticeable on unpigmented cement tile. Soiling and yellowing were slight in each case but most apparent on the light gray asphalt shingle.
EXAMPLE 2
A residential site was selected for initial evaluation of wetting requirements on discolored product. The color of the original off-white asphalt shingle roofs North face was indiscernible alter six years service life. The soiled surface with approximately 3 in 12 pitch was sectioned for the following chemical evaluations. Wetting as a function of color removal by scrubbing and bleaching was examined for a series of surfactants in addition to uniformity in application of metal salt solution and resin emulsion. Surfactant selections were based upon preliminary examination of chemical compatibility and integrity of polymer films prepared on glass plates.
__________________________________________________________________________ MILD 3% SODIUM ZINC ACETATE 7 STYRENATEDSURFACTANT, 3% SCRUB HYPOCHLORITE DIHYDRATE, 0.2% ACRYLIC, 10%__________________________________________________________________________1 poor fair fair goodDisodium dihexadecyl diphenyl oxidedisulfonate2 poor fair fair goodSodium salt polymeric carboxylic acid3 fair fair fair goodAlkyl benzene sulfonate/alkanolamide/ethoxylate4 poor fair fair goodPolyoxyethylene (12) tridecyl alcohol5 poor good good goodEthyl hexyl sulfate sodium salt6 poor excellent good goodSodium ethoxylated alcohol sulfosuccinate__________________________________________________________________________ 1. Dowfax (R) 8390, Dow Chemical Co. 2. Tamol 850, Rhom&Haas Co. 3. Witcodet 100, Witco Chemical Corp. 4. Renex 30, ICI Inc. 5. Witcolate D51 & 6. Emcol 4300, Witco Chemical Co. 7. Rhodoplas GS 125, RhonePoulenc.
The roof surface, vertically sectioned in sixths, was treated with individual surfactants and mildly scrubbed to assess color removal as a first step. Sodium hypochlorite was then spray applied slowly, avoiding run off as much as possible, until the original shingle appearance was restored. Efficiency of the chemical bleaching via surface wetting was the major observable effect in this sequence. Zinc acetate solution was applied over the entire surface followed by resin emulsion over the lower half; both at approximately 1 gal. per 500 sq. ft. Two years have lapsed since the roof was treated with no evidence of reoccurring discoloration.
EXAMPLE 3
A Planned Unit Development of one hundred villas developed severe irregular discoloration on North facing roof exposures during a seven year life. A maintenance service was contracted to restore the original beige asphalt shingle roof appearance which involved initial cleaning/bleaching/rinsing followed by a subsequent annual maintenance treatment to remove reoccurring discoloration. A single 1500 sq. ft. roof with 4 in 12 pitch was isolated from the service at the mid point between cleaning cycles for comparative inhibitor evaluation. The test roof was treated in turn with sodium ethoxylated alcohol sulfo succinate (0.3%), zinc acetate (0.3%) and Rhoplex E-2540 acrylic emulsion (7.0%) at rates of approximately 1 gal. per 500 sq. ft. The test roof has shown no evidence of reoccurring discoloration during the 2 and 1/2 years since the inhibitor treatment was applied. The remaining roofs continue to be cleaned annually to remove the objectionable reoccurring discoloration, i.e. 2 additional cleaning cycles completed.
EXAMPLE 4
A 7 year old 4000 sq. ft. single family home with beige asphalt shingles was selected as a worst case of discoloration on a recessed shaded portion of the North facing roof with 6 in 12 pitch. The depth of microbial growth and the slope rendered the roof accessible only from the adjoining elevated sections on either side which exhibited irregular relatively moderate discoloration. The elevated surfaces were cleaned with 3% sodium hypochlorite solution containing 0.5% sodium 2-ethyl hexyl sulfate spray applied at a rate controlled to circumvent any run off. Using 5% sodium hypochlorite solution containing 0.05% dioctyl sulfo succinate sodium salt, the recessed portion was also cleaned without chemical loss. Chemical efficiency approaching that of solution reaction was achieved through controlled surface wetting; eliminating first black and then purple coloration in restoring the original shingle color without run-off.
Only the recessed portion of the roof was treated to permit comparative evaluation of zinc inhibitor system. The 0.2% solution of zinc sulfate heptahydrate was spray applied without additional wetting agent followed by a 5.0% active emulsion of Rhoplex EC 1685; each at approximately 1 gal. per 500 sq. ft. Neither the cleaned elevated or cleaned and treated recessed roof sections show any evidence of reoccurring discoloration approaching 2 years exposure.
EXAMPLE 5
Major manufacturer's composite asphalt shingles and cement tile samples were treated to evaluate alternative inhibitor systems. For this purpose, individual production samples of asphalt shingles, slurry coated and uncoated cement tiles were spray coated with 0.5% sodium ethoxylated alcohol sulfo succinate solution followed in turn with 0.25% copper sulfate or 0.25% stannous chloride and 3.5% active Rhoplex AC 264 acrylic copolymer emulsion. The treated samples, acceptable on visual examination and devoid of blushing on exposure, are well into the second year of exposure with no evidence of discoloration. Notably, accelerated exposures tests are also going forward at several sun-belt locations. | This invention discloses weatherable elastomeric and thermoplastic composite polymer films incorporating organometallic complexes for protection of exterior surfaces against the growth of dark colored algae. The process involves the surface reaction of water soluble polyvalent metallic salts with surfactants at reduced surface tension in the presence of film forming emulsion polymers. The lipophilic organometallic reaction products thus formed are encapsulated by polymer films with demonstrated exterior weathering durability in roof mastics and architectural coatings. By virtue of their vapor transmission, adhesion and elastic properties, the composite polymer films incorporating compatible algicidal organometallics extend both the life and appearance of exterior substrates. | 2 |
BACKGROUND OF THE INVENTION
Conventional, glulam wood beams manufacturing are usually manufactured with perfectly squared wood planks corresponding to the width of the desired beam less the wood necessary to plane down the beam so as to obtain perfectly smooth surfaces,
The planing down step is often necessary in view of the fact that the glulam beams can be used as decorating elements as well as structural elements. This double use of glulam beans requires that the surface be exempt of any defects such as the presence of flash on the planks.
On the other hand, an optimum exploitation of forest resources requires that saw mills exact as much squad planks as possible. This objective is particularly difficult to reach when the trees are of small diameter. In this case, the proportion of planks with bark can be important since the diameter of the tree is sometimes insufficient to provide planks of standard dimensions to produce perfectly squared surfaces. However, this type of tree with small trunk diameter, constitutes an important stock of resources of coniferous trees in the subpolar circle in the northern hemisphere. The mechanical resistance of this type of wood is however very good due to the slow growth of the trees which produces a width of high densities and furthermore, is type of wood usually is devoided of large timber knots which can comprimise the mechanical resistance.
Furthermore, the planks with greater width generally used in the preparation of glulam wood beams are made with trunks exhibiting large diameter and they have the tendency to change shape upon drying. This property renders the glueing of the planks difficult. This property renders the glueing of the plank difficult by eating tensions within the beams.
Due to the difficulty to extract planks of sufficient width and exempt of a flash, the above mentioned northern forest resource has been neglected up to now for the manufacturing of plank for the use in glulam wood beams.
The instant invention overcomes the limitation of the prior art by providing a beam and a method of making beams using plank obtained from trees having small trunk diameters.
SUMMARY OF THE INVENTION
The instant instant invention provides a wood beam composed of rectangular strips, said strips comprising planks of identical length and having a width substantially smaller than the desired width of the beam, said beam being characterized by the presence of two strips forming the top and the bottom of said beam and a central part comprising either planks or strips, said beam being further characterized by the presence of flash in the interior and by the top, bottom and sides external surfaces being essentially plane.
In an other embodiment there is further provided wood beam composed of rectangular strips, said strips comprising planks of identical length and having a width substantially smaller than the desired width of the beam, said plank being characterized by having two longitudinal plane surfaces substantially parallel constituting the top and the bottom of said plank and having two longitudinal plane surfaces constituting the sides of said planks, the sides being substantially perpendicular to the top surface and the bottom surface, the bottom surface intersecting at a right angle each of the two sides, the top surface being linked to the sides by intersecting said sides at right angles or by the natural curvature of the from which the plank is obtained thus forming flash, said strips being formed by two or more planks adhered by their sides thus forming lateral joints and in such a way that the bottom of the planks form a uniform plane surface and that the sides of the two planks at the lateral ends of the strips, non adjacent to another plank, intersect the top surface and the bottom surface at a right angle, the beam being formed by the assembly and reciprocal adherence of the strips, said beam being characterized by the presence in its interior of planks at least some of which exhibiting flash, said beam being also characterized by a top and a bottom each composed by a strip the bottom of which constituting the exterior of the beam, the strips included between the top strip and the bottom strip forming a central part, said beam being also characterized by two sides having a plane surface perpendicular to the top and bottom of the beam.
The instant invention either provides a method for making the beam according said method comprising the steps of:
obtaining planks having two longitudinal plane surfaces substantially parallel constituting the top and the bottom of said planks and having two longitudinal plane surfaces constituting the sides of said planks, the sides being substantially perpendicular to the top and the bottom surface, the bottom surface making a right angle with each of the two sides, the top surface being linked to the sides by either a right angle or the natural curvature of the trunk from which the plank is obtained thus forming flash; drying the planks to obtain a hydrometric degree compatible with the application of art adhesive; sorting the planks to eliminate those that do not conform with pre-established selection criteria selected from general geometry, absence of timber knots effecting the mechanical resistance of the planks and mechanical resistance properties; treating the sides of the planks to optimize the efficiency of a selected adhesive; selecting the planks sorted according to their width to assemble the strips having a length corresponding to the desired length of the beam; applying the adhesive on said sides of the planks and placing the planks side by side in such a way that the sides are in reciprocal contact and that the bottom of the planks form a plane surface to constitute strips having a width equal to or greater than the desired width of the beam and applying a lateral pressure to optimize adhesion of the plank; joining the strips by their ends to form finger joints; applying an adhesive on the top surface of the strips; and assembling the strips to form a beam having the desired dimensions and applying pressure to optimize the adhesion of she strips.
There is further provided a method in which the planks in the strips differ in their width and are assembled in panels according to a repetitive pattern relative to their width, said panels being cut along the longitudinal axis of the planks to obtain strips of desired width, the cutting being made such that the sides of the strips intersect the bottom and top surfaces of said planks at a right angle and that said sides are constituted essentially of the duramen of the wood.
BRIEF DESCRIPTION OF THE DRAWINGS
These and other features of the invention will become more apparent from the following description in which reference is made to the appended drawings wherein:
FIG. 1 is a perspective view of a plank used in the instant invention for the making of glulam beams;
FIG. 2 is a sectional view of the plank of FIG. 1 showing the presence of a flash;
FIG. 3 is a perspective view of a strip of the instant invention;
FIG. 4 is a perspective view of a beam of the instant invention;
FIG. 5 is a perspective view of two types of finger joints;
FIG. 6 is a perspective view of a wood beam comprising out of line finger joints;
FIG. 7 is a side view of a panel used in the manufacturing of strips;
FIG. 8 is a perspective view illustrating the method for obtaining strips width of dispersed finger joints;
FIG. 9 is a sectional view of a beam comprising strips in which the strips forming the top and bottom of the beams are strips with dispersed finger joints;
FIGS. 10-15 are sectional views of wood beams of the instant invention illustrating possible organization of the planks and strips within the beam; and
FIG. 16 is a schematic diagram representing the increased yield achievable by tolerating flash in the preparation of planks.
DETAILED DESCRIPTION OF THE INVENTION
The wood beam of the instant invention is characterized in that it is formed with strips. These strips are in turn constituted from an assembly of planks. The planks, of which an example 10 is illustrated in FIG. 1, exhibit two longitudinal plane surfaces substantially parallel constituting tie top 12 and the bottom 14 and two longitudinal plane surfaces constituting the sides 16 . The planks are also characterized by a length 13 , a width 15 and a thickness 17 . The width of a given plank is not necessarily uniform at all points along the length but may vary slightly. This variation is due to the natural decrease in trunk diameter from which the plank is obtained. This variation of the width is acceptable for the manufacturing of the wood beams of the instant invention. The sides of the planks are substantially perpendicular to the top surface and the bottom surface and they intersect the bottom at a right angle (90°), thus forming two sharp edges 18 . The top surface is linked to the sides by either a right angle to form a sharp edge, or by a curved surface corresponding to the natural curvature of the trunk as indicated at 11 .
The presence of a curved surface linking the top surface to one of the sides may be defined as an empty volume of wood when compared to a plank exhibiting four sharp edges. This volume 19 is defined by the space included between the curved surface of the trunk and the imaginary extension of the side and of the top surface (FIG. 2 ). This empty volume, in the instant description, is referred to as flash. Flash may be due, for example, to the sawing of a trunk with a diameter insufficient to provide planks of a given thickness and of a given width exhibiting four sharp edges along the entire plank length (perfectly squared plank).
One of the important aspects of the invention is to provide a glulam wood beam and a method of making the same, allowing the use of planks exhibiting flash and consequently permitting the use of trees having small diameter trunks. This aspect not only allows the exploitation of a neglected forest resource in the manufacturing of glulam but it also allows a significant increase in the yield of gross product/finish product. The beam, despite the presence of flash, exhibits mechanical properties that conform to the standards in the construction industry.
Due to the presence of flash, the thickness of the planks is not necessarily uniform. The thickness of a plank in the present description will be defined by the thickness measured between the top plane surface and the bottom plane surface.
The thickness and the width (Thickness×width) of the planks used in the manufacturing of the beams of the instant invention vary and are preferably, without being limited to these dimensions, two inches by two inches (2″×2″), two inches by three inches (2″×3″), two inches by four inches (2″×4″) and two inches by six inches (2″×6″). Similarly, the lengths will be, without being limited to these values, preferably between six feet (6′) and 20 feet (20′).
The present invention thus allows the manufacturing of a wood beam with desired dimensions using planks containing flash and having width substantially smaller than the desired width of the wood beam.
The strips 20 (FIG. 3) of the woodbeam comprise planks of identical length and thickness, but which may have different width, assembled by their sides to form lateral joints 21 so that the bottom surface 23 of the strip is plane and constituted by the bottom surface of the planks 14 . The strips are characterized by a length 22 corresponding to the length of the planks, a thickness 26 corresponding to the thickness of the planks and a width 24 corresponding to the sum of the width 15 and of the planks 14 .
The sides 25 of the strips are formed by the sides of the planks that are not adjacent to other planks and positioned at the lateral ends of the strips. The sides of the strips intersect the bottom surface and the top surface of the plank at a right angle, thus forming two sharp edges 27 .
A frequently encountered problem in the manufacturing of glulam beams using planks having width substantially similar to the width of the beam is that the planks when dried, have a tendency to change shape due to the non uniform shortening of wood fibres. This deformation often results in the “curving” of the plank and is usually more pronounced for planks of greater dimensions. This deformation is not desirable since it generates tensions that can be strong enough to cause the rupture of the joints within the strips and the beam. Advantageously, the instant invention considerably reduces this effect by using planks having widths substantially smaller than the width of the beam. Furthermore, the presence of flash in lateral joints provides tension breaking points within the strips contributing to the stabilization of the beam.
In a further aspect of the instant invention, the wood beam 30 (FIG. 4) is constituted by strips 20 horizontally superimposed and adhered together to obtain a wood beam of a desired thickness. The arrangement of the strips within the beam is such that the lateral joints 21 of two adjacent strips are perceptibly out of line. This non alignment of the lateral joints confers mechanical properties to the beam that are equal or greater than the norms established by the construction industry. The two strips bordering the thickness of the beam form the top 31 and the bottom 33 of the beam and are placed in such away at the bottom of the strip forms the external surface of the beam and ensures that this surface is plane and devoided of flash. The strips included between the top and bottom strips form a central pant 32 of the beam. The sides of the beam 35 are constituted by the sides of the strips to form a substantially plane surface. Once the beam is assembled, the surfaces are planed in order to obtain an essentially plane surface and to reduce the width of the beam to the desired width. The ends of the beam may comprise flash.
The strips may also be assembled according to different models. Some of these non liming examples are described in Example 3 below.
According to yet another aspect of the instant invention, the strips may be joined by their ends (finger joints) to obtain strips of desired length. FIG. 5 illustrates two types of jointing that can be used: face jointing 40 and flat jointing 42 . Although the examples used herein to illustrate the invention are described with face jointing, other types of finger joint, as would be obvious to one skilled in the art, are also considered to be part of the invention.
The strips thus jointed are assembled into beams as described above in such away that the finger joints of two adjacent strips in the beam are out of line. This arrangement may be visualized by referring to FIG. 6 in which out of line finger joints 40 are illustrated.
The beam of the instant invention may be manufactured with any type of wood compatible with the norms of the industry. However, in a preferred embodiment of the instant invention the wood is obtained from coniferous species that can be found in the region of the sub polar crown of the northern hemisphere which have a slow growth and a relatively small diameter. Among the different type of trees from this region, the black spruce is preferred for the man manufacturing of the beam of the instant invention. In a preferred embodiment, the external surfaces of the beam are essentially made of wood fibers located near the centre of the trunk called duramen.
The instant invention also provides a method for making the beams described above which will now be described.
The first step consists of obtaining planks originating from tree trunks having small diameters, preferably the black spruce, but other species of trees may also be used as long as their mechanical properties are compatible with the norms, and which may comprise flash.
In the second step, the planks are dried to obtain planks with an hygrometric degree compatible with the adhesive used in the manufacturing of glulam wood beams. This hygrometric degree can vary between 8 and 12% but may be modified as would be obvious to one skilled in the art to obtain physical properties that are optimal for the adhesion and for the resistance of the wood.
After the drying step, the planks are sorted on the basis of pre-established criteria that are well known to persons skilled in the art. These criteria include, but are not limited to: the general geometry, absence of visual flaws (colouration, insect bites, decay, chips, cracks), the absence of timber knots at the ends of the planks, the classification of the mechanical resistance according to tolerance criteria. In particular, the sorting allows the elimination of planks having timber knots that interfere with the alignment of wood fibers. These knots can reduce the mechanical resistance of the planks. The discarded planks are recycled to be used in other wood products in which their presence may be acceptable thus reducing wastes to a minimum. This elimination of the planks having compromising timber knots is an important element of the instant application since traditionally, in the manufacturing of glulam beams; these planks are “repaired” by cutting out the knots from the planks and by then joining the two sections of the planks thus generated by a finger joint. This method is time consuming and expensive and in addition introduces flaws in the planks that may lower their mechanical resistance. Advantageously, the present invention preferably uses tree species generally exhibiting small timber knots that do not compromise the mechanical resistance of the planks.
With regard to the instant invention, the planks are classified in two categories of resistance: superior resistance and adequate resistance. The mechanical properties of the planks of these two categories meet the norms of the construction industry. This classification allows the planks to be located in the beam at critical positions to optimize its mechanical properties. It will be appreciated that the classification of the planks in more than two categories, without departing from the scope of the instant invention, is also possible.
The sides of the planks thus sorted are treated to optimize the adhesion surface that will be involved in the assembly of the strips. This treatment may include, but is not limited to planing.
The next step consists in the selection of planks that will be included in the strips. The planks, which may be of different width, are selected to obtain a combination of planks which will produce, once assembled, a strip of the desired width. It will be appreciated that the width may be slightly greater an the desired width of the beam. This slight excess in width allows the beam to be assembled with imperfectly aligned sides which will subsequently be planed to produce a smooth surface and to reduce the width of the beam to the desired width. The selection also ensures that the sides of the strips do not comprise any flash. This selection results in an optimal use of the plank stock.
Once the selection of the planks has been completed, an adhesive is applied on the sides of the plank, except the sides that are located at the lateral ends of the strips. The planks are then placed side by side in such a way that the sides are in contact with each other and that the bottom of the planks form a plane surface and that the length of the strip is uniform. The strips are then submitted to a lateral pressure of an adequate duration to optimize the reciprocal adherence of the sides.
The strips are then jointed by their ends using flat or face jointing or any other type of joints as would be obvious to one skilled in the art.
An adhesive is then applied to the top surface of the planks and the strips are assembled to form the beam. The strips are ranged within the beam in such a manner as to ensure that the finger joints are substantially out of line relative to one another. The beam will then be enclosed in a press to optimize the reciprocal adhesion of the strips.
The glueing of the strips is a conventional glulam glueing using straight or curved presses that can be either vertical or horizontal, with or without heat and with or without high frequencies or microwaves.
Finally, the beam is planed to smooth all surfaces and to reduce the length, the thickness and the width to the desired dimensions.
The top and the bottom of the beam are the most mechanically solicitated part of the beam. Advantageously, the method of the present invention allows the composition of the beam to be programmed so that the planks which exhibit adequate resistance properties be included in the central part of the beam and that the planks exhibiting superior resistance properties be included in the strips forming the top and the bottom of the beam.
According to yet another aspect of the method of the instant invention, the planks are selected and assembled in panels. These panels are subsequently cut in strips of the desired width in such a way that the sides of the strips are essentially made of wood fibers that are located essentially in the duramen.
The cutting of the panels into strips will now be described referring to FIG. 7 . Panel 60 is constituted of plans, which may exhibit differing width, adhesively assembled by their sides and arranged according to a repetitive pattern relative to their width (Example: 1×2″×4″, 2×2″×3″, 1×2″×4″, 2×2″×3″, etc.). The first plank of the panel is cut at a position X O located at a distance D O from its side, substantially in the duramen and parallel to the longitudinal axis of the strips and by ensuring that the side thus formed is devoided of flash. That is to say the axis defining the cutting line is located in the plane top surface. The second cutting is made at a position X 1 , equivalent in the pattern to X o , and located at a distance D 1 from X O corresponding to the desired width of the strip. This second cutting is also made substantially in the duramen. The lateral joints are located at a position X J located at a distance D J from X O . The first strip is thus obtained. The third cutting is then made at the distance D 1 from X 1 to obtain the second strip. Additional cuttings, always at a distance D 1 from the last cut, enables one tp obtain a series of identical strips using the same panel.
The cutting of the panels into strips is programmed in such a way that the lateral joints of the strips that will be adjacent in the beam will be out of line once the beam is assembled. To achieve this, the first planks of identical panels are cut at a position X O that differs for each panel. The lateral joints of the different panels are thus located at positions X J that differ relative to the sides of the strips. The strips from the different panels are then assembled into beams in which the lateral joints of adjacent strips are out of line.
The assembly of the planks in panels allows an optimum use of the presses and thus considerably reduces the time required for this manufacturing step.
This technique for the assembly of strips with planks of pre-selected width into panels that are subsequently cut into strips allows, by the judicious choice of planks, the production of all beam widths sold on the market using a limited number of plank width. This aspect of the invention is illustrated in Example 2 described below.
According to yet another aspect of the invention the width of the beams is a multiple of the desired width. The assembly of these beams is programmed to allow their longitudinal cutting in such a way as to obtain two or more beams of the desired width and that the new sides thus generated exhibit a substantially plane surface essentially made of the duramen. Thus, the cutting of the beam into two or more beams is accomplished without calling near or in the lateral joints to avoid discovering flash.
The invention is also directed at a method of making strips with dispersed finger joints using the beams assembled according to the above described method.
As illustrated in FIG. 8, it is possible to obtain strips with dispersed finger joints using beams assembled according to the method of the instant invention. The beam is cut along a longitudinal axis 81 perpendicular to the finger joints 40 and in such a way that the axis defining the cutting line does not coincide with the lateral joints. There is thus obtained a strip 83 with dispersed finger joints. The strips can be used to form the top and bottom of beams of the instant invention and to provide an increased mechanical stability to beams that are constituted by strips having non dispersed finger joints.
DESCRIPTION OF PREFERRED EMBODIMENT
The present invention will be further illustrated in the following examples. However, it is to be understood that these examples are for illustrative purposes only, and should not be used to limit the scope of the present invention in any manner.
EXAMPLE 1
Precomposition of individual strips panels
A. Individual strips
A strip of a width of twelve inches (273 mm) may be obtained by assembling three planks with three two by four (2″×4″) planks. The sides of the two planks located at the lateral ends of the strips form sharp edges (devoided of flash) with the top and the bottom of the planks.
Panels
A width of thirteen inches (289 mm) may be obtained by assembling planks into panels that are then cut at the appropriate position. For example, the panel may be composed of one 2″×4″ plank, three 2″×3″ planks, etc. The cutting of the panel into strips is accomplished by cutting the 2″×4″: planks at a position X 0 and X 1 according to the method described above to obtain a strip with a width of thirteen inches.
EXAMPLE 2
Assembly of beams of various width using planks of various width
The following table presents the width of beams that can be obtained using strips comprising 2″×3″, 2″×4″ and 2″×6″ planks. The table also contains information on the loss of material during the manufacture of the beams. Also shown is the ratio of original wood material necessary to produce one meter cubed of finished products as well as the width of beams available on the market.
TABLE
Finished product
ratio starting
beam dimension
Lost of material
material (m 3
beam dimension
(inches and mm) of
(m 3 finished product for
starting material
(inches) available
the instant
Recurring
1 m 3 of starting material)
for 1 m 3 finished
commercially
invention
of beams
Length
Cutting
Planing
product
2½
2⅛
54 MM
¼ strip B
0.9
0.685
0.948
1.711
3
3⅛
3⅛
79.3 MM
⅓ strip A
0.9
0.75
0.953
1.555
3½
3½
88.9 MM
⅓ strip E
0.9
0.785
0.959
1.555
4⅛
105 MM
strip D
5
4⅞
122.5 MM
½ strip B
0.9
0.778
0.96
1.488
5⅛
5¼
134 MM
½ strip C
0.9
0.785
0.967
1.464
5½
5½
139.7 MM
½ strip E
0.9
0.785
0.967
1.464
6¾
6⅝
170 MM
⅔ strip A
0.9
0.807
0.97
1.419
7¼
7½
190 MM
¾ strip B
0.9
0.807
0.971
1.418
8¾
10
256 MM
strip B
0.9
0.816
0.965
1.411
10¾
10¼
261 MM
strip A
0.9
0.826
0.965
1.394
11
280 MM
strip C
0.9
0.823
0.965
1.399
11 12/16
300 MM
strip E
0.9
0.826
0.965
1.394
From the table, it can be seen that:
Strip A can be obtained using three 2″ × 4″ planks.
Strip B is four 2″ × 3″ planks.
Strip C is three 2″ × 3″ and one 2″ × 4″ planks.
Strip D is (hypothetical) 2″ × 3.5″ planks.
Strip E is one 2″ × 3″, one 2″ × 6″ and one 2″ × 4″ planks.
From the table, it can be seen that:
Strip A can be obtained using three 2″×4″ planks,
Strip B is four 2″×3″ plank.
Strip C is three 2″×3″ and one 2″×4″ planks.
Strip D is hypothetical) 2″×3.5″ planks,
Strip E is one 2″×3″, one 2″×6″ and one 2″×4″ planks,
Thus, according to the table, a beam having a width of ten inches may be manufactured using Strip B (the difference in the width between strip B (12″) and the width of the finished beam is due to the cutting of the sides of the strip, and the planing). In addition, the beam made using Strip B may be cut into ¾-¼ to form two beams having a width of 7½ inches and 2⅛ inches respectively. At this step additional wood is lost by the cutting of the beam. The dimension that can be obtained using the method of the instant invention are not limited to the dimension reported in the table. Any combination of plank width and beam cuing that can yield a beam compatible with the above described beam is considered to be included within the scope of the instant invention.
EXAMPLE 3
Examples of beams comprising flash according to the instant invention
The models of beams described below will be better understood by referring to FIGS. 10-15.
A. In the beam of FIG. 10, the central part 101 comprises individual squared planks having a width equal to the width of the strip of the top and bottom strips of the beam.
B. The beam of FIG. 11 is formed by two strips 111 vertically adhered and in which the lateral joints of the central part are out of line.
C. The beam illustrated in FIG. 12 is composed of three strips 121 vertically adhered and in which the later joints of the central part are substantially co-linear.
D. The beam illustrated in FIG. 13 is composed of three strips 131 vertically adhered and in which the lateral joints forming the central part are co-linear. The top and the bottom part of the beam are formed by strips devoided of flash and being optionally reinforced with fiberglass, carbon or airmide bands. In addition, the width of the central part is smaller than the bottom and top strips of the beam.
E. In the beam illustrated in FIG. 14 the central part of the beam 141 is composed of individual squared planks having a width smaller than the width of the strips of the bottom and top strips of the beam.
F. The beam illustrated in FIG. 15 exhibits a central part with empty spaces 151 (not resulting from the presence of flash) between the strips which are separated by intercalated planks 153 between adjacent strips.
EXAMPLE 4
Example of a calculation reflecting the improvement in the yield of finished products due to the use of small diameter trunks
To obtain two 2″×4″ plans with four sharp edges without flash, it is necessary to use a trunk diameter of at least 130 mm. However, if 15 mm of flash is still rated, it is possible to use a trunk having a diameter of 110 mm.
With reference to FIG. 16 and to the calculation shown below, an improved differential yield of 40% is calculated. ( 130 / 2 ) 2 × π ( 110 / 2 ) 2 × π = 1.396 ( 40 % )
These examples illustrate the formation of beams using strips. However, the same beam may also be obtained by assembling individual planks appropriately selected. In addition, the beams described above are examples only. Any other model that would by obvious to a person skilled in the art is considered to be included within the scope of the invention. | There is provided a glulam wood beam comprising planks having a width substantially smaller than the width of the beam, assembled into snips. The beam is characterized by the presence of flash in the interior by external surfaces made essentially of duramen. There is further provided a method for making the wood beam of the instant invention wherein the strips are derived from panels and in which the cutting of the panels into strips is programmed to ensure that the subsequent assembly of the strips will result in beams having external surfaces comprised essentially of duramen, thus providing a beam with enhanced mechanical resistance. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to a liquid crystal display device, and is directed more particularly to a liquid crystal display device in which the life span of a liquid crystal display used therein can be greatly prolonged.
2. Description of the Prior Art
Since a liquid crystal display device consumes little electric power and can be driven by a low drive voltage, it is used as various display devices such as numerical display, letter display, bar graphical display, television video display, and so on.
It is known that if the liquid crystal is driven by a DC voltage, its life span is deteriorated or greatly shortened, so that in general the liquid crystal is driven by an AC voltage. In the latter case, if any DC voltage component remains across the liquid crystal, its life span becomes gradually shorter. Since the remaining or residual DC voltage component badly effects the life time span of the liquid crystal even if its value is in the order of mV (milli-volt), it is desired to suppress the residual DC voltage across the liquid crystal lower than 50 mV. In fact, even if the remaining DC component across the liquid crystal is relatively low, this remaining DC component is accumulated and then badly affects the liquid crystal.
In a prior art liquid crystal drive method, a liquid crystal cell is directly supplied at one of its opposing electrodes with a drive waveform from an AC drive source terminal and at its other electrode with the same through an exclusive OR gate circuit. With such a prior art method, the duty cycle of the drive waveform is deformed and hence a remaining DC component for the applied voltage is applied across the liquid crystal cell with the result that its life time span is deteriorated or becomes short. The above defect especially appears as the drive frequency becomes high.
In another prior art liquid crystal drive method, by means of a resistor division, the mid-point potential of the drive waveform is applied across a liquid crystal. In this case there may occur a DC offset due to the resistive error of the resistors and hence a DC component will remain across the liquid crystal.
It may be considered as another drive method for a liquid crystal that a non-polar capacity is provided so as to prevent a DC component from remaining. In this case, however, it is necessary to use a capacity and to provide a non-polar capacity for each of a plurality of liquid crystal cells (segments) which are arranged to be, for example, a figure "8" or a predetermined pattern in parallel relation so as to achieve various displays such as a numerical display, bar graphic display and so on. Therefore the construction becomes large, complicated and expensive. In this case, since the remaining DC component is consumed by a resistor, the electric power consumed by the whole device becomes great.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a novel liquid crystal display device free from the defects inherent to the prior art devices.
Another object of the invention is to provide a liquid crystal display device in which a remaining DC component caused by voltage fluctuation of a drive waveform, offset, disturbance of the duty cycle, impedance variations of a driven circuit, and so on can be removed positively.
A further object of the invention is to provide a liquid crystal display device in which the life span of a liquid crystal used therein can be greatly prolonged.
With the present invention, in a liquid crystal display device having an integrator and a liquid crystal cell such as an electric field type liquid crystal, nematic liquid crystal or dynamic scattering type liquid crystal, a drive waveform from a driver circuit is applied to one of opposing electrodes of the liquid crystal cell which is supplied at its other electrode with a mean DC voltage which is produced in such a manner that the drive waveform is integrated by an integrator at a time constant lower than the fundamental frequency component in correspondence to the drive waveform.
According to an aspect of the present invention there is provided a liquid crystal display device which comprises a liquid crystal display cell interposed between a first group of electrodes and a second group of electrodes, a driver circuit for applying an exciting voltage to the first group of electrodes, and a circuit for applying a mean DC voltage obtained by integrating the exciting voltage to the second group of electrodes.
The other objects, features and advantages of the present invention will become apparent from the following description taken in conjunction with the accompanying drawings through which like elements are marked with the same reference numerals and symbols.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1 and 2 are circuit diagrams showing prior art drive circuits for a liquid crystal display device, respectively:
FIG. 3 is an equivalent circuit of a liquid crystal cell;
FIG. 4 is a waveform diagram of a prior art drive signal for a liquid crystal cell;
FIGS. 5, 6 and 7, inclusive, are circuit diagrams showing prior art drive circuits for a liquid crystal display device, respectively; and
FIGS. 8, 9 and 10, inclusive, are circuit diagrams showing drive circuits for a liquid crystal device according to the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
For better understanding of the present invention, an example of the prior art method of driving a liquid crystal cell used in a liquid crystal display device will be now described with reference to FIG. 1. In FIG. 1, 1 designates a liquid crystal cell which is supplied at one of its opposing electrodes with a drive waveform from an AC drive source terminal t 1 directly and at its other terminal with the drive waveform through an exclusive OR gate circuit 2. In this case, when the OR gate circuit 2 is supplied at its control terminal t c with a signal "1", both ends, i.e. opposing electrodes of the liquid crystal cell 1, are supplied with the waveform which is applied to the exclusive OR gate circuit 2, one of the waveforms being of inverse phase with respect to the other. As a result, the liquid crystal cell 1 is supplied with a voltage two times the applied waveform and hence turns ON. When a signal "0" is applied to the OR gate circuit 2 at its control terminal t c , the waveforms of the same phase are applied across the cell 1. Thus, at this time the cell 1 turns OFF.
With the above prior art drive method, when the duty cycle of the drive waveforms is 50:50, no DC component appears when the cell 1 is in an ON-state. However, when the duty cycle is disturbed or becomes, for example, 49:51, a residual DC component of 2% of the applied voltage is applied across the cell 2. When the cell 1 is driven through a driver circuit such as a C-MOS transistor, the unbalance of duty cycle due to the above order of delay is caused frequently. Thus, the liquid crystal cell cannot be used for a long time by the above prior art drive method. If the drive frequency is made high, the above tendency appears. For example, if the duty is 49:51 and the applied voltage is 5 V, the residual DC component becomes 100 mV.
Next, the prior art drive circuit will be described. In general, the liquid crystal cell 1 is driven through a C-MOS transistor in the art as shown in FIG. 2, In the figure, reference letters TR 1 and TR 2 designate a P-channel MOS-FET and an N-channel MOS-FET which form the driver circuit or the C-MOS transistor.
FIG. 3 is an equivalent circuit of the liquid crystal 1, in which a resistor R s is about several KΩ in resistance value, a resistor R P is about 1 TΩ (tera-ohm), and a capacitor C L is about several hundreds PF/cm 2 in capacity, respectively.
Turning back to the drive circuit of FIG. 2, when the two MOS-FETs TR 1 and TR 2 are equal in impedance during the ON-state thereof, impedances viewed from the load systems to +E and -E terminals become equal. Under such a condition, when a rectangular waveform having the duty of 50:50 is applied to an input terminal a of the C-MOS transistor, the output waveform therefrom becomes symmetrical with respect to the potential ##EQU1## regardless of the load impedance and hence no residual DC component remains. However, if there is error in the impedances of the MOS-FETs TR 1 and TR 2 , the output from the C-MOS transistor is offset either positively negatively and hence there remains a residual DC component. Since the liquid crystal 1 is expressed equivalently as shown in FIG. 3 and becomes almost completely a capacity load, the liquid crystal 1 is now taken as a load. If the MOS-FETs TR 1 and TR 2 are different in impedance, for example, the impedance of the MOS-FET TR 1 is higher than that of the MOS-FET TR 2 , the waveform which is applied to the liquid crystal 1 becomes rounded off at its shoulders at the positive side as shown in FIG. 4. On the contrary, when the impedance of the MOS-FET TR 2 is higher than that of the other MOS-FET TR 1 , the shoulders of the applied waveform at the negative side, which are marked with dotted line circles in FIG. 4, becomes rounded off. That is, when the impedances of the MOS-FETs TR 1 and TR 2 are unbalanced, a mean DC voltage does not become zero and hence there remains a residual DC component.
In general, a C-MOS transistor which is formed such that both conductivity types or N- and P-type MOS-FETs TR 1 and TR 2 are integrated on a common semiconductor substrate, both the MOS-FETs TR 1 and TR 2 of the both conductivity types cannot have uniform characteristics in impurity concentration and area in view of their manufacturing point and hence error appears in their impedance. As a result, when the C-MOS transistor is used as the driver circuit for the liquid crystal, the residual DC component remains across the liquid crystal without exception and hence its life time span is deteriorated or shortened.
FIG. 5 is another example of the prior art drive method for the liquid crystal 1. In this prior art, the mid-point potential of the drive waveform, which is provided by a divider consisting of two resistors R 1 , is applied to the liquid crystal 1. In this case, there may be a fear that a DC offset is caused by the error of the resistance value of the resistors R 1 . Therefore, even if the resistors R 1 having an accuracy of 1% are used, a DC component of 50 mV remains when the drive voltage is selected as 5 V. In FIG. 5, C 1 represents capacitors for by-passing an AC component.
A further example of the prior art drive circuit is shown in FIG. 6. As shown in FIG. 6, a non-polar capacity C 2 is provided in the circuit shown in FIG. 5 for blocking the DC component. In this case, it is necessary to use a capacitor having a large capacity, for example, 0.1 to 1 μF as the non-polar capacitor C 2 . In FIG. 6, R 2 represents a resistor connected in parallel to the liquid crystal 1 through which resistor R 2 , the DC component, flows.
FIG. 7 shows a still further example of the prior art drive circuit. In a display device which will achieve various displays such as a numerical display and so on, a plurality of liquid crystal cells (segments) 1 are arranged with a predetermined pattern such as a figure "8" or parallel arrangement, so that it is necessary to provide the capacitor C 2 for each of the plurality of liquid crystal cells 1 as shown in FIG. 7 and hence the display device becomes complicated and large in size. In this case, since the residual DC component is consumed by the resistors R 2 , the power consumption of the whole device increases. In FIG. 7, 2 generally indicates an electrical or mechanical switch which is controlled by a display signal from the driver circuit to select the liquid crystal cells 1 in response to the display signal and to apply therethrough the drive voltage signal to the selected liquid crystals 1.
As described previously, the present invention is to provide a liquid crystal display device which is free from the defects of the prior art, can positively remove a residual DC component produced by the voltage fluctuation of the drive waveform from the drive circuit, offset, the disturbance of the duty cycle of the drive waveform, the impedance change of the driver circuit and so on, and hence can prolong the life time of the liquid crystal cell.
An example of the present invention will be now described with reference to FIG. 8 in which reference numerals and symbols are the same as those used in FIGS. 1 to 7, and designate the same elements and their detailed description will be omitted. In this example of the invention, for example, the drive waveform from a driver circuit having the C-MOS transistor is applied to one of the opposing electrodes of the liquid crystal cell 1 such as an electric field type liquid crystal, nematic liquid crystal, or dynamic scattering type liquid crystal. A mean DC voltage, which is provided by integrating the drive waveform from the C-MOS transistor with an integrator 10 at the time constant lower than the fundamental frequency component of the drive waveform and hence corresponds to the drive waveform, is applied to the other electrode of the liquid crystal cell 1. In this case, if the impedance of the output from the integrator 10 is too high as is, it is possible that the output from the integrator 10 is applied to an impedance converter 11 for lowering impedance and then the output from the impedance converter 11 is applied to the liquid crystal 1.
A practical circuit of the example shown in FIG. 8 will be described with reference to FIG. 9. In the circuit of FIG. 9, the integrator 10 is formed of a resistor R having the resistance value of, for example, 1 MΩ and a capacitor C having the capacity of, for example, 0.1 μF and the impedance converter 11 is formed of a voltage follower operational amplifier. In this example, since the offset of the voltage follower operational amplifier serving as the impedance converter 11 is sufficiently small, it poses almost no problem. However, if the constant of the integrator 10 is selected suitably and/or the drive frequency is high, the impedance converter 11 can be omitted. For example, if the frequency of the fundamental wave of the drive waveform is selected as 100 H z and the capacity of the integrating capacitor C is selected as 1 μF, the impedance of the output from the integrator 10 becomes about 1.6 KΩ. This impedance is sufficiently small as compared with that of the liquid crystal cell 1, so that in this case the integrated output can be applied to the liquid crystal cell 1 without being impedance-converted.
FIG. 10 shows such an example that the present invention applied to a liquid crystal display device in which a plurality of liquid crystal cells 1 are arranged in the figure "8" or parallel and the plurality of cells 1 are selectively driven by the display signal from the driver having the C-MOS transistor through the electrical or mechanical switch 2 which is controlled by the display signal. As shown in FIG. 10, it is enough that the single integrator 10 and, if necessary, impedance converter 11 are commonly connected to the plurality of liquid crystal cells 1, so that even if a display device includes a number of liquid crystal cells 1, the number of the circuit elements is prevented from being increased and hence the device is prevented from becoming large in size and expensive. Further, the liquid crystal can be free from affects such as the unbalances of the duty cycle and the impedance of the output driver circuit, the scattering and fluctuation of the power source and so on, and the residual DC component can be reduced or removed, so that the life span of the liquid crystal can be prolonged. The present invention is especially useful when applied to the case where the liquid crystal is driven by a high voltage and high frequency.
Although various minor modifications may be suggested by those versed in the art, it should be understood that I wish to embody within the scope of the patent warranted hereon, all such embodiments as reasonably and properly come within the scope of my contribution to the art. | A liquid crystal display device having a liquid crystal display cell disposed between a first electrode and a second electrode is disclosed. A circuit for applying an exciting voltage to the first electrode is also provided. An integrator integrates the exciting voltage to produce a mean DC voltage. The mean DC voltage is applied to the second electrode. If necessary, an impedance converter is provided to convert the impedance of the output from the integrator so that it is lower than that of the liquid crystal cell. | 6 |
SUMMARY OF THE INVENTION
[0001] The present invention relates to a shape memory actuator device, comprising of a cable, rigid or flexible, having an end connected to a controlled mechanism and a sheath inside which the cable is fitted, in which at least a portion of the cable is made up of a shape memory material, susceptible to undergo a shape change subsequent to its heating up, to operate the controlled mechanism, and in which it is also foreseen an electric supply circuit to feed through the shape memory cable an electric current in order to cause it to heat up.
[0002] A shape memory actuator device of a type described above has been proposed by the same applicant in WO03/003137 A1. An improvement of such device has also been the object of the claim of the European patent 03015862.0 always by the same applicant.
[0003] With the view of further improving the device previously submitted, the object of the present invention is a shape memory actuator device having all the characteristics which have been stated above and besides characterized in that it is provided with means suitable to detect a position of an end stop of the shape memory cable subsequent to its heating up and to cut off the electric supply to such cable following such detection.
[0004] Thanks to such a characteristic, the shape memory cable cannot be subject to excessive unnecessary heating up, after the controlled mechanism has already been brought to the desired operative position.
[0005] Preferably, the actuator according to the invention is of the type (known from WO03/003137 A1) in which said sheath is assembled in respect to a fixed support structure in such a way to be free to move longitudinally only in the direction to activate the controlled mechanism, and also in which the said sheath is coupled to the controlled mechanism in such a way to be able to transmit directly to it a movement in the aforesaid operative direction and to be uncoupled instead from the controlled element in respect to a movement in the direction opposite to the operative one, in such a way that said actuator is apt to be utilized either through a manual operation, using the sheath as an element of mechanical transmission, or by exploiting the shape change of the shape memory cable, obtainable through its heating up.
[0006] The actuator according to the invention finds several applications, one of which for example is constituted by the control of a door lock of a motor vehicle. In such an application, it is desirable to be able to operate the opening of the lock either electrically, or mechanically. Of course, with the opening of the lock is meant here the operation through which the lock is “unhooked” allowing the opening of the door and not the operation through which the locking block is removed in the closed condition. Thanks to the use of the actuator according to the invention, the unhooking of the lock can be executed either electrically, for example also through a remote control, or mechanically, acting on the door handle of the motor vehicle. A particular advantageous application is that of a lock of a bonnet or of a back hatch door of the motor vehicle, where it must be possible to operate either electrically or mechanically from the inside of the motor vehicle, in case that a person has remained inadvertently closed inside the motor vehicle. Thanks to the additional characteristics foreseen according to the invention, the shape memory cable being part of the actuator is protected from the risk of damaging by overheating.
[0007] Preferably, the said means apt to detect a position of the end stop of the shape memory cable are integrated in the actuator.
BRIEF DESCRIPTION OFF THE DRAWINGS
[0008] Further characteristics and advantages of the invention will result in the description which follows with reference to the enclosed drawings, supplied purely as a non limitative example, in which:
[0009] FIG. 1 is a perspective view partially cross sectioned of a form of realization of the actuator device previously proposed by the same applicant, corresponding to FIG. 5 of the international patent claim above identified,
[0010] FIG. 2 is a perspective view partially cross sectioned of the shape memory cable being part of the actuator, according to the solution already proposed in the European patent claim also above identified,
[0011] FIGS. 3, 4 show a detail of the actuator device according to the present invention in two different operative conditions,
[0012] FIGS. 5, 6 are two cross section views of two variations of the actuator according to the invention, and
[0013] FIGS. 7, 8 show two cross sections according to the lines VII and VIII of FIGS. 5, 6 .
DETAILED DESCRIPTION OF THE INVENTION
[0014] With reference to FIG. 1 , an example is here illustrated of an application of the actuator previously proposed to operate the lock of the bonnet or the back hatch door of the motor vehicle.
[0015] Regulations are foreseen that will compel the manufacturer to foresee the possibility to operate the lock manually from inside, to allow the opening of the hatch door to a person who might have accidentally been closed inside the motor vehicle. In the illustrated example, the actuator can be operated manually through a ring 100 which is connected through a cable 101 to the sheath 3 of a flexible cable actuator device. On the sheath 3 is secured a bushing 102 intended to come into contact against a fixed stop 103 being part of the structure 104 of the locking device of the hatch door. The cooperating action of the bushing 102 integral with the sheath 3 and of the end stop 103 prevents a movement of the sheath 3 in an opposite direction to the one of activation. Inside the sheath 3 is fitted a flexible cable 2 of memory shape material (let it be clearly understood that it is also possible to realize the device with a rigid cable instead of a flexible one) which is secured at an end 2 a to a cylindrical body 5 which is in turn connected, through an opening 105 made in the wall of the casing of the lock 104 , to the controlled mechanism of the lock (not illustrated). Means of electricity supply (not illustrated) are also foreseen to apply an electric tension to the two opposite ends of the shape memory cable 2 , with the aim to cause it to shorten. When the actuator is operated manually acting on the ring 100 , the mechanical traction is transmitted through the sheath 3 which is shifting towards the right (with reference to FIG. 1 ) causing a distancing of the bushing 102 from the fixed stop 103 . The movement of the sheath 3 causes a corresponding movement of the cylindrical body 5 , since at the extremity of the sheath 3 is fastened a ring 11 which is resting against an extremity surface 5 a of an internal cavity of the cylindrical body 5 . The movement of this last one causes in consequence an activation of the controlled mechanism, which, as already indicated, is connected to the cylindrical body 5 by a connection passing through the opening 105 .
[0016] In the case, instead, of electric activation, the sheath 3 stand still, because it cannot move towards the left due to the resting of the bushing 102 against the fixed stop 103 , while the shape memory cable 2 shortens, provoking a sliding of the cylinder 5 over the sheath 3 (by which the ring 11 distances itself from the resting surface 5 a ) and again an activation of the controlled mechanism.
[0017] The advantage in using the sheath of the actuator device as an element of mechanical transmission in the case of manual activation consists in the fact that in such a way it is possible to guarantee always the functioning of the device, even in the case of an accidental breakage of the flexible shape memory cable.
[0018] It is possible to observe that in the case of the previously proposed solution, illustrated in FIG. 1 , between the cable 2 and the sheath 3 a distancing layer 106 of synthetic material is interposed which is united to the sheath 3 and is integral with it. Such a layer has only a distancing function, so that during the functioning of the device, a relative movement is created of the flexible cable in respect to it.
[0019] In the case of the solution, also already proposed, illustrated in FIG. 2 , instead, a structure of a different type is associated to the flexible cable. Also in this case between the flexible cable 2 of the shape memory material and the relative flexible sheath 3 , a distancing layer 106 is foreseen, which in the illustrated case is constituted of a braided wire.
[0020] The difference in respect to the solution illustrated in the FIG. 1 lies in the fact that in this case over the cable of shape memory material 2 is moulded a coating layer 110 that adheres to the shape memory cable 2 and is selected in elastomer/silicone or synthetic materials so that it facilitates either the cooling of the cable 2 after the switch off of the current, or the return of the cable 2 in its resting configuration, due to the effect of the elastic return of the coating 110 .
[0021] Preferably the coating 110 is moulded on top of the cable 2 through an operation of simultaneous extrusion of the material constituting cable 2 and by the coating 110 . In other words, during the production process, the cable 2 and the relative coating 110 are obtained simultaneously, through a process of co-extrusion, which presents the advantage to obtain the desired structure with a single operation, without the necessity of additional assembly operations.
[0022] The coating 110 , which is adherent to the cable 2 , performs the function of a spring distributed longitudinally, which is subjected to compression when the cable 2 shortens following its activation and consequently facilitates the return of the cable to the resting position through its elastic return.
[0023] The shape memory cable could be of any configuration. Besides it is possible to co-extrude several shape memory cables inside the same coating. A configuration of the cable as a U is of particular interest, with a forward tract and a return tract and the two extremities of the cable adjacent between them, which amongst other things gives the advantage of an easy electrical connection of the cable to the electricity supply means.
[0024] In the FIGS. 3-8 , the common parts to those of FIGS. 1, 2 are indicated by the same reference number. With reference in particular to FIGS. 3, 4 inside the body 5 ( FIG. 1 ) which is connected rigidly to the terminal end 2 a of the shape memory cable 2 , two metallic terminals 301 , 302 are predisposed which are connected respectively to the earth and to the positive pole in the electric supply circuit of the shape memory cable 2 . The two terminals 301 , 302 present two overhanging placed lamellae 301 a, 302 a, electrically deformable by flexing, which are normally in contact between them, assuring the continuity of the electric connection of the shape memory cable 2 to the electric supply means. The base portions of the terminals 301 , 302 are securely fixed inside the body 5 . Furthermore a coil spring 303 is coaxially placed around the cable 2 inside the cavity of the body 5 , between the base part of the terminal 301 and the extremity of the sheath 3 and of the relative support 11 . To such support a pointed appendix 304 is solidly integrated.
[0025] FIG. 3 shows the configuration of the device in the resting position. When the actuator is activated through an electric supply to the shape memory cable 2 , the end terminal 2 a of the cable 2 lowers itself (with reference to FIGS. 3, 4 ) in respect to the terminal portion of the sheath 3 until it reaches the position of end stop illustrated in FIG. 4 . In such position the pointed appendix 304 penetrates between the two lamellae 301 a, 302 a of the terminals 301 , 302 opening them wide and separating them one from the other so to disconnect the continuity of the supply circuit of the cable 2 . The electricity supply of the cable is therefore disconnected, protecting such cable from the risk of overheating. In the case for example of the application to the opening of the lock of a bonnet or a back hatch door of a motor vehicle, it so prevents the cable becoming damaged by excessive heat, which becomes totally unnecessary once the opening of the lock has been obtained. Naturally, the activation of the shape memory cable 2 provokes the movement above described against the action of the spring 303 , which provides the return of the device to the rest position when the power supply is disconnected.
[0026] FIGS. 5, 7 show the solution already mentioned above where the same cable 2 is sent back at U so to present two branches parallel between them 2 ′, 2 ″ secured to the body 5 corresponding to their two end terminals 2 a, adjacent between them. The whole of the two branches 2 ′, 2 ″ is contained inside the same sheath 3 .
[0027] FIGS. 6, 8 show a further variation that always foresees two shape memory wires 2 ′, 2 ″ parallel between them, which in this case however are two wires separated one from the other, contained inside the same sheath 3 and secured at the extremities 2 a to the body 5 (not illustrated).
[0028] In both cases shown in FIGS. 5, 7 and 6 , 8 , the disposition of the terminals 301 , 302 and the pointed appendix 304 is analogous to that already described with reference to FIGS. 3, 4 .
[0029] Naturally, keeping firm the principle of the invention, the particulars of the construction and the forms of realization could extensively change in regard to what has been described and illustrated only as an example, without leaving from the present invention. | A shape memory actuator device, comprising of a shape memory cable assembled through a sheath and susceptible of being supplied with an electric current to cause it to heat up. The sheath is placed in such a way to allow a manual activation of the controlled mechanism, acting as a transmission element, alternatively to the electric activation through the shape memory cable. Means are foreseen to detect the stop end position of the shape memory cable following its heating up in order to disconnect the electricity supply to such cable and to protect it from the risk of overheating. It is possible to foresee more shape memory cables placed parallel between them. | 4 |
TECHNICAL FIELD
The invention relates to a hybrid powertrain with a mechanism for starting an engine and a method of controlling a hybrid powertrain.
BACKGROUND OF THE INVENTION
Hybrid powertrains have two or more power sources. Some hybrid vehicles are operable in an electric-only operating mode in which drive power is provided exclusively by one or more electric motor/generators that utilize power stored in an energy storage device (ESD) such as a battery. For hybrid vehicles that have an internal combustion engine as the other power source, operation in an electric-only mode improves fuel economy and reduces emissions. When the ESD is discharged to a predetermined level or when additional output torque is required, the engine is started. Starting the engine is typically accomplished using a dedicated starter motor or by engaging a clutch that directly connects the engine and the motor/generator, referred to as a starting clutch. Dedicated starter motors add weight and cost.
SUMMARY OF THE INVENTION
A hybrid powertrain is provided that provides engine starting from an electric-only mode with a reduced torque load on the motor/generator. The powertrain includes an engine and a motor/generator, which may be a single motor/generator in a strong or full hybrid, but is not limited to such. The motor provides propulsion torque in an electric-only operating mode, and is configured to apply torque to a transmission input member. A first clutch is selectively engagable to connect the engine output member for common rotation with the transmission input member. An engine starting mechanism is provided that multiplies motor torque used to start the engine so that less is diverted from propelling the vehicle, enabling a smaller motor/generator to be used. The engine starting mechanism includes a first and a second gear train, as well as a second clutch having a first portion connected with the transmission input member via the first gear train and a second portion connected with the engine output member via the second gear train. The second clutch is selectively engagable to connect the first and second portions for common rotation, thereby transferring torque from the transmission input member to the engine output member with torque multiplication. The second clutch may be a hydraulic clutch of smaller capacity than the first clutch. In some embodiments, the second clutch is an active material clutch, also referred to as a smart clutch, such as a magnetorheological fluid (MRF) clutch or an electrorheological fluid (ERF) clutch. An MRF is a type of smart fluid with magnetic particles suspended in a carrier fluid. When subjected to a magnetic field, the apparent viscosity of the fluid increases, allowing the fluid's ability to transmit force to be controlled. Examples of suitable particles include straight iron powders, reduced iron powders, iron oxide powder/straight iron powder mixtures and iron oxide powder/reduced iron powder mixtures. An ERF is a suspension of nonconducting particles in an electrically insulating fluid. The apparent viscosity of an ERF changes in response to an electric field, allowing the fluid's ability to transmit force to be controlled.
The use of torque multiplying gear trains and the second clutch reduces the reserve torque requirement for the motor to start the engine, which reduces the possibility of torque sag, i.e., the diversion of output torque from the driveline when the motor does not have sufficient torque reserve to start the engine. This allows for a smaller motor/generator than with a starting clutch that directly connects the transmission input member and the engine output member. The engine starting mechanism also reduces control challenges associated with starting the engine directly with a typical engine starting clutch which has a slower response time due to fill time of a hydraulic clutch, as well as nonlinear behavior due to variations in the compressibility of fluid caused by entrained air. Finally, start quality is improved by a reduction in driveline torque disturbance as the speed of the engine output member and the speed of the transmission input member may be synchronized before the first clutch is engaged.
A method controlling the powertrain described above includes engaging the second clutch to transfer torque from the motor/generator to the engine to start the engine during an electric-only operating mode, and may include releasing the second clutch after the engine is started, synchronizing the speed of the engine output member with the speed of the transmission input member, and then engaging the first clutch to thereby transfer engine torque to the transmission input member.
The above features and advantages and other features and advantages of the present invention are readily apparent from the following detailed description of the best modes for carrying out the invention when taken in connection with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of a hybrid powertrain with an engine start mechanism;
FIG. 2 is a flow chart illustrating a method of controlling the powertrain of FIG. 1 ; and
FIG. 3 is a schematic partial cross-sectional side view of an exemplary MRF clutch for the engine start mechanism of FIG. 1 .
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, wherein like reference numbers refer to like components throughout the several views, FIG. 1 shows a hybrid powertrain 10 having an engine 12 and a hybrid transmission 14 . The transmission 14 has a transmission input member 16 and a transmission output member 18 . A transmission gearing arrangement 20 transfers torque from the input member 16 to the output member 18 . The transmission gearing arrangement 20 includes a plurality of selectively engagable clutches and brakes, as well as gears that may be planetary gear sets or intermeshing gear trains. The clutches and brakes are engagable in different combinations to affect torque transfer at different torque ratios such as overdrive and underdrive ratios, as is known.
A single motor/generator 22 has a rotor 24 mounted for rotation with the input member 16 and a stator 26 grounded to a stationary (i.e., nonrotatable) member 28 , such as a transmission casing. An energy storage device (ESD) 30 holds stored electrical energy that is selectively applied to the stator 26 through a power inverter 32 under the direction of an electronic controller 34 . The ESD 30 and motor/generator 22 are sufficiently sized so that the powertrain 10 may provide sufficient propulsion torque to the output member 18 using only the motor/generator 22 , and not the engine 12 , as a power source under many operating conditions, establishing what is referred to as an electric-only operating mode.
The controller 34 receives a variety of input signals indicative of operating conditions via sensors such as a throttle position sensor, wheel speed sensors, etc. Under certain operating conditions, these input signals are equivalent to an engine start request. The controller 34 then operates an engine starting mechanism 38 in order to start the engine 12 and deliver engine torque to the input member 16 without creating appreciable torque sag by motor torque diverted to start the engine 12 . The engine starting mechanism 38 includes an engine starting clutch 40 and a first gear train having a first gear 42 connected for rotation with the transmission input member 16 (i.e., a first shaft) and meshing with a second gear 44 mounted for rotation on a second shaft 46 . Shaft 46 is rotatably supported by the transmission casing 28 by support portions 47 of the casing 28 extending from the casing 28 to the shaft 46 on either side of the second gear 44 , with bearings 49 between the support portions 47 and gear 44 . A second gear train includes a third gear 48 and a fourth gear 52 . The third gear 48 is a spur gear mounted on a third shaft 50 that is rotatably supported by the casing 28 by support portion 47 with bearings 49 between the support portion 47 and the third gear 48 . The fourth gear 52 is rotatably supported by an engine output member 54 , such as a crankshaft that may be turned to start the engine 12 . The fourth gear 52 may be a ring gear or flex plate of the engine 12 .
A first portion 64 and a second portion 68 of the engine starting clutch 40 are selectively engagable to transmit torque from the shaft 46 to the shaft 50 , thus creating a powerflow path from the motor/generator 22 to the engine 12 through the gears 42 , 44 , 48 , 52 , which are configured to multiply torque from the transmission input member 16 to the engine output member 54 . The portions 64 , 68 may be friction plates and reaction plates (in the case of a hydraulic clutch), a drum and rotor (in the case of an MRF clutch), or other engagable portions of known clutch types. Specifically, when operating conditions warrant, the controller 34 provides an actuating signal to the starting clutch 40 . In a preferred embodiment, the gears 42 and 44 are designed to have a gear ratio (ratio of speed of gear 44 to gear 42 ) of approximately 1:1 and the gears 48 and 52 are designed to have a gear ratio (the ratio of speed of gear 52 to speed of gear 48 ) of approximately 2.5:1. That is, motor torque provided through the first gear train 42 , 44 is multiplied by 2.5 through the second gear train. Thus, the engine output member 54 spins at a lower speed than the rotor 24 of motor/generator 22 to start the engine 12 . Once the engine 12 is started, the fired engine speed is controlled by controller 34 , or by another controller in communication with controller 34 , to bring the speed of the engine output member 54 within a predetermined range or, or equal to, the speed of the input member 16 . Once a controlled speed is reached, the controller 34 signals a valve body 56 to direct hydraulic pressure to a main clutch 60 to fill an apply cavity that engages opposing clutch plates of the clutch 60 , transferring torque from the engine 12 to the transmission 14 . The starting clutch 40 is disengaged when the engine 12 is started prior to engaging the main clutch 60 . Prior to start of the engine 12 and engagement of starting clutch 40 , clutch slip in the clutch 40 is equal in magnitude to the speed of the gear 44 . Once the engine 12 is started and before main clutch 60 is engaged, starting clutch 40 is disengaged. When main clutch 60 is engaged, the slip in the starting clutch 40 increases in magnitude.
Referring to FIG. 2 , a method 100 of controlling a hybrid powertrain is described with respect to hybrid powertrain 10 . First, in block 102 , controller 34 receives an engine start request, which is one or more sensor signals indicative of operating conditions warranting starting the engine 12 during an electric-only operating mode. Next, in block 104 , the controller 34 causes the starting clutch 40 to be engaged bringing the engine 12 up to firing speed. The mechanism by which the controller 34 engages clutch 40 depends on the type of clutch used.
Once the engine 12 is firing, the clutch 40 is then disengaged by the controller 34 in block 106 . In block 108 , engine speed is then synchronized with the speed of the motor/generator 22 using speed sensors (not shown) or otherwise, and an engine control module (not shown). The main clutch 60 is then applied in block 110 , completing the transition from an electric-only operating mode to a hybrid operating mode.
The clutch 40 may be a hydraulic clutch, or an active material clutch, sometimes referred to as a “smart clutch”. The clutch capacity of clutch 40 is lower than the clutch capacity of main clutch 60 because it need not handle the greater torque load of the engine output member 54 . Thus, even if the clutch 40 is a hydraulic clutch, it will be filled faster, at a lower fill volume, than the main clutch 60 . Alternatively, the clutch 40 may be a smart clutch, such as an MRF or ERF clutch. A smart clutch has the advantage of precise engagement and disengagement times, as the clutch connection is controllable by applying an electric or magnetic field, rather than dependent on hydraulic fluid building to a sufficient pressure.
Exemplary Embodiment of an Engine Starting Clutch
Referring to FIG. 3 , an exemplary MRF clutch 40 selectively joins or couples a pair of rotatable members, exemplified herein as the respective input and output members (i.e., shaft 46 and shaft 50 , respectively). A connecting member or sleeve 62 can be directly connected to or interposed between the input member 46 and the first portion 64 of the MRF clutch 40 , referred to as rotatable outer housing or drum 64 , to rotate in conjunction therewith. That is, rotation of the shaft 46 in conjunction with an actuated MRF clutch 40 ultimately rotates the drum 64 , with the MRF clutch 40 operable for selectively transferring or transmitting torque from the shaft 46 to the shaft 50 as described below.
The MRF clutch 40 includes a magnetically permeable stator 66 within the drum 64 , the second portion 68 , referred to as rotor 68 , and a magnetic field generator 70 . The rotor 68 , having a rotational degree of freedom with respect to the stator 66 , is journaled, splined, or otherwise directly connected to the shaft 50 to rotate in conjunction therewith about a rotational axis 72 . The rotor 68 includes an axial member 74 which at least partially defines at least a pair of respective inner and outer working gaps 78 A and 78 B as discussed in more detail below, with a volume of MR fluid 80 substantially filling the working gaps 78 A, 78 B. Although not shown in FIG. 3 for clarity, one or more intermediate working gaps may be disposed between the working gaps 78 A, 78 B.
The magnetic field generator 70 is in field communication with the MR fluid 80 in each of the working gaps 78 A, 78 B, with the magnetic field illustrated generally in FIG. 3 by a set of magnetic flux lines 82 . The stator 66 and the rotor 68 each include respective magnetic or magnetically-permeable portions 84 , 86 and non-magnetic portions 90 , 92 , which serve to guide the magnetic field or flux lines 82 in a manner suitable for the purposes disclosed herein. Suitable magnetizable materials for use as the magnetic portions 84 , 86 and stator 66 can include, but are not limited to, iron, steel, carbonyl iron, etc., or a combination comprising at least one of the exemplary magnetizable materials described above. Suitable non-magnetic materials for use as the non-magnetic materials 90 , 92 can include, but are not limited to, stainless steel, aluminum, brass, plastics, etc., or a combination thereof Alternatively, an air gap may be employed in place of or in addition to the use of non-magnetic portions, as will be understood by those of ordinary skill in the art.
The magnetic field generator 70 can be configured as an electromagnet as shown in FIG. 3 , including a magnetic core 94 and a field coil 96 that is electrically energized via the ESD 30 of FIG. 1 . Exemplary fluid seals 98 A, 98 B serve to prevent leakage of the MR fluid 80 from the working gaps 78 A, 78 B. While exemplary fluid seals 98 A, 98 B are depicted in FIG. 3 , it will be appreciated that other arrangements or sealing devices may also be employed.
An exemplary composition for the MR fluid 80 includes magnetizable particles, a carrier fluid, and additives. By way of example, the magnetizable particles of the MR fluid 80 can include paramagnetic, super-paramagnetic, or ferromagnetic compounds or a combination thereof. The magnetizable particles can be comprised of materials such as but not limited to iron, iron oxide, iron nitride, iron carbide, carbonyl iron, chromium dioxide, low carbon steel, silicon steel, nickel, cobalt, or the like, or a combination thereof. The term “iron oxide” can include all forms of pure iron oxide, such as, for example, Fe 2 O 3 and Fe 3 O 4 , as well as those containing small amounts of other elements such as manganese, zinc, barium, etc. Specific examples of iron oxide include ferrites and magnetites. In addition, the magnetizable particles can be comprised of alloys of iron, such as, for example, those containing aluminum, silicon, cobalt, nickel, vanadium, molybdenum, chromium, tungsten, manganese, copper, or a combination thereof.
When energized via the ESD 30 or other suitable energy storage device, the magnetic field generator 70 creates a magnetic field (flux lines 82 ), which ultimately passes through the MR fluid 80 filling the working gaps 78 A, 78 B. That is, a magnetic field is electrically induced around the wires of the field coil 96 , radiating outward therefrom to produce the resultant magnetic field (flux lines 82 ). As will be understood by those of ordinary skill in the art, the magnetic field naturally weakens in a direction progressing radially-outward away from the wires of the field coil 96 , with the magnetic field strengthening in closer proximity to the field coil 96 . While shown schematically as a single box in FIG. 3 for clarity, it is understood that the magnetic field lines of an actual magnetic field are concentrically circular with respect to the magnetic field generator 70 , and the direction of circulation of the magnetic field itself is dependent upon the direction of current flow within the field coil 96 . These factors are at least partially controllable via the controller 34 of FIG. 1 and the ESD 30 .
When the field coil 96 is electrically energized, the magnetic particles suspended in the carrier of the MR fluid 80 will align with the induced magnetic field (flux lines 82 ), thereby increasing the apparent viscosity of the MR fluid 80 . The increase in apparent viscosity increases the shear strength of the MR fluid 80 , resulting in torque transfer from the input member 46 to the output member 50 through the MRF clutch 40 . The output member 50 can then be used directly or indirectly for any suitable purpose, such as to start the engine 12 of FIG. 1 . Because energizing and responsiveness of fluid 80 thereto is nearly instantaneous, engine starting is carried out quickly and efficiently with the engine starting mechanism 40 .
While the best modes for carrying out the invention have been described in detail, those familiar with the art to which this invention relates will recognize various alternative designs and embodiments for practicing the invention within the scope of the appended claims. | A hybrid powertrain is provided that provides engine starting from an electric-only mode with a reduced torque load on the motor/generator. The powertrain includes an engine and a motor/generator, which may be a single motor/generator in a strong or full hybrid, but is not limited to such. The motor provides propulsion torque in an electric-only operating mode, and is configured to apply torque to a transmission input member. A first clutch is selectively engagable to connect the engine output member for common rotation with the transmission input member. An engine starting mechanism is provided that multiplies motor torque used to start the engine so that less is diverted from propelling the vehicle, enabling a smaller motor/generator to be used. A method of controlling such a powertrain is also provided. | 1 |
FIELD OF THE INVENTION
[0001] The present invention relates to a table poker game and particularly to an apparatus to increase attraction of table poker games.
BACKGROUND OF THE INVENTION
[0002] A table poker game is to allow players to bet on different game results on a betting table. According to the probability of appearance of the game results on the betting table, different game results have different odds. If the game result matches a player's bet, the player gets the payment according to the odds and player's wager.
[0003] Most common table poker games, such as baccarat, have established odds according to different game results. For instance, in the game of baccarat, the probability of appearance of banker pair or player pair is 7.47%. If the odds is established at 1 to 11, return rate for the player is merely 89.6%.
[0004] As the conventional table poker games generally have a lower return rate for the players, the players would easily feel unfair about the game results after playing for a period of time and lose interest. Thus the attraction of those games to the players decreases, and the utilization of the poker tables also drops gradually to result in lower return of investment.
SUMMARY OF THE INVENTION
[0005] The primary object of the present invention is to provide an apparatus to dynamically increase odds of table poker games.
[0006] To achieve the foregoing object, the apparatus of the invention allows a banker and a player to play a table game which generates a plurality of game results. The apparatus includes a pack of poker cards, a betting table and an electronic display panel. The poker cards are used by the banker to perform the table game according to a set rule. The table game generates at least one game results, and has a game probability according to the appearance of the game result.
[0007] The betting table has a plurality of betting zones to represent different game results. The betting table can be a solid table or an electronic table containing an electronic screen. The betting zones are displayed on the electronic screen which can be a touch panel. Each of the betting zones allows players to place a bet and has a payment odds. The product of the game probability and payment odds is a player's return rate. The value of the payment odds is a given value, which is controlled so that the player's return rate is not greater than 100%.
[0008] According to different game rules, the payment odds can include bets returning to the player or bets not returning to the player. The bets returning to the player are included in the payment odds when calculating the aforesaid player's return rate, namely the payment odds equals to retrieving multiples when the player winning the bet. In another condition, if the bets returning to the player are not included in the payment odds, the retrieving multiples when the player winning the bet not only include the multiples of the payment odds, but also include the player's original bet, hence the player's return rate should be modified to the product of the sum of the payment odds and one time of the player's bet (i.e. actual retrieving multiples when the player wining the bet) and the game probability.
[0009] The electronic display panel includes at least one display zone corresponding to the betting zone, and can be mounted at one side of the betting table (a solid one), or embedded in the electronic screen of the betting table. The display zone displays a dynamic raising odds to allow the banker to choose a higher one between the payment odds and dynamic raising odds to pay the player's bet. The dynamic raising odds is any one selected from multiple raising odds. The values and numbers of the raising odds are set by the banker. Each of the raising odds has an appearing probability. The accumulation sum of the product of the raising odds and their corresponding appearing probabilities is defined as an accumulation average odds. The product of the accumulation average odds and game probability is a player's raising return rate. The raising odds and their corresponding appearing probabilities can be controlled and adjusted to let the player's raising return rate approach to a given target value.
[0010] Similarly, if the payment odds does not include the bets returning to the player, the player's raising return rate should be modified to the product of the sum of the accumulation average odds and one time of the player's bet (i.e. actual retrieving multiples when the player wining the bet) and the game probability.
[0011] By means of the apparatus set forth above, the payment odds of the game results can be replaced by the dynamic raising odds, namely when the player wins the bet, he/she can get payment according to the dynamic raising odds, hence the player's return rate increases. The dynamic raising odds is versatile and appears frequently, thus is more appealing and gives players more incentive to place the bets. As a result, utilization of the poker table increases to achieve maximum economic benefit. By controlling the player's raising return rate within an acceptable range, utilization of the poker table increases and economic benefit also can be maintained as desired.
[0012] The foregoing, as well as additional objects, features and advantages of the invention will be more readily apparent from the following detailed description, which proceeds with reference to the accompanying embodiments and drawings. The embodiments serve only for illustrative purpose and are not the limitations of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 is a schematic view of the structure of a solid table of the invention.
[0014] FIG. 2 is a schematic view of the betting table of a solid table of the invention.
[0015] FIG. 3 is a schematic view showing a screen of an electronic display panel of the invention.
[0016] FIG. 4 is a schematic view of the structure of an electronic table of the invention.
[0017] FIG. 5 is a schematic view of the betting table of an electronic table of the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0018] Please refer to FIGS. 1 , 2 and 3 for an embodiment of the invention, taking baccarat as an example of the table poker game for discussion.
[0019] In the baccarat game, a banker 10 and a player (not shown in the drawings) take part in the game with five possible game results: banker's hand win, tie, player's hand win, banker pair and player pair. It is to be noted that when the first two cards of the banker 10 or player are the same, the game result is banker pair or player pair. As the banker pair and player pair could appear with any one of the banker's hand win, tie and player's win at the same time, the game result of banker pair or player pair is judged independently and not related to the banker's win, tie or player's win.
[0020] This embodiment includes a pack of poker cards 20 , a betting table 30 and an electronic display panel 40 . The poker cards 20 are used in the baccarat game and can generate at least one of the five game results (any one of banker's hand win, tie and player's hand win plus banker pair or player pair). The probability of generating each of the five game results is defined as a game probability.
[0021] The betting table 30 can be implemented by at least two types. The betting table 30 can be a solid table as shown in FIG. 1 with five betting zones 31 to represent five game results. The betting table 30 is divided into nine sections (marked by 1-9) to allow nine players to place bets at the same time. The five betting zones 31 are printed and marked on the surface of the table. FIGS. 4 and 5 illustrate another type of the betting table 30 A which can be an electronic table containing an electronic screen 32 . The five betting zones 31 of the betting table 30 A are displayed on the electronic screen 32 which can be a touch panel.
[0022] The five betting zones 31 allow the players to place bets and each has a payment odds. The product of the game probability and payment odds is a player's return rate. The payment odds is a given value which is controlled so that the player's return rate is not greater than 100%. In the event that the payment odds does not include the bets returning to the player, the player's return rate should be modified to the product of the sum of the payment odds and one time of the player's bet (i.e. actual retrieving multiples when the player winning the bet) and the game probability.
[0023] The electronic display panel 40 includes at least one display zone 41 corresponding to the betting zone 31 . When the number of the betting zones 31 is not many, the electronic display panel 40 can contain sufficient display zones 41 to one-to-one correspond to the betting zones 31 . In the event that a greater number of the betting zones 31 are formed, a choice can be freely made as required.
[0024] When the betting table 30 is a solid table, the electronic display panel 40 can be mounted at one side of the betting table 30 (referring to FIG. 1 ). When the betting table 30 A is an electronic table, the electronic display panel 40 A can be embedded in the electronic screen 32 of the betting table 30 A (referring to FIG. 4 ).
[0025] The display zone 41 displays a dynamic raising odds 411 to allow the banker 10 to choose a higher one between the payment odds and dynamic raising odds 411 to pay the player's bet. The dynamic raising odds 411 is any one selected from multiple raising odds. The values and numbers of the raising odds are set by the banker 10 . Each of the raising odds has an appearing probability. The accumulation sum of the product of the raising odds and their corresponding appearing probabilities is defined as an accumulation average odds. The product of the accumulation average odds and game probability is a player's raising return rate. The raising odds and their corresponding appearing probabilities can be controlled and adjusted to let the player's raising return rate approach to a given target value.
[0026] Similarly, if the dynamic raising odds 411 does not include the bets returning to the player, the player's raising return rate should be modified to the product of the sum of the accumulation average odds and one time of the player's bet (i.e. actual retrieving multiples when the player winning the bet) and game probability.
[0027] Take a game result of banker pair as an example for discussion as follows. The probability of winning the bet of banker pair is 7.47%, and the given payment odds is 1 to 11, which is the present conventional public odds. The given target value is 94% (namely store benefit is 6%, which also can be determined by itself). The number of the raising odds (not including the bets returning to the player) chose by the dynamic raising odds 411 is five with values of 1 to 11, 1 to 12, 1 to 13, 1 to 14 and 1 to 15. The appearing probabilities corresponding to the raising odds are processed and adjusted to be 62%, 25%, 8%, 3% and 2%. Incorporating the aforesaid values with the raising odds to obtain the player's raising return rate expressed as follows:
[0000] (1+11*62%+12*25%+13*8%+14*3%+15*2%)*7.47%=93.97%
[0028] Thus the player's raising return rate approaches to the target value of 94% to meet requirement.
[0029] Next, take a game result of tie as an example for discussion. The probability of winning the bet of tie is 9.52%, and the given payment odds is 1 to 8. The given target value is 94%. The number of the raising odds (not including the bets returning to the player) chose by the dynamic raising odds 411 is three with values of 1 to 8, 1 to 10 and 1 to 12. The appearing probabilities corresponding to the raising odds are processed and adjusted to be 63%, 30% and 7%. Incorporating the aforesaid values with the raising odds to obtain the player's raising return rate expressed as follows:
[0000] (1+8*63%+10*30%+12*7%)*9.52%=94.06%
[0030] Thus the player's raising return rate approaches to the target value of 94% to meet requirement.
[0031] Other game results, such as banker's hand win, player's hand win and player pair can also be adapted as previously discussed to generate different raising odds with varying appearing probabilities. For instance, due to game characteristics, if the game result is banker's hand win or player's hand win, the raising odds chose by the dynamic raising odds 411 is limited to 1 to 1; if the game result is player pair or banker pair, the number of the raising odds chose by the dynamic raising odds 411 is five with values of 1 to 11, 1 to 12, 1 to 13, 1 to 14 and 1 to 15.
[0032] Refer to FIG. 4 . In this embodiment, the raising odds chose by the dynamic raising odds 411 for the game results of banker's hand win, tie, player's win, banker pair and player pair is respectively 1 to 1. 1 to 10, 1 to 1, 1 to 14 and 1 to 11. These values can be reset when each game is restarted.
[0033] As a conclusion, in the invention, the payment odds can be replaced by the dynamic raising odds 411 so that the players can get payment according to the dynamic raising odds 411 upon winning the bet, thus the player's return rate increases. Moreover, as the dynamic raising odds 411 is versatile and appears frequently, it is more appealing to the players and offers more incentive to the players to place bets. As a result, utilization of the poker table increases. Since the player's raising return rate can be controlled within an acceptable range, economic benefit of the store also can be maintained. | An apparatus for table poker games aims to increase odds of the table poker games. The apparatus includes an electronic display panel which has at least one display zone to represent a corresponding betting zone and display a dynamic raising odds. Banker can pay player's bets according to the dynamic raising odds. Thus an expected value of the table poker games can be increased to give players extra award, thereby can increase the attraction of the table poker games and also enhance utilization of the poker tables. | 0 |
FIELD OF THE INVENTION
This invention is directed to novel arylsulfonyl tetrazole compounds, their method of preparation, and their use as improved coupling agents in polynucleotide synthesis.
DESCRIPTION OF THE PRIOR ART
5-Arylthioalkyl-tetrazoles have been prepared by reaction of the arylthioalkyl nitrile with an azide compound, and 5-arylsulfonylalkyl-tetrazoles prepared by further reaction with an oxidizing agent (see U.S. Pat. No. 3,337,576 Buchanan et al). 5-Para-nitrobenzene-sulfonamido-tetrazoles have been prepared by reacting 5-amino-tetrazole monohydrate with para-nitrobenzene sulfonyl chloride (see U.S. Pat. No. 2,209,243 Winnek). Both of these types of 5-tetrazole derivatives had biological activity.
Certain arylsulfonyl-1,2,4-triazoles were prepared from arylsulfonyl chloride and 1,2,4-triazole, and were found to have biological activity (see U.S. Pat. No. 3,293,259 Wolf).
No references have been noted to arysuflonyl tetrazoles nor their utility as coupling agents.
In polynucleotide synthesis the coupling of nucleotides is carried out by condensing the free phosphate group of one nucleotide to the free hydroxyl group of a second nucleotide or nucleoside, and such couplings can be repeated many times.
The development of dicyclohexylcarbodiimide (DCC), mesitylenesulfonyl chloride (MS) and triisopropylbenzenesulfonyl chloride (TPS) as reasonably effective condensing or coupling reagents has played a significant role in the synthesis of polynucleotides by the diester method (see S. A. Narang, K. Itakura, C. P. Bahl and N. Katagiri -- J. Am. Chem. Soc. Vol. 96, page 7074, 1974). In the case of the triester synthetic approach (see K. Itakura, N. Katagiri, C. P. Bahl, R. H. Wightman and S. A. Narang -- J. Am. Chem. Soc. Vol. 97, page 7327, 1975), triisopropylbenzenesulfonyl chloride (TPS) has been used almost exclusively as the condensing reagent because dicyclohexylcarbodiimide (DCC) will not activate phosphodiester functions and mesitylenesulfonyl chloride (MS) causes extensive sulfonation of the primary 5'-hydroxyl group of the nucleotide component thus blocking possible condensation.
The search for new condensing reagents was initiated because of our continued realization of low yields (ca. 20%) when attempting condensation with TPS of products containing purine bases, especially guanine. These low yields might be attributed to the liberation of hydrogen chloride from the triisopropylbenzenesulfonyl chloride (TPS) during the condensation reaction.
SUMMARY OF THE INVENTION
Arylsulfonyl tetrazoles have been prepared of the general formula ##STR2## where R 1 , R 2 and R 3 are selected from hydrogen, lower alkyl, and lower alkoxy groups, and these compounds have been found to be advantageous coupling agents. These 1-arylsulfonyl-tetrazoles can preferably have as aryl groups, unsubstituted phenyl or mono- or di-substituted-phenyl, or 2,4,6-trisubstituted-phenyl groups. The substituents can most suitably be lower alkyl or lower alkoxy groups having from 1 to 4 carbon atoms. Suitable aryl groups include phenyl, para-tolyl, para-ethylphenyl, paralower alkoxyphenyl (e.g. anisyl), mesityl, and 2,4,6-triisopropylphenyl. The phenyl compound tends to be more reactive and less stable than the substituted-phenyl compounds.
These arylsulfonyl tetrazoles can be prepared by reacting, in a non-polar organic solvent, an arylsulfonyl chloride with tetrazole, in the presence of a basic amine catalyst. Suitable solvents include dioxane, chloroform, carbon tetrachloride and benzene. Suitable basic amine catalysts include triethylamine, aniline and lutidine. Approximately equimolar amounts of the two reactants will normally be used. After the reaction is complete a precipitate will usually be present in the cooled reaction medium, and this precipitate should be removed and the liquor processed to recover the soluble arysulfonyl tetrazole.
In polynucleotide synthesis, an appropriate N-protected nucleotide or oligonucleotide phosphate and an appropriate N-protected nucleotide or oligonucleotide containing a free 5'-hydroxyl group are mixed in an appropriate aprotic organic solvent medium and treated with the arysulfonic tetrazole coupling agent. From about 2 to about 3 molar equivalents of coupling agent based on the 5'-protected component are suitable. The coupling or condensing reaction will normally take about 1-2 hours at room temperature. The reaction mixture is then inactivated and processed to recover the phosphoester product.
DESCRIPTION OF PREFERRED EMBODIMENTS
The following Examples illustrate the various aspects of the invention, and are not to be construed in a limiting sense. Alternative components and conditions will be apparent to those skilled in the art.
EXAMPLE 1
Preparation of Arylsulfonyltetrazoles
To a solution of dioxane (2 ml) containing triethylamine (10.1 mmoles) was added the appropriate arysulfonyl chloride (10 mmoles) and tetrazole (10 mmoles) with cooling. After 2 hours, the precipitate was filtered off, discarded, and the liquor evaporated to dryness. The solid residue was dissolved in chloroform (˜50 ml) and washed with water (2 × 20 ml). The chloroform solution was dried over anhydrous sodium sulfate and after evaporation of solvent, the residue was recrystallized from an appropriate organic solvent as stated below. The isolated yield was 70-80%. Each of the compounds was characterized by its melting point, elemental analysis and NMR spectra as detailed below.
1-(Benzenesulfonyl) -tetrazole (BS-tetr.): White crystals m.p. 86-92° (Recrystallized from benzene) Elem Anal. Calcd. for C 7 H 6 N 4 O 2 S: C, 36.36; H, 3.05; N, 28.27. Found: C, 36.50; H, 3.00; N, 28.24. NMR (CDCL 3 , ppm from trimethyl silicane TMS) 9.25 (1H, S, CH in tetrazole); 8.0 (5H, m. aromatic ring).
1-(Mesitylenesulfonyl)-tetrazole (MS-tetr.): White crystals m.p. 108-119° (Recrystallized from benzene) Elem. Anal. Calcd. C 10 H 12 N 4 O 2 S: C, 47.61; H, 4.79; N, 22.21. Found: C, 47.69; H, 4.84; N, 22.30. NMR (CDCL 3 ppm from TMS) 9.21 (1H, S, CH in tetrazole), 7.5 (2H, S, aromatic ring); 2.7 (6H, S, CH 3 ) ortho, 2.36 (3H, S, CH 3 para).
1-(2,4,6-Triisopropylbenzenesulfonyl)-Tetrazole (TPS-tetr.): White crystals m.p. 95°-97° (Recrystallized from benzenepetroleum ether), Elem. Anal. Calcd. C 16 H 24 N 4 O 2 S: C, 57.12; H, 7.19; N, 16.65 . Found: C, 57.25; H, 7.20; N, 16.69. NMR (CDCL 3 , ppm from TMS) 9.28 (1H, S, CH in tetrazole); 7.4 (2H, S, aromatic ring); 4.15 (2H, M, CH in ortho); 3.14 (1H, M, CH in para); 1.28 (18H, pseudoquartet, CH 3 ).
EXAMPLE 2
Synthesis of Polynucleotides of Defined Sequences
A 5'-O-dimethoxytrityl-N-protected oligonucleotide-3'-p-chlorophenyl phosphate (1 molar equiv. ) and an appropriate N-protected oligonucleotide containing free 5'-hydroxyl (1.2 molar equiv.) were mixed in anhydrous pyridine (5ml per g) and treated with arylsulfonyl tetrazole (3 molar equiv. based on 5'-protected component) at room temperature. When the reaction was over (after 1-2 hours) as checked by tlc on silica-gel, the reaction mixture was decomposed with water (10 ml per g) with cooling followed by extraction with chloroform (100 ml per g). The chloroform layer was washed with 0.1 M triethylammonium bicarbonate (50 ml × 3) followed by water, dried over anhydrous sodium sulfate and evaporated to a gum in the presence of excess of toluene under reduced pressure. The gum was dissolved in choroform and purified by silica-gel column chromatography. The column was monitored by checking an aliquot from every second fraction collector tube on silica-gel tlc plate using chloroform-methanol (1-10% v/v) as eluent.
The following Table 1 gives comparisons of the yields of various di- and trinucleotide products using triisopropylbenzenesulfonyl chloride (TPS), a prior art coupling agent, and two arylsufonyl tetrazole coupling agents according to the invention. The reaction time was 0.5 hour in each case. The yields are seen to be significantly improved using the coupling agents of the invention. For the di- or trinucleotides as in Table 1, a reaction time of 0.5 hour was sufficient, but for higher polynucleotides a longer reaction time will normally be required.
TABLE 1__________________________________________________________________________5'-Protected 3'-Protected Product % Yield (using 2 molar equiv.)component component based on 5'-protected component(1 molar equiv.) (1.2 molar equiv.) TPS MS-tetr. TPS-tetr.__________________________________________________________________________ Fully protected dinucleotides[(MeO).sub.2 Tr]dbzA-ClPh dbzAτCE [(MeO).sub.2 Tr]dbzAτbzAτCE 30 75 78[(MeO).sub.2 Tr]T-ClPh dacGτCE [(MeO).sub.2 Tr]dTτacGτCE 34 65 68[(MeO).sub.2 Tr]dacG-ClPh dbzAτCE [(MeO).sub.2 Tr]dacGτbzAτCE 22 66 52[(MeO).sub.2 Tr]dbzC-ClPh dacGτCE [(MeO).sub.2 Tr]dbzCτacGτCE 38 70 80[(MeO).sub.2 Tr]dbzA-ClPh dTτCE [(MeO).sub.2 Tr]dbzAτTτCE 52 73 81[(MeO).sub.2 Tr]dbzA-ClPh dbzCτCE [(MeO).sub.2 Tr]dbzAτbzCτCE 68 74 70[(MeO).sub.2 Tr]T-ClPh dbzAτCE [(MeO).sub.2 Tr]dTτbzAτCE 62 72 78[(MeO).sub.2 Tr]dbzC-ClPh dbzCτCE [(MeO).sub.2 Tr]dbzCτbzCτCE 71 83 80[(MeO).sub.2 Tr]dbzC-ClPh TτCE [(MeO).sub.2 Tr]dbzCτTτCE 68 79 82 Fully protected trinucleotides[(MeO).sub.2 Tr]dbzAτbzA-ClPh TτCE [(MeO).sub.2 Tr]dbzAτbzAτTτCE 45 74 71[(MeO).sub.2 Tr]dbzAτT-ClPh dbzAτCE [(MeO).sub.2 Tr]dbzAτTτbzAτCE 51 76 78[(MeO).sub.2 Tr]dbzAτT-ClPh T(oAc) [(MeO).sub.2 Tr]dbzAτTτT(oAc) 59 82 78[(MeO).sub.2 Tr]dbzAτbzC-ClPh dbzAτCE [(MeO).sub.2 Tr]dbzAτbzCτbzAτCE 52 70 72[(MeO).sub.2 Tr]dTτacG-ClPh TτCE [(MeO).sub.2 Tr]dTτacGτTτCE 32 64 52[(MeO).sub.2 Tr]TτbzA-ClPh TτCE [(MeO).sub.2 Tr]dTτbzAτTτCE 55 72 70[(MeO).sub.2 Tr]dacGτbzA-ClPh dacGτCE [(MeO).sub.2 Tr]dacGτbzAτacGτCE 18 58 40[(MeO).sub.2 Tr]dbzC-ClPh dacGτacG(oAc) [(MeO).sub.2 Tr]dbzCτacGτacG(oAc) 20 68 59[(MeO).sub.2 Tr]dbzCτbzC-ClPh dacGτCE [(MeO).sub.2 Tr]dbzCτbzCτacGτCE 32 61 58[(MeO).sub.2 Tr]dbzCτT-ClPh dbzCτCE [(MeO).sub.2 Tr]dbzCτTτbzCτCE 65 76 80__________________________________________________________________________ | Arylsulfonyl tetrazoles of the formula ##STR1## where R 1 , R 2 and R 3 are selected from hydrogen, lower alkyl and lower alkoxy groups, and their preparation are described.
These compounds have been found to be advantageous condensing or coupling agents via phosphoester formation in polynucleotide synthesis. | 2 |
RELATED APPLICATIONS
[0001] This application claims the benefit of US Provisional Application No. 61297587, filed Jan. 22, 2010.
TECHNICAL FIELD
[0002] This invention relates to carbon-free fuels. More specifically, this invention relates to the use of an ammoniacal, ammonia salt solution as a fuel.
BACKGROUND OF THE INVENTION
[0003] In 2005, the United States Department of Energy (DOE) updated its goals for hydrogen production. The DOE noted that one kilogram of hydrogen contains approximately the same energy as one gallon of gasoline, termed as a gallon of “gasoline equivalent,” or “gge.” The DOE therefore set the goal for the DOE's hydrogen program to develop methods and techniques capable of producing hydrogen for between $2-$3 per gge by 2015. In the intervening three years, the DOE has funded millions of dollars of research at DOE owned federal laboratories to attain this goal. To date, no one has reported any results that have done so.
[0004] The reason that the DOE is interested in hydrogen is because when burned hydrogen produces no carbon dioxide effluent. As such, hydrogen is a potential fuel that does not generate so-called greenhouse gasses, including carbon dioxide. Unfortunately, hydrogen is costly, and is difficult to store and transport.
[0005] A better alternative to hydrogen is anhydrous ammonia. Like hydrogen, ammonia contains no carbon. As such, when burned, ammonia does not produce carbon dioxide. Ammonia has also long been shown to be a useful fuel. Both turbine and internal combustion engines have been shown to run effectively on ammonia. However, the use of ammonia as an engine fuel is not without drawbacks.
[0006] One such drawback is related to the fact that at room temperature and atmospheric pressure, ammonia exists as a vapor. However, the critical temperature of ammonia (T c =132.6° C.) is much greater than standard room temperature. As such, ammonia may be stored as a non-cyrogenic liquid (in contrast with liquid hydrogen, T c =−240° C.) at elevated pressure.
[0007] An additional drawback related to the use of ammonia as a combustion fuel is its limited flammability (16-25% ammonia by volume in air, compared to 4-74% hydrogen in air), as well as its low flame speed (ca. 0.11 m/s for ammonia, compared to ca. 3.8 m/s for hydrogen), which limits its utility for high-speed engines and burners.
[0008] Accordingly, there is a need by those having ordinary skill in the art to devise alternative fuels to ammonia that provide the benefits of ammonia while escaping some of the drawbacks. The present invention provides such an alternative.
SUMMARY OF THE INVENTION
[0009] One aspect of the invention is the use of a solution of salt within ammonia as a fuel. The preferred ammonia/salt solution is an ammonium nitrate solute (NH 4 NO 3 ) within the solvent anhydrous ammonia (NH 3 ). The solution may also contain a small amount of water (H 2 O), although water is neither necessary nor desirable.
[0010] The preferred application for this fuel solution is for use in internal combustion engines and gas combustion turbines. The invention improves on prior art ammonia-based fuel mixtures because the addition of salts reduces the vapor pressure of ammonia, allowing it to be stored in tanks at pressures closer to or at atmospheric pressure. The invention also improves on prior art ammonia-based fuel mixtures because it does not contain carbon, which if present would produce undesired carbon dioxide or carbon monoxide upon combustion. The invention also improves on prior art ammonia-based fuel mixtures because it does contain molecularly-fixed oxygen, which increases the combustibility of the mixture relative to pure ammonia when burned in air. The oxygen in the fuel solution also enhances the combustion flame speed relative to pure ammonia, which is of benefit to its use in piston-based and rotary combustion engine applications.
[0011] Ammonium nitrate may be dissolved in ammonia at room temperature (the desired temperature for the storage and use of the fuel solution) up to a concentration of at least 3.62 grams of ammonium nitrate per gram of ammonia.
[0012] As increasing amounts of ammonium nitrate are added to liquid ammonia, the vapor pressure of the mixture is reduced, reaching a vapor pressure of nearly atmospheric pressure at saturation. Thus, one aspect of the present invention is that the fuel solution's vapor pressure may be tuned as appropriate for the intended combustion device by the addition of a specific amount of ammonium nitrate solute to the ammonia solvent. In this manner, the fuel of the present invention may be configured to provide a specific vapor pressure to an engine or other combustion device at a given fuel storage temperature.
[0013] The salt/ammonia solution will also have an increased internal oxygen content when compared to pure ammonia, and increasing amounts of ammonium nitrate within the solution will aid the oxidation of the fuel during its combustion in air. Therefore, the combustibility and flame speed of a fuel solution may also be tuned as appropriate for the intended combustion device by the addition of a specific amount of ammonium nitrate solute to the ammonia solvent. In this manner, the fuel of the present invention may be configured to provide a fuel having a specific combustibility and flame speed for an intended combustion device.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] For the purposes of promoting an understanding of the principles of the invention, a series of experiments were conducted reducing the present invention to practice.
[0015] A salt/ammonia fuel mixture was created by measuring 24.0 grams of ammonium nitrate salt crystals into a stainless steel jar with a usable volume of approximately 100 cubic centimeters. The container was then sealed and connected to a gas line providing gaseous anhydrous ammonia from a small cylinder at room temperature. The stainless steel jar was then immersed in an ice water bath while ammonia was allowed to flow into the jar, where it condensed within as a liquid. The amount of ammonia transferred to the jar was determined by weighing. The final solution had a density of approximately 0.8 grams per milliliter and comprised a solution of approximately 30 weight percent ammonium nitrate in liquid ammonia. The stainless steel jar, which was also fitted with a dip tube, was connected to a small automotive liquid fuel injector. The injector was triggered by intermittent connection to an automotive 12 volt lead acid battery. Liquid salt/ammonia solution was sprayed through the injector into a free-burning propane flame, where the solution was ignited, burning with an orange-yellow flame. In contrast, a spray consisting of pure anhydrous ammonia (with no added ammonium nitrate salt) did not visibly ignite within the flame.
[0016] While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character. Only certain embodiments have been shown and described, and all changes, equivalents, and modifications that come within the spirit of the invention described herein are desired to be protected. Any experiments, experimental examples, or experimental results provided herein are intended to be illustrative of the present invention and should not be considered limiting or restrictive with regard to the invention scope. Further, any theory, mechanism of operation, proof, or finding stated herein is meant to further enhance understanding of the present invention and is not intended to limit the present invention in any way to such theory, mechanism of operation, proof, or finding.
[0017] Thus, the specifics of this description and the attached drawings should not be interpreted to limit the scope of this invention to the specifics thereof Rather, the scope of this invention should be evaluated with reference to the claims appended hereto. In reading the claims it is intended that when words such as “a”, “an”, “at least one”, and “at least a portion” are used there is no intention to limit the claims to only one item unless specifically stated to the contrary in the claims. Further, when the language “at least a portion” and/or “a portion” is used, the claims may include a portion and/or the entire items unless specifically stated to the contrary. Likewise, where the term “input” or “output” is used in connection with an electric device or fluid processing unit, it should be understood to comprehend singular or plural and one or more signal channels or fluid lines as appropriate in the context. Finally, all publications, patents, and patent applications cited in this specification are herein incorporated by reference to the extent not inconsistent with the present disclosure as if each were specifically and individually indicated to be incorporated by reference and set forth in its entirety herein. | The use of a solution of salt within ammonia as a fuel. The preferred ammonia/salt solution is an ammonium nitrate solute (NH 4 NO 3 ) within the solvent anhydrous ammonia (NH 3 ). The solution may also contain a small amount of water (H 2 O). | 2 |
BACKGROUND AND SUMMARY OF THE INVENTION
This invention relates generally to the field of physiological diagnosis and, more particularly, to a diagnostic instrument for determining temperature discrimination.
Heretofore in the field of medical diagnosis, various efforts have been attempted to develop instruments for testing the reaction of a patient to cutaneously received sensations for the purpose of establishing the condition of the peripheral nerves as well as of the central nervous system. One expedient for gaining insight to the condition of the peripheral nerves and the central nervous system is by means of testing cutaneous thermal discrimination. Previously, devices for testing thermal discrimination have required preparation preliminary to usage and in some cases are also cumbersome and must be used at a fixed location, as in a doctor's office. A relatively recent effort for developing testing equipment for this purpose has involved a device incorporating a multiplicity of so-called "thermal discs", but the same are relatively bulky and large, so that patients are usually brought to the device for tests, and also require some preliminary preparation.
Heretofore there has not been available an instrument that requires no preliminary preparation of such limited size as to be amenable to transport, as within a doctor's conventional bag, or even the pocket of a jacket, for testing the temperature responsiveness of the patient's skin.
Therefore, it is an object of the present invention to provide a diagnostic instrument which is of such relatively reduced size that it may be easily carried within the pocket of a physician just as with a pencil, and which instrument is useful in determining the cutaneous thermal discrimination of the patient for providing a key to the state of the patient's peripheral nerves and central nervous system.
It is another object of the present invention to provide an instrument of the character stated which is formed of a marked simplicity of cheaply produced components; which does not involve any moving parts so that the same is durable and resistant to damage through usage.
It is a further object of the present invention to provide an instrument of the character stated which does not necessitate any preliminary conditioning or waiting for usage, being in a constant state of readiness.
It is another object of the present invention to provide an instrument of the character stated which is operated by a physician, physician-in-training, or paramedical personnel, and requiring only the simplest instruction and guidance.
It is another object of the present invention to provide an instrument of the type stated which as indicated above may be most economically manufactured; the use of which obviates costly, elaborate testing equipment as heretofore found in offices and laboratories, and which through its facile portability permits of another area of diagnosis of a patient who may be remote from a hospital or doctor's office.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a diagnostic instrument constructed in accordance with and embodying the present invention, illustrating the same in a condition of use.
FIG. 2 is a side elevational view.
FIG. 3 is an end view of the instrument taken from the left hand side of FIG. 2.
FIG. 4 is an end view taken from the right hand side of FIG. 2.
FIG. 5 is a vertical transverse sectional view taken on the line 5--5 of FIG. 2.
FIG. 6 is a vertical transverse sectional view taken on the line 6--6 of FIG. 2.
FIG. 7 is a horizontal transverse sectional view taken on the line 7--7 of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now by reference characters to the drawings which illustrate the preferred embodiment of the present invention, A designates a diagnostic instrument comprising an elongated narrow body fabricated preferably of wood, which may be, desirably, but not necessarily, circular in cross section. Provided within said body 1 is a bore 2, the base of which, as at 3, is located in the intermediate portion of body 1, and which bore opens at its end remote from its base through one end of said body, as at 4. Snugly received, as by a jam fit, within bore 2, is the stem 5 of a metallic component 6, which for purposes of facilitating description will be herein referred to as a "rivet", the inner end of which may abut against bore base 3 and which rivet encompasses a diametrally increased head 7 having a diameter preferably of like extent as the cross section of body 1. As may best be seen in FIGS. 2 and 7, rivet head 7 is endwise rounded, as at 8. The opposite end of body 1 remote from head 7 is also preferably rounded, as at a, with the same curvature as head 7, for purposes presently appearing.
As indicated above, body 1 is fabricated desirably of wood but may also be made of plastic, rubber, or other material having recognizedly poor or relatively low heat conductivity properties. Rivet 6 is made of metal having relatively high heat conductivity properties but in any event is of such metal as to effect heat transfer at a rate sufficiently greater than that of the material of construction of body 1 to establish a marked and definitive differential with respect to said body. Accordingly, rivet 6 may be formed of any suitable metal or alloy thereof, such as copper, steel, silver, bronze, etc. It will thus be seen that one end of instrument A is constituted of body 1 (see FIG. 3) while the opposite end is comprised of head 7 of rivet 6; it being observed that said head 7 obscures or prevents exposure of any adjacent portions of body 1.
As may best be indicated in FIG. 1, instrument A is of such size as to be easily manipulated by the hand of the user, and which may have a length of approximately 4 " with a cross section of approximately 1/2 ". Thus instrument A is relatively small, compact, and of light weight, easily carried in the user's pocket or with an instrument bag. The stem of rivet 6 is, as indicated, substantially 1/2 the length of body 1 and should, hence, approximate 2 " for purposes presently appearing. Additionally, with a body of the dimensions above outlined, rivet 6 should desirably have a weight within the range of 14 grams and with the maximum cross section of head 7 being at least 1/2 ".
As pointed out hereinabove, the selection of materials of construction for body 1 and rivet 6 is premised upon a differential in the capacity to transfer heat. Therefore, upon contacting a patient's skin with rivet head 7, a distinctly cooler sensation will be experienced than when the opposite end of instrument A is applied to the same location. This differential in sensations results from the fact that body 1, if made of wood, plastic, or rubber, is a poor conductor of heat so that the individual will experience substantially no temperature sensation in view of the fact that heat will not be readily transferred from the skin to such material. On the other hand, when the metallic end of instrument A or rivet head 7 is applied to the patient's skin a relatively cool sensation will be experienced in view of the ready transfer of heat from the contacted body area to the rivet in view of its aforesaid properties.
Therefore, one might term the rivet head 7 of instrument A the "cool" or "cold" end of instrument A and the opposite end consisting of the material body 1 as the "warm" or "hot" end.
In operation, instrument A is to be utilized at room temperature and with the ends being alternatively applied to a selected zone of the patient, such as the face (see FIG. 1) or the dorsum of the hand or the foot. It will be recognized that body temperature is normally above room temperature, there being a difference of between 5° to 10° C. Each end is applied to the select zone for a period of 1 to 2 seconds, and a normal individual will readily indicate to the operator whether one end feels cooler than the other. Clearly the metallic end will be the one indicated as cooler unless the patient is suffering diminution in, or loss of, cutaneous sensory capacity, such as patients with peripheral neuropathy. Thus, the operator will alternatingly apply the different ends to the patient to obtain a percentage of correct answers which percentage quantitaties the integrity of a patient's temperature discrimination. It has been found that a range of above 50% and up to 100% is correct so as to eliminate the possibility that a patient might correctly guess 1/2 of the choices by chance alone.
Because the test depends upon the temperature differential between the patient's body and instrument A, which latter will be at room temperature, it is important that if the patient's hands or feet are cold, the same should be warmed to body temperature before testing.
From the foregoing one may readily appreciate that rivet 6 has certain critical design aspects; one being that the surface area provided by head 7 be of adequate extent so as to make contact with a sufficient area of the patient's skin so that enough nerve endings are engaged to make the test effective since engagement with a relatively small zone could be misleading. A surface area greater than 1 centimeter square gives reproducible results on the dorsum of the patient's foot, which zone is the least sensitive. Areas of less extent, although effective on the face and possibly upon the hand would not have the reliability if applied to the dorsum of the foot.
In addition to the exposed surface area of rivet 6 the same must be of sufficient mass so that the same will not rapidly approach body temperature during the period of usage. It is manifestly apparent that the cool sensation effected by head 7 be retained through the period of testing which, as suggested, necessitates repeated application. If the mass were relatively small the said rivet would quickly approach body temperature by such repeated application and thus lose its effectiveness. In such an eventuality, the test could not be completed without periods of interruption within which the rivet 6 could be restored to its testing condition. 14 grams has been discovered as a desired weight, but actually experience has taught that a metallic member weighing more than 10 grams has proved adequate for complete testing without interruptions requisite to permit the rivet to return to room temperature.
Accordingly, in view of the foregoing it will be seen that diagnostic instrument A is of marked simplicity of construction, consisting of but two easily produced and interfitted components. However, the metallic element must possess certain critical dimensional and weight properties for efficient and efficaciously effected testing. Furthermore, instrument A is of such limited size as to be transported in a facile manner and thus be usable at any given site, whether within the patient's home, at the scene of an accident, etc., as distinguished from the more complex and bulky devices which have been used heretofore to test cutaneous sensory reaction, all of which require presentation of the patient at the prescribed location of the equipment.
As indicated above, the end of body 1 remote from head 7 is rounded and with like curvature as said head 7. Although such end curvature of body 1 does not bear upon the functionality of the same, such is desirable in order to prevent a patient from differentiating between head 7 and end a by a sensory detection in any geometrical differences. Thus, for instance, with head 7 being rounded and the opposite end of body 1 being of other configuration, such as flat, slightly concave, or even of different convexity, a patient could provide the "correct" answers regardless of the thermal reaction to the instruction ends and thereby frustrate the entire examination. | A diagnostic instrument for use in determining the cutaneous sensory capacity of a patient which comprises an elongate body having a bore proceeding from one end and terminating spacedly from the other end. Fitted within said bore is a metallic member having an enlarged head projecting beyond the bore opening for covering the adjacent end of the body. Said body is fabricated of material, such as wood, rubber, plastic or synthetic material having heat transfer properties relatively reduced with respect to the heat conductivity of the metallic member. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a weight member for a golf club head.
[0003] 2. Description of Related Art
[0004] A typical golf club head body for a golf club head usually adopts a material having a high coefficient of restitution to allow a golf ball stricken by the golf club to fly through a longer distance. Since a material with a high vibration-absorbing capacity may absorb most part of vibration of the golf club generated as a result of striking a golf ball, titanium or titanium alloy is often selected as the material for reducing the vibration transmitted to the hands of the golfer even if the golf ball is not hit by the sweet spot of the striking plate of the golf club head. Nevertheless, since titanium has a density of about 4.51 g/cm 3 , the center of gravity of the golf club, which is a product of assembling a shaft with a golf club head that uses titanium (such as 6-4 Ti) as the main composition, is not in an appropriate location. A solution to this problem is inserting a weight member into the golf club head to adjust the location of the center of gravity.
[0005] FIG. 1 of the drawings illustrates a golf club head body 1 having a recession 11 and a weight member 2 to be embedded by tight fitting into the recession 11 . Then, surface finishing is performed on the golf club head body 1 and the weight member 2 to provide a golf club head. The weight member 2 is made of a material that has a high density and that is rigid and fragile. The precision formation of the weight member 2 for mating with the recession 11 of the golf club head body 1 is difficult, and the weight member 2 is apt to break while pressing the weight member 2 into the golf club head body 1 . Further, a gap between the recession 11 and the weight member 2 is generated after the surface finishing and thus requires subsequent filling of the gap. The tight engagement between the surfaces of the golf club head body 1 and the weight member 2 are adversely affected. Further, since the filling material for filling the gap between the recession 11 and the weight member 2 is a high molecular polymer, the weight member 2 tends to disengage from the golf club head body 1 after long-term striking of golf balls for a period of time.
[0006] FIG. 2 shows another conventional golf club head, wherein a weight member 4 is placed in a recession 31 of a golf club head body 3 and then fixed in place by welding. Although the engaging strength between the golf club head body 3 and the weight member 4 is improved by welding, the high temperature generated during welding causes melting of both the golf club head body 3 and the weight member 4 , variation in the welding pool disturbance, welding speed, electric current, and heat transmitted to the golf club head body 3 and the weight member 4 affects the depth of the welding bead 32 . As a result, the welding bead 32 is irregular in shape, resulting in difficult quality control and adversely affecting the appearance. Further, in a case that the golf club head body 3 is made of titanium or titanium alloy, the welding heat checking often occurs, as titanium has a poor welding effect with other metal. In particular, titanium can only be welded with zirconium, niobium, tantalum, and hafnium.
OBJECTS OF THE INVENTION
[0007] An object of the present invention is to provide a golf club head including a golf club head body and a weight member made of a material having a melting point higher than that of the golf club head body, avoiding melting of the weight member during a welding procedure for fixing the weight member in the golf club head body. The appearance of the golf club head is aesthetic, and the process quality control is improved.
[0008] Another object of the present invention is to provide a golf club head including a golf club head body and a weight member received in a recession of the golf club head body, wherein a gap between the golf club head body and the weight member is filled by a welding material used during the welding procedure, thereby preventing the weight member from disengaging from the golf club head body and improving the quality of the golf club head.
SUMMARY OF THE INVENTION
[0009] To achieve the aforementioned objects, the present invention provides a golf club head comprising a golf club head body and a weight member. The golf club head member has a recession in which the weight member is mounted. The weight member is securely mounted in the recession of the golf club head body by means of a welding procedure using a welding material. The weight member is made of a material having a melting point higher than that of the golf club head body, avoiding melting of the weight member during the welding procedure. Only a portion of the golf club head body fuses with the welding material while using the welding material for proceeding with the welding procedure for the weight member.
[0010] Other objects, advantages and novel features of this invention will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is an exploded perspective view of a conventional golf club head;
[0012] FIG. 2 is a top view of another conventional golf club head;
[0013] FIG. 3 is an exploded perspective view of a golf club head in accordance with the present invention;
[0014] FIG. 4 is a sectional view of the golf club head in accordance with the present invention;
[0015] FIG. 5 is an enlarged sectional view of the golf club head in accordance with the present invention after welding;
[0016] FIG. 6 is an enlarged view of a circled portion of FIG. 5 ;
[0017] FIG. 7 is an enlarged sectional view of the golf club head in accordance with the present invention after surface finishing;
[0018] FIG. 8 is a top view of the golf club head in accordance with the present invention after surface finishing;
[0019] FIG. 9 is a view similar to FIG. 7 , illustrating a modified embodiment of the golf club head in accordance with the present invention;
[0020] FIG. 10 is a view similar to FIG. 7 , illustrating another modified embodiment of the golf club head in accordance with the present invention; and
[0021] FIG. 11 is a metallographic view illustrating the welding boundary between the welding member and stainless in the embodiment of FIG. 10 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Preferred embodiments of the present invention are now to be described hereinafter in detail, in which the same reference numerals are used in the preferred embodiments for the same parts as those in the prior art to avoid redundant description.
[0023] Referring to FIG. 3 , an embodiment of a golf club head in accordance with the present invention includes a golf club head body 5 and a weight member 6 . The golf club head body 5 includes a recession 51 for receiving the weight member 6 . The weight member 6 includes a protrusion 61 on a side thereof, forming a shoulder 611 . The golf club head body 5 may be made by carbon steel of S20C, 8620, or SUS 304. The weight member 6 is made of a material having a high melting point, such as tungsten (W) having a melting point of 3410° C. and a density of 19.3 g/cm 3 , tantalum (Ta) having a melting point of 2996° C. and a density of 16.65 g/cm 3 , molybdenum (Mo) having a melting point of 2610° C. and a density of 10.2 g/cm 3 , niobium (Nb) having a melting point of 2468° C. and a density of 8.57 g/cm 3 . Alternatively, an alloy using other metal material having a high melting point can be used. The material having a high melting point could not melt in an ordinary high-frequency waves melter. Thus, the weight member 6 is preferably made by means of powder metallurgy.
[0024] Referring to FIG. 4 , when the protrusion 61 of the weight member 6 is received in the recession 51 of the golf club head body 5 , a channel “a” is defined between the recession 51 and the protrusion 61 of the weight member 6 .
[0025] Referring to FIGS. 5 and 6 , a welding material (filling material) 7 is placed into the channel “a” between the recession 51 of the golf club head body 5 and the protrusion 61 of the weight member 6 . The welding material 7 can be the same as that of the golf club head body 5 . Alternatively, the welding material may include the main compositions for forming the golf club head body 5 . In a case that the material of the golf club head body 5 is consisted of carbon 0.07 wt %, silicon 1.0 wt %, manganese 0.7 wt %, phosphor 0.035 wt %, sulfur 0.03 wt %, copper 2.5-3.2 wt %, nickel 3.6-4.6 wt %, and chromium 15.5-17.7 wt %, with iron being the remaining portion, the welding material includes silicon (Si), manganese (Mn), copper (Cu), nickel (Ni), Chromium (Cr), and iron (Fe). Then, a welding procedure such as tungsten inert gas arc welding or other welding process can be performed to allow the welding material 7 to be melted and fills the channel “a”. Since the weight member 6 is made of a material or alloy having a high melting point and since the welding material 7 includes the composing metals the same as those for the golf club head 5 , when fusing the golf club head body 5 and the welding material 7 , the weight member 6 are not melted while the golf club head body 5 melts partially (see the phantom line in FIG. 6 ).
[0026] Referring to FIGS. 7 and 8 , when the molten portions of the golf club head body 5 and the welding material 7 cool and solidify, the welding material 7 and the golf club head body 5 join each other and form an engaging portion “b”. In this case, since the golf club head body 5 and the welding material 7 use the same material, they are not affected by the dilution ratio during welding; namely, they fuse together as a one-piece member. The engaging portion “b” fixes the weight member 6 in the recession 51 of the golf club head body 5 . After welding, the welding material 7 forms a bulge (see the phantom lines) on the surfaces of the golf club head body 5 and the weight member 6 . The bulge can be removed by subsequent finishing (e.g., grinding), providing a flat surface for the golf club head body 5 . Since the weight member 6 (including the protrusion 61 ) does not melt when the welding material 7 fuses, no fusion occurs between the golf club head body 5 and the weight member 6 . Thus, a clear contour of the weight member 6 can still be seen on the golf club head body 5 , as illustrated in FIG. 8 . Further, the engaging portion “b” provides a tight and seamless engaging face between the golf club head body 5 and the weight member 6 , which not only allows the weight member 6 to be tightly engaged in the recession 51 of the golf club head body 5 but also improves the engaging strength between the golf club head body 5 and the weight member 6 .
[0027] FIG. 9 illustrates a modified embodiment of the invention, wherein like reference numerals denote like elements, and only the difference between the modified embodiment and the first embodiment is disclosed to avoid redundancy. In this embodiment, the golf club head includes a golf club head body 5 and a weight member 6 . The golf club head body 5 includes a recession 51 for receiving the weight member 6 . The weight member 6 includes a protrusion 61 integrally formed on a side thereof, wherein the protrusion 61 has a peripheral wall 612 that is inclined upward. When the weight member 6 is placed in the recession 51 , a channel “a” is formed between the recession 51 and the peripheral wall 612 of the protrusion 61 . After welding, the welding material 7 fills the channel “a” and forms a bulge on the surface of the golf club head body 5 . The bulge can be ground off by subsequent surface finishing.
[0028] FIG. 10 illustrates another modified embodiment of the invention, wherein like reference numerals denote like elements. FIG. 11 is a metallographic view illustrating the welding boundary between the welding member and stainless in the embodiment of FIG. 10 . Only the difference between the modified embodiment and the first embodiment is disclosed to avoid redundancy. In this embodiment, the golf club head includes a golf club head body 5 and a weight member 6 . The golf club head body 5 includes a recession 51 for receiving the weight member 6 and a flange 52 that is integrally formed on a peripheral wall portion delimiting an opening of the recession 51 . The weight member 6 includes a protrusion 61 on a side thereof. The flange 52 is of a material the same as that of the golf club head, body 5 and acts as a welding material during the welding procedure. When the weight member 6 is placed in the recession 51 , a channel “a” is formed between a peripheral wall delimiting the recession 51 and the protrusion 61 of the weight member 6 . Further, the golf club head body 5 is preferably made of titanium or of a material using titanium as the main composition (such as 6-4 Ti). Alternatively, the golf club head body 5 can be made of low carbon steel or low alloy steel. Thus, the weight member 6 does not melt when a portion of the golf club head body 5 and the welding material 7 fuse with each other. As a result, no intermetallics are formed, and heat checking of welding is avoided.
[0029] During the welding procedure, the flange 52 melts and forms the welding material 7 that fills the channel “a” (c.f. FIGS. 5 and 6 ). An engaging portion “b” is formed in the channel “a” after solidification and thus fixes the weight member 6 in the recession 51 of the golf club head body 5 . Finally, the surfaces of the golf club head body 5 and the weight member 6 are finished.
[0030] While the principles of this invention have been disclosed in connection with specific embodiments, it should be understood by those skilled in the art that these descriptions are not intended to limit the scope of the invention, and that any modification and variation without departing the spirit of the invention is intended to be covered by the scope of this invention defined only by the appended claims. | A golf club head includes a golf club head body and a weight member. The golf club head member has a recession in which the weight member is mounted. The weight member is securely mounted in the recession of the golf club head body by a welding procedure that uses a welding material. The weight member is made of a material having a melting point higher than that of the golf club head body, avoiding melting of the weight member during the welding procedure. Only a portion of the golf club head body fuses with the welding material while using the welding material for proceeding with the welding procedure for the weight member. | 0 |
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