description stringlengths 2.98k 3.35M | abstract stringlengths 94 10.6k | cpc int64 0 8 |
|---|---|---|
FIELD OF THE INVENTION
[0001] The present invention relates to a new assembly for packaging a high power dimmable LED light source that can be further incorporated into a larger lighting assembly. More specifically, this invention relates to a replaceable lighting head assembly comprised of a high output LED socket torch, a vertically aligned thermal heat sink and an electrical connector.
BACKGROUND OF THE INVENTION
[0002] The present invention relates to a new assembly for packaging a high power dimmable LED light source that can be further incorporated into a larger lighting assembly. More specifically, this invention relates to a replaceable lighting head assembly comprised of a high output LED socket torch, a vertically aligned thermal heat sink and an electrical connector. In itself, this section acts as an electrical inter-connect as well as a thermal heat sink interface suitable for small package integration. The secondary housing unit of this assembly provides a thermal pathway for the heat received from the heat sink to the external environment and acts as a conduit for easy access to the external electrical source. If desired, it can also act as a base for further fixture design functions. This assembly, when integrated into the design of a light housing, provides a means by which to manipulate the light beam of the lighting fixture.
[0003] The evolution of electric lighting began in the late 1800's with the first incandescent bulb—essentially a “glowing wire in a bottle”. In spite of all the improvements, the light bulb that we use today is really not much different than the one invented by Thomas Edison. Inherent problems such as premature failures due to delicate glass structure or filaments, environmental concerns with the mercury, lead or toxic and flammable gases used, and intrinsic inefficiencies are still a concern. Less than 10% of the energy required to burn an incandescent light bulb is converted to light. Even flourescent lighting—today's most efficient light source, converts only 30-40% into light. Although not yet at the levels of flourescent lighting, LED's have the potential to convert up to 90% of the energy they receive into light. Further, light from conventional sources is emitted in all directions, requiring the use of optics to re-direct the beam in the desired direction for effective illumination. Each time the light is redirected, fixture efficiency decreases. The light generated by an LED, however, is directional so its efficiency doesn't have to necessarily match other light sources to be more effective.
[0004] Much of the energy a standard filament light source consumes is converted into hot infrared rays that radiate out within the light beam, thus requiring extra caution when handling the bulb. Because of the heat generated, restrictions to the type and size of the casing around these bulbs must be maintained—all of which reduce the flexibility of the lighting system.
[0005] Since the human eye is naturally drawn to the brightest source of illumination, flexibility is often required in the distribution of the light. General and accent lighting applications utilize this premise to direct the attention of the viewer to particular areas or items. If the first thing a viewer sees is the harsh light source, then their first impression may be negative. The increased size of the bulb casing results in a larger area from which the light emanates, thus requiring greater attention to positioning of the fixture to avoid direct eye contact with the light source itself.
[0006] This flexibility is sometimes related to the light being used in a space that has changing requirements. An example is a retail space where different products are displayed in different ways each week. In this example, spot lights may be desirable for small items and wider beam lights may be appropriate for larger items. The option available today is to use fixtures with integral reflectors that have different beam spreads. One example of this is low-voltage halogen lamps, of which MR-16 is a common type. The MR-16's are available in several light beam spreads from very narrow spot to very wide flood. This strategy causes complications when lamps are changed after burning out. All MR-16's are very similar in appearance, and beam patterns within a space are only maintained after re-lamping if the exact same lamp is used to replace the burned out lamp. This strategy also requires many different lamp types to be kept on hand.
[0007] In outdoor lighting, a fixture should be flexible enough to allow landscape or architectural features to be highlighted as elements change, such as when trees or bushes grow—as well as being discrete enough as to not draw the attention of the eye. If not, the resulting brightness one sees actually makes it harder to observe the surrounding environment as it causes everything else to appear darker. Further, traditional light sources have a relatively short life span, necessitating bulb replacement. This can be both time consuming and dangerous if such fixtures are mounted in an elevated position such as on the soffit of a building or high in a tree.
[0008] Contrast to that, LED light sources offer small, directional pinpoints of light. Their size and directionality support highly controllable lighting systems capable of delivering high flux output at relatively low current levels for long periods of time. But in order to achieve this, thermal issues associated with high output LED lighting systems must be addressed. The challenge is to conduct the heat generated within the LED onto the fixture and then to dissipate that heat, via convection, to the surrounding ambient air. Proper design, therefore, must be given to the sizing of the heat sink to create both a pleasing aesthetic look and functional heat dissipation.
[0009] It would thus be desirable to provide a lighting assembly contained within a small footprint that can be incorporated into various fixture designs. It would be further advantageous if that lighting assembly allows for easy adjustment of the light beam spread in addition to allowing for changes in light intensity through the use of collimating lenses—without having to change the bulb. It would be of further benefit if such assembly were to include a state-of-the-art high output LED for its long life, reduced maintenance cost and reduced cost of ownership—that is replaceable so that when advances in the industry become available the light source can be updated by the consumer.
[0010] High output LED light sources are increasingly becoming the choice of illumination. These dimmable solid-state devices have no filament to break or glass to shatter, no mercury, toxic gases or lead to contaminate the environment and no infrared or UV in the light beam. They are fast approaching the efficiency of fluorescent light sources with new performance standards being achieved regularly.
[0011] High output LED's differ from conventional LED light sources in that they are able to separate their thermal and electrical pathways. This enables them to draw more heat away from the emitter core and thus significantly reduce thermal resistance. As a result, high output LED's can handle significantly more power than conventional LED's. However, the higher electrical input also means they tend to operate at higher operating temperatures which can degrade their performance. Heat that is not effectively dissipated can shift colors, reduce brightness and significantly shorten their life span.
[0012] Moreover, most heat sink configurations currently available are directed to a planar circuit board mount with a heat spreader or a horizontal finned heat sink design. Neither of these arrangements is suitable for small vertical package integration or compact lighting head construction.
ADVANTAGES AND SUMMARY OF THE INVENTION
[0013] The present invention is a lighting assembly that provides for heat dissipation to achieve manufacturing efficiencies and product consistencies. The heat dissipating system removes heat from the LED that would otherwise shorten its life and/or reduce its brightness. Further, the present invention provides a lighting assembly wherein the light can be directed onto a single element or expanded to cover a wide area by its adjustable nature when called upon. The present invention further allows for easy replacement of the light source as called for when changes in light output, light pattern, or light color is desired—or as new performance standards are achieved.
[0014] The present invention further provides a lighting head assembly that contains a high output dimmable LED socket torch attached to a vertically aligned thermal heat sink interface with a friction lock electrical interconnect. This assembly can be incorporated directly into the design of the fixture housing or inserted into the secondary housing unit to provide a thermal pathway for the heat generated by the LED and to provide for easy access to the external electrical source. This second component also serves as a foundation for additional design features—such as a sliding cylinder that adds further flexibility to the illumination system by allowing the expansion or contraction of the light beam or changing the intensity of the light beam through use of a collimating lens.
[0015] The present invention further provides for simplified connection of the light assembly to the external power source and controller. Several controller options are readily available within the industry that allow for use of high power LED's in a variety of operating modes.
[0016] Further details, objects and advantages of the present invention will be come apparent through the following descriptions, and will be included and incorporated herein.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a perspective view of one embodiment of the lighting head assembly 100 of the present invention.
[0018] FIG. 2 is a perspective view of one embodiment of the high output LED socket torch 200 , vertically aligned thermal heat sink 13 and electrical connector assembly 15 and 19 .
[0019] FIG. 3 and 4 are exploded side perspectives of an embodiment of the high output LED socket torch 200 , vertically aligned thermal heat sink 13 and electrical connector assembly 15 and 19 of the present invention 100 .
[0020] FIG. 5 is an exploded perspective of one embodiment of the lighting head assembly 100 with sliding cylinder 30 removed.
[0021] FIG. 6 is a cross-sectional view of the lighting head assembly 100 with sliding cylinder 30 in place.
[0022] FIG. 7 is a sectional view of one embodiment of the LED emitter package 700 ;
[0023] FIG. 8, 9 and 10 show alternative embodiments of LED emitter packages 700 a, 700 b and 700 c.
[0024] FIG. 11 is an exploded perspective of the high output LED socket torch 200 b vertically aligned thermal heat sink 13 b and electrical connector assembly 15 and 19 showing one type of coupler embodiment for alternative LED emitter packages.
[0025] FIG. 12 is an exploded perspective of the lighting head assembly 100 b using an alternative LED socket torch 200 b and coupler 10 b with sliding cylinder 30 removed.
[0026] FIG. 13, 14 and 15 are side views of a complete lighting head assembly 100 with a tubular supplementary fixture design element 40 attached to the sliding cylinder 30 showing the contraction and expansion of the light beam 400 .
[0027] FIG. 16 is a side view of the complete lighting head assembly 100 and one embodiment with a tubular supplementary fixture design element 40 attached to the sliding cylinder 30 and a collimating lens 42 inserted to manipulate the size and intensity of the light beam 400 .
[0028] FIG. 17 and 18 shows an example of an alternative style element 40 d, that can be attached directly to the sliding cylinder 30 or supplementary fixture design element 40 and the subsequent manipulation of the light beam 400 .
[0029] FIG. 19A, 19B , 19 C and 19 D show alternative embodiments of lighting head assembly 100 each with a supplementary fixture design element 40 b with different shaped slit openings attached to the sliding cylinder 30 .
[0030] FIG. 20A and 20B show one embodiment of method of use of the present invention 100 on hanging object(s).
[0031] FIG. 21A and 21B show alternative embodiment of lighting head assembly 100 each with a supplementary fixture design element 40 c that attaches to the inside of the sliding cylinder 30 and also serves to lock the friction ring 31 in place.
[0032] FIG. 22 shows one embodiment of another method of use of the present invention 100 on walkways.
DETAILED DESCRIPTION OF EMBODIMENTS
[0033] The description that follows is presented to enable one skilled in the art to make and use the present invention, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be apparent to those skilled in the art, and the general principals discussed below may be applied to other embodiments and applications without departing from the scope and spirit of the invention. Therefore, the invention is not intended to be limited to the embodiments disclosed, but the invention is to be given the largest possible scope which is consistent with the principals and features described herein.
[0034] It will be understood that in the event parts of different embodiments have similar functions or uses, they may have been given similar or identical reference numerals and descriptions. It will be understood that such duplication of reference numerals is intended solely for efficiency and ease of understanding the present invention, and are not to be construed as limiting in any way, or as implying that the various embodiments themselves are identical.
[0035] The lighting head assembly 100 includes a high output LED socket torch 200 , a vertically aligned thermal heat sink 13 , an electrical connector assembly 15 and 19 and coupler 10 that fastens the lighting head assembly 100 to the secondary housing unit 20 . A sliding cylinder 30 attaches to the secondary housing unit 20 to provide a base to add various fixture design elements 40 , 40 b, 40 c and 40 d.
[0036] As will hereinafter be more fully described, the present invention illustrates a lighting head assembly 100 that may be further incorporated into other lighting devices. In general, the present invention 100 is comprised of a replaceable high output LED socket torch 200 that provides essential heat transfer and electrical connectivity to a secondary housing unit 20 that further provides for manipulation of the light beam 400 . The present invention 100 therefore provides a convenient and economical assembly that has not been previously available in the prior art.
[0037] The present invention 100 is specifically configured to incorporate high output LED lamps 700 into a socket torch package that can then be used in a lighting fixture. The high output LED lamp 700 as shown here is a Luxeon emitter. However, it should be understood that the mounting arrangement described is equally applicable to other high output LED lamps 700 as shown in FIGS. 8, 9 and 10 .
[0038] As shown in FIG. 7 , the LED 700 has a mounting base 3 and a plastic lens 1 that encloses the LED emitter chip 2 . The LED 700 also includes two contact leads 5 that extend from opposite sides of the mounting base 3 to which power is connected to energize the emitter chip 2 . Since the emitter chip 2 in this type of high output LED lamp 700 has a greater surface area than conventional LED's, a great deal more heat is generated along with the increased light output. For this reason, a heat transfer slug 4 for the specific purpose of engagement with a supplementary heat sink 13 is provided. Within the LED 700 , the heat transfer slug 4 extends from the base 3 of the emitter chip 2 , to the bottom inside surface of the mounting base 3 , thus providing an thermal pathway to transfer the heat generated by the emitter chip 2 .
[0039] In FIG. 3 , the bottom portion of the LED base 3 mounts inside the upper portion of the emitter ring 11 , comprised of a thin non-conductive material capable of handling the anticipated temperature range within that area. The remaining portion of the emitter ring 11 then mounts over the heat transfer rod 12 , which is made of a thermally conductive solid cylindrical material. The end surface area of the rod 12 is sufficiently polished such that good thermal contact is made with the heat transfer slug 4 . In one embodiment, the heat transfer rod 12 is made of aluminum, however, other thermally conductive materials can also be used.
[0040] As shown in FIG. 4 , the contact leads 5 of the LED 700 are then pressed down over the non-conductive emitter ring 11 surface. The heat transfer rod 12 , with LED assembly 700 attached, is then inserted into the tubular vertically aligned thermal heat sink 13 up to the bottom rim of the emitter ring 11 .
[0041] In one embodiment, the vertically aligned thermal heat sink 13 is cylindrically shaped and extending in a direction to surround the heat transfer rod 12 . The outside diameter of the heat transfer rod 12 is slightly less than the inside diameter of the vertically aligned thermal heat sink 13 resulting in an intimate fit between the two thermally conductive materials such that sufficient contact is made to facilitate the transfer of heat from the heat transfer rod 12 to the vertically aligned heat sink 13 . In one embodiment, the vertically aligned thermal heat sink 13 is made of aluminum. However, other thermally conductive materials or compounds for improving thermal transfer can also be used.
[0042] To further facilitate the transfer of heat and to aid in the strength of the connections, a thermally conductive adhesive or thermal compound may be applied at all heat transfer connections.
[0043] A groove 14 is present on opposite sides of one end of the vertically aligned heat sink 13 . These grooves extend slightly past the bottom rim of the inserted heat transfer rod 12 and align with the two contact leads 5 that extend from the sides of the LED 700 .
[0044] The electrical wires 16 of the electrical connector assembly 15 and 19 run inside the vertically aligned heat sink 13 , then feed through the cavity created by each of these grooves 14 . The wire ends are then soldered to the contact leads 5 of the LED 700 over the area of the non-conductive material of the emitter ring 11 such that no electrical contact is made with the rest of the assembly.
[0045] The other end of the electrical wires 16 are connected via soldering to the back end of the pin headers 15 of the vertical friction lock 19 . This electrical connector assembly 15 and 19 is then encased within the 14-22 AWG nylon closed end connector 17 that has the tip of its stem opened to allow the electrical wires 16 to pass. In one embodiment, the 14-22 AWG nylon closed end connector 17 serves to center and contains the vertical friction lock for mating with the crimp terminal housing 21 . It should be understood that this function can be achieved using various alternatives materials. An anti-oxidant grease can be applied to each of the soldered connections and then covered with a non-conductive heat shrink material or similar electrically isolating material.
[0046] As shown in FIGS. 4, 5 & 6 , electrical connector assembly 15 and 19 and 14-22 AWG nylon closed end connector 17 are then placed inside the coupler 10 so that the upper rim of the coupler 10 extends up to the bottom portion of the LED base 3 , covering the emitter ring 11 , the soldered connections of the two contact leads 5 , the heat shrink material and the grooves 14 of the vertically aligned thermal heat sink 13 . The upper half of the coupler 10 is then filled with a non-conductive potting epoxy 18 to encapsulate the area. The bottom half of the coupler 10 is left un-potted to allow coupling to the secondary housing unit 20 .
[0047] As shown in FIG. 5 and 6 , a sliding cylinder ring stop 27 is attached to the secondary housing unit 20 just beyond the reach of the bottom rim of the coupler 10 to prevent its dislodging by the sliding cylinder 30 when the lighting head assembly 100 is inserted. In one embodiment, the coupler 10 is of an electrically conductive metal material requiring separation from the soldered connections. Alternatively, if the coupler 10 is not intended to aid in the dissipation of heat in the overall fixture design, the coupler 10 can be made of a non-electrically conductive material. In which case the use of the electrically isolating material would not be necessary.
[0048] It will be understood by those skilled in the art that any type of flared or shaped glare shield can be utilized in the present invention by coupling directly to the slidable cylinder 30 in order to focus, shape or direct the light emitted therefrom. Thus, an auxiliary flared or shaped glare shield can be moved backward and forward, along the secondary housing unit 20 , and over and around the LED socket torch portion 200 of the lighting head assembly of the present invention. The present invention provides a sliding cylinder 30 disposed around or on top of the secondary housing unit portion 20 in which any LED socket torch package or bulb 200 of the present invention can be utilized. Thus, depending upon the shape of an adapter glare shield fitting attached to the sliding cylinder 30 , the combination of sliding cylinder 30 and flared or shaped glare shield or beam shaper or other lens fitting can slide down over the LED light torch socket 200 in order to focus, shape, broaden or narrow the beam of light emitted therefrom.
[0049] As shown in FIG. 8, 9 and 10 , 11 and 12 , larger LED lamps 700 a, 700 b and 700 c can be accommodated within the lighting head assembly 100 by scaling the components including LED base 3 b, coupler 10 b, heat transfer rod 12 b, thermal heat sink 13 b, secondary housing unit 20 b, nylon closed end connector 25 b and sliding cylinder stop 27 b to fit the size of the LED lamps 700 a, 700 b and 700 c.
[0050] In one embodiment, a single LED may comprise a plurality of emitter chips. Often red diode(s) are placed with green diode(s) and blue diode(s). In other cases, other combinations of colors can be used. As shown in FIG. 8 , the LED lamp 700 a has a single emitter chip 2 ′ within each lens 1 ′. In the LED lamp 700 b shown in FIG. 9 , a single lens 1 ″ houses multiple emitter chips 2 ″.
[0051] The replaceable high output LED socket torch 200 is inserted into the secondary housing unit 20 to provide thermal transfer of the heat sink 13 to the external environment or can be inserted into a thermal design embodied within a fixture that is equally effective.
[0052] In one embodiment, the vertically aligned thermal heat sink 13 is cylindrically shaped. The outside diameter is slightly less than the inside diameter of the secondary housing unit 20 resulting in an intimate fit between the two thermally conductive materials when inserted. Therefore, when inserted, heat from the vertically aligned thermal heat sink 13 is conducted to the secondary housing unit 20 and then released to the environment through convection. A heat sink compound can be applied to further aid in the heat transfer. Further, if a permanent connection is desired, then a heat sink adhesive can be applied.
[0053] It should be understood that the mounting arrangement described is equally applicable to various dimensions and shapes of the mating units as long as the fit allows for the thermal transfer of heat.
[0054] The replaceable high output LED socket torch 200 is electrically connected to the secondary housing unit 20 through connection of the electrical connector assembly 15 and 19 and the crimp terminal housing 21 , as best shown in FIG. 5 .
[0055] Another embodiment shown in FIGS. 5 & 6 illustrates the lower portion of the crimp terminal housing 21 encased in a 14 - 22 AWG or similar nylon or other material closed end connector 23 that has the tip of its stem opened to allow the electrical wires 26 to pass. In one embodiment, 14-22 AWG nylon closed end connector 23 serves to align the crimp terminal housing 21 within the secondary housing unit 20 and provides a means to connect the spring 24 to the crimp terminal housing 21 .
[0056] Also as shown in FIG. 5 , the spring 24 provides insertion resistance necessary for mating of the pin headers 15 of the vertical friction lock 19 to the wire crimp terminals 22 found within the crimp terminal housing, and aids in the positioning of the crimp terminal housing 21 for accepting the vertical friction lock 19 of the electrical connector assembly 15 and 19 At the base of the spring 24 is a 12-10 AWG nylon closed end connector 25 that has the tip of its stem opened to allow the electrical wires 26 to pass. The 12-10 AWG nylon closed end connector 25 serves to center and contain the spring 24 at its proper depth although other means could achieve the same desired effect.
[0057] Electrical wire leads 26 extending beyond the secondary housing unit 20 provide connection of the light assembly 100 to a variety of external power sources and controllers. Several options are readily available within the industry that allow for use of high output LED's in a variety of operating modes and wiring configurations. Alternate assemblies could use additional wiring to connect multiple LED emitter chips that are packaged within a single die 700 a or within a single cavity 700 b. Therefore, combinations of 2 or more wires might be used to individually control each emitter chip within the LED die.
[0058] As shown in FIG. 6, 13 , 14 , 15 and 16 , the cylindrical shape of the secondary housing unit 20 allows for a cylindrically shaped coupler to be manipulated up or down its length. In one embodiment a sliding cylinder 30 is added to the secondary housing unit 20 to provide a means by which to manipulate the light beam 400 and/or aid in the transfer of heat to the environment.
[0059] One opening of the sliding cylinder 30 aligns the shaft of the secondary housing unit 20 to fit within a friction ring 31 used to avoid metal to metal contact when the secondary housing unit 20 is manipulated within the sliding cylinder 30 . In one embodiment, the friction ring 31 is comprised of High Density Polyethylene (HDPE) tubing for its excellent chemical, fatigue, wear resistance and heat tolerance. Other materials could serve the same purpose of providing sufficient frictional grip to prevent the secondary housing unit 20 from slipping once it is positioned, while still allowing for shaft movement when desired.
[0060] The friction ring 31 is held in place on one end by the narrowing cavity of the sliding cylinder 30 , and on the other by the thermally conductive friction ring lock 32 . The inside diameter of the friction ring lock 32 is slightly greater than the outside diameter of the secondary housing unit 20 and the outside diameter of the friction ring lock 32 is slightly smaller than the inside diameter of the sliding cylinder 30 resulting in an intimate fit between the thermally conductive materials. Therefore, the friction ring lock 32 serves to transfer heat from the secondary housing unit 20 to the sliding cylinder 30 . The friction ring 31 can also be locked in place by use of a supplementary fixture design element 40 c that attaches to the inside of the sliding cylinder 30 .
[0061] It should be understood that the mounting arrangement described is equally applicable to sliding couplers of differing designs, shapes and sizes.
[0062] In one embodiment, as shown in FIGS. 13-16 , the sliding cylinder 30 serves as a base on to which additional design elements can be attached. By adding a removable tubular glare shield 40 over or within the flared opening of the sliding cylinder 30 and sliding it up and down the shaft of the secondary housing unit 20 , the LED 700 can be manipulated to the forefront or backmost region of the glare shield 40 to produce a light beam 400 that alters from spot as shown in FIG. 13 to flood as shown in FIG. 15 . Alternatively, the sliding cylinder 30 itself can be shaped to achieve the above-mentioned functions.
[0063] As best shown in FIG. 16 , by inserting one of the many collimating lenses 42 and their supplementary lens holders 41 readily available in the industry within the removable glare shield 40 , the shape and intensity of the light beam 400 can be further manipulated within set patterns.
[0064] As shown in FIGS. 17 & 18 , additional design elements 40 d can be added to the secondary housing unit 20 by coupling either over or inside the sliding cylinder 30 or tubular glare shield 40 , or by use of different size tubing, couplers and/or cylinders to produce alternative fixture designs and functions.
[0065] As best shown in FIG. 19A, 19B , 19 C and 19 D, the use of oval, rectangular or other shapes of design elements attached to the removable glare shield 40 b can be used to achieve the corresponding desired light beam 400 pattern. As shown in FIG. 20A and 20B , in this manner, items on a horizontal or vertical plane can be “framed” with light beam 400 from the adjustable fixture.
[0066] FIGS. 21A and 21B show an alternative method of controlling shape of light beam 400 by attaching supplementary fixture design element 40 c within the sliding cylinder 30 . The further away the LED unit 700 is from the opening of supplementary fixture design element 40 c, the narrower the light beam 400 , and vice versa. In this manner, user(s) can easily change the effect of light beam 400 from spot light to flood light effects.
[0067] FIG. 22 shows one embodiment of another method of use of the present invention 100 on a walkway. By altering the light beam 400 effects, user(s) can generate a desirable lighting ambiance for both practical and aesthetic purposes.
[0068] Modifications and alterations to the above described embodiments will become manifest to those skilled in the art upon reading and understanding the preceding detailed description. It is intended that the various modifications are to be within the scope of the present invention insofar as they come within the scope of the appended claims or the equivalents thereof.
[0069] In order to better utilize the advantageous features high output LED's offer, proper thermal design is imperative. The objective is to dissipate the electrical energy the LED receives that is not converted into light, to the surrounding ambient air. To achieve this, the amount of energy the final fixture design will need to dissipate should be calculated. The following shows a general outline for calculating thermal heat sink requirement of a luminaire or other LED socket touch package of the present invention 100 operating under various conditions.
[0070] Step 1) Take the manufacturer specified maximum allowable junction temperature of the LED emitter. Subtract the maximum ambient air temperature the fixture is likely to encounter and Divide by the Power Dissipated (P d ) of the LED as measured in Watts [Forward current (I f )*Forward voltage (V f )] Or:
R⊖ junction-ambient =( T junction-ambient )/ Pd
[0071] Step 2) Subtract the manufacturer specified junction thermal resistance of the LED to emitter slug 4(R⊖ j-b ) Or:
(R⊖ junction-ambient )−(R⊖ j-b )
[0072] Which will give you the amount of energy—as measured in ° Celsius (ΔT)/Watts (P d ), which needs to be dissipated within the exposed surface area of the heat sink of the fixture.
EXAMPLE 1
[0073] A Blue Luxeon III emitter with an average V f of 3.7 Volts, driven at 700 mA would require a heat sink that can dissipate 2.59 Watts of energy (making no adjustments for the energy that is converted to light). Assuming a maximum ambient air temperature of 40° C. (104° F.) that the designer feels the fixture is likely to encounter, and the maximum junction temperature the emitter can handle of 135° C. (varies with model of LED), and the manufacturer's specified thermal resistance of the LED emitter chip to slug of 13° C./W (as defined by the manufacturer), then
( R⊖ junction-ambient )−( Rβ j-b )=23.68° C./W
[0074] A luminaire or other LED socket torch package of the present invention operating under these conditions would need approximately 2 to 6 sq. inches of heat sink surface area depending on the material used and its orientation.
EXAMPLE 2
[0075] If you wanted to increase the light output of this same LED socket torch, then you could increase the current at which the LED is driven. By increasing the current from 0.700 mA to 1.0 MA, the heat sink would have to now dissipate 3.7 Watts of energy. The necessary surface area would change to 12.68° C./W which equates to anywhere from 9 to 12 sq. inches of heat sink surface area—depending on the materials used in the construction of the luminaire and its orientation.
EXAMPLE 3
[0076] If you changed the maximum temperature you want the LED's emitter junction to reach to 90° C. under the same expected conditions in order to increase the life of the LED, then driven at 1.0 mA you would have to increase the surface area of the heat sink to approximately 20 sq. inches or more.
[0077] Various strategies are available to keep the LED emitter chip 2 below its rated operating junction temperature which include: 1] Control the maximum operating ambient air temperature to be encountered by the luminaire 2] Control the orientation of the heat sink portion of the luminaire (vertical versus horizontal, etc.), 3] Manage the Power Dissipated by the LED by limiting the current applied to the LED and/or using only LED's within an allowable forward voltage range, 4] Select an appropriate heat sink material with sufficient thermal conductivity, 5] Use an LED with a higher operating temperature rating, 6] Provide sufficient heat sink surface area within the luminaire.
[0078] Of these, providing sufficient heat sink surface area and selecting appropriate heat sink materials fall within the fixture design process. For example, referring to FIG. 13 if the secondary housing unit 20 has an outside diameter of ½ inch, then the Surface Area=2*Π* radius*height or 1.57 sq. inches of Surface Area per inch of length. A sliding cylinder 30 that tapers from 0.625 to 0.875 inches and is 1 ½ inches long would have a Surface Area of 3.73 sq. inches and a glare shield 40 that has an outside diameter of 1 inch would have 3.14 sq. inches of Surface Area per inch of length.
[0079] Various combinations can be configured to meet surface area requirements. A luminaire requiring 10 sq. inches of heat sink surface area could be met with a secondary housing unit ( 20 ) 6 ½ inches in length or a combination of 4 ½ inches of secondary housing unit used in conjunction with the sliding cylinder 30 . Using materials with better thermal conductivity (e.g. copper vs. stainless steel) can greatly effect the amount of heat sink surface area required.
[0080] Further, as temperature tolerances of next-generation high output LED's increase, heat sink requirements will be reduced—opening new design possibilities with higher current operation for increased light output. With implementation of the present invention, lighting designers will be able to incorporate a replaceable lighting assembly contained within a small footprint into various fixture designs that allow for easy adjustment of the light beam spread, pattern, color and intensity.
[0081] The present invention is a lighting head assembly having: a directional, high output, replaceable LED socket torch; a vertically aligned thermal heat sink shaft for communicating thermal energy away from the LED socket torch in a direction opposite the orientation of directionality of the LED; a cylindrical housing having a proximal end and a distal end, the proximal end for receiving and maintaining the socket torch in intimate contact with the heat sink shaft; and an electrical connection disposed within the housing for coupling the LED socket torch to an external electrical source adjacent the distal end of the cylindrical housing.
[0082] In an embodiment, the replaceable LED socket torch comprises: an LED emitter; a base portion formed of a heat-resistant material, the LED emitter coupled directly to the base portion; an essentially transparent protective covering over the LED emitter connected to the base portion; an intermediate heat sink, the heat sink in intimate contact with the base portion for providing efficient thermal conduction away from the LED emitter; a distal end having a socket connector mounting portion, thus providing a secure, releasable and reconnectable mechanical connection between the replaceable LED socket torch and the lighting head assembly; and at least two electrical leads connected to the LED emitter extending beyond the base portion, at least one of the at least two electrical leads electrically isolated from the heat sink, the at least 2 electrical leads terminating at the distal end, thus providing at least two contacts for communication of electrical energy to the lighting head assembly.
[0083] In an embodiment, of the lighting head assembly, a slidable focusing element is coupled to the housing and light torch assembly for focusing the light created by the LED emitter as desired.
[0084] In an embodiment, of the lighting head assembly, a mounting bracket is coupled to the cylindrical housing for mounting the lighting head assembly as desired
[0085] The present invention is a directional, high output, replaceable LED socket torch for use in lighting applications, the LED socket torch comprising: an LED emitter having an electrically isolated base and plurality of electrical inputs; a heat sink shaft in intimate contact with the base of the LED emitter; an emitter ring for coupling the heat sink shaft to the LED emitter; a housing having a proximal end and a distal end, the LED emitter seated within the housing at the proximal end such that the heat sink shaft extends distally there within; an end socket connector seated within the distal end of the housing; and electrical contacts extending through the housing from the plurality of electrical inputs of the LED emitter to the end connector, whereby upon coupling the LED socket torch to a source of electrical energy, light is produced by the LED emitter and heat formed by the LED emitter is transferred through the base to the heat sink shaft for dissipation through the end socket connector.
[0086] In an embodiment of the LED socket torch, the electrical contacts further comprise wire prongs extending distally from the distal end of the housing.
[0087] The present invention is a lighting head assembly for providing directional, high-output illumination, the lighting head assembly having: a high output, replaceable LED socket torch comprising:
[0088] an LED emitter having an electrically isolated base and plurality of electrical inputs which provides high-output beam of illumination; a vertically aligned thermal heat sink shaft in intimate contact with the base of the LED emitter for dissipating heat generated by the LED emitter; an emitter ring for maintaining the heat sink shaft in intimate contact with the LED emitter; a socket torch housing having a proximal end and a distal end, the LED emitter located adjacent the proximal end such that the heat sink shaft extends axially through at least a portion of the socket torch housing at the proximal end; an end socket quick connect-type connector located at the distal end of the socket torch housing; and electrical contacts extending through the socket torch housing from the plurality of electrical inputs of the LED emitter to the end socket connector, whereby upon coupling the LED socket torch to a source of electrical energy, light is produced by the LED emitter and heat formed by the LED emitter is transferred through the electrically isolated base to the heat sink shaft for dissipation of heat therethrough; a tubular base portion housing having a proximal end and a distal end, the proximal end for receiving and maintaining the replaceable LED socket torch; a slidable tubular coupling having a proximal end and a distal end, the distal end having a predetermined internal diameter such that the distal end is disposed in intimate contact around the tubular base portion, the slidable coupling further having a proximal end, the slidable coupling having a predetermined length such that when the slidable coupling is positioned adjacent the proximal end of the tubular base portion housing the proximal end of the slidable tubular coupling shields the glare of the beam of LED illumination and permits shaping of the beam of illumination as desired; and an electrical connection disposed within the housing for coupling the LED socket torch to an external electrical source adjacent the distal end of the cylindrical housing.
[0089] In an embodiment of the present invention, the slidable tubular coupling is adapted for coupling a glare shield portion thereto.
[0090] In an embodiment of the present invention, a glare shield portion is removably coupled to the slidable tubular coupling for shaping and directing the beam of illumination as desired.
[0091] In an embodiment of the present invention, a mechanical stop is adjacent the proximal end of the tubular base portion for preventing the slidable coupling from moving past the proximal end of the tubular base portion.
[0092] In an embodiment of the present invention, the mechanical stop comprises a cylindrical ring bonded to the proximal end of the tubular base portion.
[0093] In an embodiment of the present invention, the internal diameter of the proximal end of the slidable coupling is greater than the outside diameter of the cylindrical ring, such that the proximal end of the slidable coupling is unimpeded by the cylindrical ring mechanical stop.
[0094] In an embodiment of the present invention, the proximal end of the slidable coupling has a predetermined internal diameter greater than the predetermined internal diameter of the distal end thereof.
[0095] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Although any methods and materials similar or equivalent to those described can be used in the practice or testing of the present invention, methods and materials are now described. All publications and patent documents referenced in the present invention are incorporated herein by reference.
[0096] While the principles of the invention have been made clear in illustrative embodiments, there will be immediately obvious to those skilled in the art many modifications of structure, arrangement, proportions, the elements, materials, and components used in the practice of the invention, and otherwise, which are particularly adapted to specific environments and operative requirements without departing from those principles. The appended claims are intended to cover and embrace any and all such modifications, with the limits only of the true purview, spirit and scope of the invention. | A replaceable lighting head assembly comprised of a high output LED (Light Emitting Diode) socket torch package, vertically aligned thermal heat sink, and electrical connector coupled with a secondary housing unit that conducts heat received from the heat sink to the external environment and acts as a conduit for the external electrical source. This second component also serves as a building block for further fixture design. In this manner, state-of-the-art LED's can be used to provide light within a small, durable package which in turn, provides lighting designers with the opportunity to explore new fixture designs and to improve the quality, energy-efficiency, safety and longevity of existing products. | 5 |
FIELD OF THE INVENTION
This invention relates generally to wallform systems for use in fabricating concrete walls, and particularly to apparatus for securing a worker's safety belt hook typically to modularized prefabricated wallform equipment.
BRIEF DESCRIPTION OF THE PRIOR ART
Forms for fabricating a poured-concrete wall generally comprise a pair of opposed panels rigidly buttressed by a support structure, which includes preferably-horizontal studs or joists, reinforced by walers which are arranged perpendicularly thereto. The opposed panels function as a mold for the wet concrete as it is poured and are removed after it has set. Originally, and even today (usually on smaller jobs), wallforms consisted of plywood panels with a wooden support structure, custom-built at the site and then demolished after the concrete had been poured.
This inefficient and costly process has largely been superseded by reusable, mobile wallform systems, including the prefabricated Mod-U-Form System® manufactured by the assignee of the present invention. This system comprises modular panels, in standard sizes, consisting of a panel of a facing material such as plywood braced with a steel frame. The panels can either be assembled at the construction site into a form of the desired shape, or assembled at a remote location and moved to the site as a gang. Such gangs can be reused in successive concrete pours on a given project, leading to considerable economies of labor and materials.
Wallform panels are frequently assembled into gangs of considerable size.The forms can also "climb" as a wall is formed with successive pours, each at a greater vertical height. When it becomes necessary for workmen to work at a high level, there is a need for a means for securing safety belts to the wallforms to guard against injury.
It is desirable that such a device be simple in design and make use of the preexisting hardware and other features of the Mod-U-Form type system, for reasons of economy, and that it be simple in use, for reasons of safety.
The wallform panels of this type system possess features that are useful for this purpose. First, they are designed to be held together edge-to-edge by standard wedge-bolts inserted through matching slots in the outer portions of the frames of adjacent panels. After assembly, a certain number of vacant pairs of wedge-bolt slots that have not been used for connecting adjacent panels are available for attaching other hardware.
Also, when opposed gangs of panels are placed in position to receive poured concrete, tie rods are secured between the opposed gangs in order to hold them rigidly in position and resist the pressure of the wet concrete. The ends of tie rods are inserted into voids or holes formed between the abutting side rails of adjacent ganged forms. These holes are formed by a series of scarfs or routs in outwardly facing lips of the siderails of the individual frames at the rearmost and outermost edge, which align with corresponding scarfs on adjacent frames.
Corresponding wedge bolt slots aligning with the scarfs are used to secure the looped or slotted ends of the tie rods. Again, after assembly of wallform gangs and their connection with tie rods, a certain number of vacant tie rod holes and corresponding wedge-bolt slots will be available for securing other hardware.
Examples of earlier designs for securing a worker's safety belt to such wedge-bolt slots and tie rod holes include U.S. Pat. Nos. 4,210,306 and 4,228,986 (which are incorporated herein by reference). The former discloses a "safety key" shaped generally like a conventional key and having a shank width approximating that of a wedge bolt. This key can be inserted into either a vacant narrow tie-rod opening or a vacant pair of aligned wedge-bolt slots, and secured therein with wedge-bolts (in the same manner that a tie rod would be secured). The safety belt is hooked to a hole in the "head" portion of the "key."
U.S. Pat. No. 4,228,986 discloses another such apparatus modified to overcome torque problems inherent in the earlier design. This modified design has a flat portion adapted to be positioned along one side of and parallel to a pair of adjacent siderails; with overhanging ears intended to counteract the torque problem. A slot in the flat portion is aligned with a pair of corresponding wedge-bolt slots, and standard wedge-bolts are used to secure the apparatus.
These two devices have several disadvantages. In the first, when the key is subjected to a substantial downward pull, the lower split edge forming the tie-rod hole and the shank portion of the key resting on that edge are subjected to a severe stress (the key not being free to move below the horizontal). Additionally, competitive modular wallform systems have tie-rod holes of different sizes; so that if the safety key is inserted into a hole which is larger than one for which it was designed, then the key may well be subjected to a torsional stress beyond its designed capacity.
U.S. Pat. No. 4,228,986 attempts to remedy some of these defects, but also has major disadvantages. Extending beyond the siderail from the above-mentioned flat portion of the device is a projecting portion containing a hole to which the safety belt is to be attached. Upper and lower ear portions extending from the projecting portion are intended to rest closely on the edge of the siderail and resist any rotation and torsional stress on the flat portion or on the securing wedge-bolt.
The disadvantages of the latter device lie, first, in manufacture, and second, in use. Tolerances must be adhered to very closely, if the ears are to rest properly on the edge of the siderail, so that manufacture is difficult and the devices can be used with only one type of frame. In addition, bending operations and, in one embodiment, welding operations are required, making manufacture expensive. Finally, the odd shape of the device complicates storage.
Accordingly, the object of the present invention is to provide a simple attachment for holding a safety belt onto a wallform assembly that is inexpensive to manufacture and is both easy and safe to use.
A further object is to provide a safety attachment for a wallform assembly system that does not exert excessive torsional stresses on either the attachment itself or on cooperating wedge-bolts when it is subjected to a substantial downward force, and thus be safe to use on most known modular wallforms that it fits.
The preferred embodiment of the present invention achieves these objects by providing a generally elliptical steel plate which is to be inserted into a tie-rod hole. Formed in the plate are two circular holes, one of which is used to secure the attachment in the tie-rod hole by means of a wedge-bolt inserted through the corresponding wedge-bolt slots. The other hole is used for attaching the hook on a worker's safety belt.
The attachment plate is preferably designed to be slightly thinner and substantially narrower than the tie-rod holes in which it is used. Thus it is free to rotate in a vertical plane about the typically horizontal wedge-bolt by which it is secured, thereby reducing the problem of extreme stress on the lower edge of the tie-rod hole. Also, because the holes are circular, such rotation avoids torsional stress relative to the securing wedge-bolt, reducing the risk of failure of the parts.
In this specification and the accompanying drawings, I have shown and described a preferred embodiment of my invention and have suggested various alternatives and modifications thereof, but it is to be understood that these are not intended to be exhaustive and that many other changes and modifications can be made within the scope of the invention. These suggestions herein are selected and included only for purposes of illustration in order that others skilled in the art will more fully understand the invention and the principles thereof and will thus be enabled to modify it and embody it in a variety of forms, each as may be best suited to the conditions of a particular use.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view of one face of a preferred embodiment of the safety attachment according to the present invention.
FIG. 2 is an isometric view of a portion of a wallform system with the safety attachment of FIG. 1 mounted thereon.
FIG. 3 is an isometric view showing an alternative use of the safety attachment.
DETAILED DESCRIPTION
In the embodiment shown in FIG. 1, the safety attachment is a generally elliptical flat metal plate 10. For simplicity in design and manufacture, it is advantageously constructed with a rectangular central area 12, a semicircular first end area 14, and a semicircular second end area 16. The diameters of areas 14 and 16 are seen to be equal to the width of area 12. In FIG. 1, areas 12, 14, and 16 are separated by dotted lines, but as manufactured, the attachment will be typically formed as an integral unit in one operation.
Symmetrically located along the longitudinal axis of plate 10 are a first hole 18 and a second hole 20, which are preferably circular and of equal size. The centers of holes 18 and 20 are located within end areas 14 and 16, respectively, and said holes are of such location and size that they will accomodate either a standard wedge-bolt or the hook of a standard safety belt.
FIG. 2 shows a detail of a first wallform panel 22 and a second wallform panel 24 in normal cooperating relationship with each other and with safety attachment 10. Each of said wallform panels comprises a facing 26, preferably made of plywood, which, together with the facing on the other such panel, composes the surface against which concrete is poured and hardened into a desired shape. A marginal supporting frame borders and contains said facing, aiding in the handling of said panels and providing means for linking panels together and attaching additional hardware. A detail of a portion of said frame, a vertical siderail 28, is shown in FIG. 2.
Each of said siderails is seen to have formed therein at least one wedge-bolt slot 30 and an outer longitudinal rib 32. In rib 32 is formed at least one scarf 34, which is a notch routed out of said rib and which opens outwardly, away from said facing. Scarfs 34 and wedge-bolt slots 30 of adjacent siderails are disposed in registration with one another, and said scarfs cooperate to define a void 36, which is normally used to receive the end of a tie-rod (not shown).
Also shown in FIG. 2 is a T-shaped horizontal bracket member 38, which serves as additional bracing for facing 26. Formed in member 38 are a cutout 40 and a slot 42. The portion 44 of member 38 adjacent to slot 42 on the side away from facing 26 has been bent downward, away from wedge-bolt slot 30, and welded to siderail 28.
Panels 22 and 24 are shown to be fastened together by a first wedge-bolt 46 secured in place by a second wedge-bolt 48. Wedge-bolt 46 is inserted into the corresponding wedge-bolt slots 30 of the two panels, in a direction from panel 24 to panel 22, and its head 49 (visible in dotted outline in FIG. 2) is placed directly against the inner surface of the siderail 28 of panel 24. Second wedge-bolt 48 is then inserted in a slot 50 in the shank of wedge-bolt 46 with its head 52 and point 54 disposed firmly against the inner surface of siderail 28 of panel 22. Thus, wedge-bolt 46 is secured in said pair of slots 30, firmly attaching said panels 22 and 24 to one another. Note that clearance for the point of second wedge-bolt 48 is provided by slot 42.
When used, the first end 14 of attachment 10 is inserted into void 36, and hole 18 is aligned with the pair of slots 30. Then a wedge-bolt 46 is inserted through the slots 30 and hole 18 (and secured by the other wedge-bolt 48 in the usual fashion). Hole 20, which extends beyond siderail 28, is then available to receive the hook of a safety belt (not shown).
As seen in FIG. 2, the width of attachment 10 along its short axis preferably is significantly smaller than the longest dimension of void 36. Thus the attachment is free to rotate to an extent about wedge-bolt 46, in reaction to an upward or downward force applied at the second hole 20. Hole 20 is spaced from hole 18 in the illustrated preferred embodiment by an amount adapted to position the hole 20 just beyond the siderails 28 when the attachment 10 is rotated either to the top or the bottom of the void 36.
FIG. 3 shows an alternative of the present invention. A simplified wallform panel or similar structure is shown schematically, comprising a wall 56 and a support 58. Rather than being inserted into a void between two siderails, as in the preferred embodiment, here attachment 10 has been located on the inside surface of support 58. As before, first hole 18 is aligned with wedge-bolt slot 30 in support 58. A wedge-bolt 46 is inserted which is secured with a second wedge-bolt 48, thus securing attachment 10. A hook on a safety belt (not shown) can then be inserted into hole 20. It is seen that this embodiment provides advantageous means for attaching a safety belt to a wallform or other structure when no tie-rod void of appropriate size is available. With head 49 bearing directly on attachment 10, it does not as freely rotate in the vertical plane, but will do so in reaction to sufficient force and thus will minimize any torsional forces on the wedge bolt 46 as used in FIG. 3.
Finally, in the broader aspects of this invention, several modifications can be made from the preferred embodiment described above. Several such modifications are described below. The operation of the safety attachment in other than a vertical plane is possible. Referring to FIG. 3, support 58 could be almost any structure, such as the bottom rail of a wallform panel. The thickness and hardness of the steel constituting attachment 10 is selected to be sufficient to resist failure in the event of a sharp substantial force downwardly or outwardly. Thicknesses up to 3/8 inch can be used and still not exceed that which can be accommodated in a standard safety-belt hook.
The holes 18 and 20 may be non-circular and/or of different sizes and shapes, so long as the shape chosen for the first hole 18 gives relief from direct torque on the securing wedge-bolt, and the other hole 20 can readily accommodate a safety hook therein. Similarly, the spacing of the holes 18, 20, respectively, from the edge of the attachment 10 is long enough to give adequate strength (and also necessary clearances in the intended environment). The spacing of holes 18, 20 from each other is minimally enough to insure sufficient clearance from or beyond the support structure to permit the safety hook to be applied without bending in operative positions of said attachment; and maximally not so far apart as to give excessive unsupported bending leverage. Thus, for example in FIG. 2, the hole 20, secured in the void 36 by wedge-bolt 46, should be spaced from hole 18 such that said hole 18 preferably is closely adjacent to void 36, but not within it.
By "wedge bolt" is meant a flat-sided connector of the type specifically illustrated and described in the aforementioned U.S. Pat. Nos. 4,210,306 and 4,228,986 and further includes similar bolts having at least one flat side (which fit in a standard wedge bolt slot without rotation) such as short bolts, base tie bolts, long bolts, short wedges, and threaded flat bolts of the type illustrated and described in U.S. Pat. No. 4,030,694 (therein identified as a "transition bolt"). | A concrete wall form with an attachment inserted between extending abutting flanges of form panels to secure a workman's safety belt, the attachment being pivotally mounted and comprising an oval plate having two spaced circular holes. | 4 |
FIELD OF THE INVENTION
The present invention relates to a wireless communication system.
BACKGROUND OF THE INVENTION
A wireless communication system has a configuration shown in, e.g., FIG. 1 . In the wireless communication system, transmitting and receiving stations 101 , 102 and 103 move to build a particular network (an ad hoc network) and share information even though a base station (not shown) or an access point is not present. In the ad hoc network, in response to the travel of the transmitting and receiving stations 101 , 102 and 103 , the communication is always maintained by determining a communication target and relay status in accordance with the traveled position and the line status.
FIG. 2 is a view showing a schematic configuration of a wireless communication device of the transmitting and receiving stations 101 , 102 and 103 . In FIG. 2 , a wireless communication device 200 of the transmitting and receiving stations 101 , 102 and 103 includes an antenna 201 , a transmitting unit 202 , a receiving unit 203 , a physical layer processing unit 204 , MAC (Media Access Control) layer processing unit 205 and IP (Internet Protocol) layer processing unit 206 . The wireless communication device 200 is electrically connected to a router 210 .
As for the flow of transmission data, the wireless communication device 200 performs the relay of the transmission data outputted from a terminal such as a PC (Personal Computer). An IP packet outputted from the router 210 is inputted to the wireless communication device 200 and routed in the IP layer processing unit 206 . In a case where the IP packet is routed to another transmitting and receiving station, a MAC frame is generated from the IP packet in the MAC layer processing unit 205 . At the same time, in the MAC layer processing unit 205 , a wireless channel is obtained by an autonomous distributed control. When the wireless channel is obtained, the wireless communication device 200 modulates the MAC frame information in the physical layer processing unit 204 , and transmits the modulated information from the transmitting unit 202 through the antenna 201 .
As for the flow of reception data, a signal received by the receiving unit 203 through the antenna 201 is demodulated in the physical layer processing unit 204 and then inputted to the MAC layer processing unit 205 as the MAC frame information. The MAC layer processing unit 205 checks a destination address and a frame error and confirms whether or not it is in a response order of itself. If the response is in its own response order, the MAC layer processing unit 205 generates a response frame for a previously received MAC frame to send the response frame as a reply. At the same time, the MAC layer processing unit 205 delivers an IP packet to the IP layer processing unit 206 . The IP layer processing unit 206 determines whether to discard the data or output the data to the router 210 based on the routing information.
FIG. 3 is a timing chart for explaining an operation of the wireless communication system. In FIG. 3 , a propagation delay rate is set to be almost the same as a symbol rate and the number of the transmitting and receiving stations (nodes) is three. An address code is previously set. The address code is set as address code information in the IP layer processing unit 206 and the MAC layer processing unit 205 of the wireless communication device 200 . In the set address code information, while using the address code as a key, the number of subscriber stations and a response number are stored as a pre-assignment table.
Nodes ‘A’, ‘B’ and ‘C’ have a previously determined response order when a response is requested. In FIG. 3 , a response order ( 1 ) is the highest in priority and a response order ( 3 ) is the lowest. In the same communication system, different nodes do not have the same response order. FIG. 3 shows a case where the transmission of route information and data is started after a carrier sense is performed from the node ‘A’ (after a fixed waiting time).
When the “route information and data (data representing information of voice, image and the like)” is transmitted from the node ‘A’, each receivable node performs reception of the “route information and data” transmitted by the node ‘A’. Here, the reply of another node is available when the reception of the “route information and data” is completed at the corresponding node. Among the nodes performing the reception of the “route information and data”, first, if the node ‘B’ having the response order ( 1 ) completes the reception of the “route information and data”, the node ‘B’ sends a “route information and ACK” as a reply. Among the nodes which have received the “route information and ACK” of the node ‘B’ and have lower response orders than that of the node ‘B’, one having the highest response order, i.e., the node ‘A’ having the order next to that of the node ‘B’, transmits a “route information and ACK”. Here, the node ‘A’ is a transmission source that has transmitted “route information and data” at the beginning. The node ‘A’ urges other nodes having lower response orders to transmit the “route information and ACK”. Although the node ‘A’ is the transmission source, the node ‘A’ transmits “route information and ACK” to maintain the route.
In this manner, each node transmits “route information and ACK” when it receives “route information and ACK” of a node having an immediately higher response order. Each station determines whether or not the response order is its own order by judging its own response order from information related to response orders of reception terminals included in the route information of the node ‘A’ that has transmitted “route information and data” at the beginning, and further, by judging whether the number of received responses counted up by a communication control unit or information representing response order of the transmission source including ACK corresponds to its own response order.
When receiving a reply from the node ‘C’ having the lowest response order, the node ‘A’ as the transmission source transmits “route information and termination” to notify the termination of the communication. At this time, by checking a response order included in ACK, it is determined whether the transmission has come from a transmitting and receiving station having the lowest priority or whether the number of receptions is equal to the number of subscriber stations (in this case, 3). The above process is the basic operation.
A pre-assignment method has a constraint condition that the method is applicable to only nodes capable of communicating within 1 hop, i.e., direct communication. That is to say, even if nodes have been registered in a pre-assignment group, for example, as can be seen in FIG. 4 , in a case where the nodes ‘A’ and ‘C’ cannot perform direct communication and relay is required, the pre-assignment method is not available. The transmission and reply of the nodes ‘A’ and ‘C’ do not reach each other.
As a prior art, for example, Patent Document 1 discloses a technique that efficiently specifies the operations of an IP address and a MAC address of a wireless network by an ad hoc routing protocol.
Patent Document 1: Japanese Patent Application Publication No. 2013-110521
In the aforementioned prior art, there are constraints as follows: a pre-assignment communication is available only when the direct communication is possible; and the same address code information is set and kept by a manager or the like in all wireless devices belonging to an ad hoc network. In a case of having the same address code, if the number of subscriber stations and response numbers are different, the communication is not possible.
Moreover, in an ad hoc network where participation and departure of communication subjects are frequent, it is difficult for a manager to maintain the above constraints and to set and manage the most efficient address information while judging whether or not direct communication is possible.
SUMMARY OF THE INVENTION
In view of the above, an object of the present invention is to easily generate address code information with a minimum delay when establishing an ad hoc network.
In accordance with an aspect, there is provided a wireless communication system in which a plurality of communication devices performs transmission and reception, each communication device including a signal processing unit/transmitting unit, a MAC layer processing unit and an IP layer processing unit, wherein the IP layer processing unit includes an ad hoc network processing unit, an address information management unit, a relay information storage unit and an ARP information storage unit, and the ARP information storage unit stores an adaptive address code information table and the relay information storage unit stores a relay information table.
In the wireless communication system, a relay communication device among the plurality of communication devices converts an address code of transmission side to an address code of a transmission destination.
In the wireless communication system, the adaptive address code information table contains an address code, a participation number, a response number and plural IP addresses, and the relay information table contains a destination, a relay device and a relay number.
Effect of the Invention
In accordance with the present invention, when establishing an ad hoc network, it is possible to generate address code information with a minimum delay.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view showing a concept of a wireless communication system.
FIG. 2 is a view showing a schematic configuration of a wireless communication device.
FIG. 3 is a timing chart for explaining an operation of the wireless communication system.
FIG. 4 is a view showing a concept of relay in the wireless communication system.
FIG. 5 is a view showing a concept of a case of transmitting ad hoc network information in the wireless communication system in accordance with an embodiment of the present invention.
FIG. 6 is a view for explaining an IP address when establishing an ad hoc network in the wireless communication system.
FIGS. 7A to 7D are views for explaining adaptive address code information when establishing the ad hoc network in the wireless communication system in accordance with the embodiment of the present invention.
FIG. 8 is a view for explaining an ARP information update when establishing the ad hoc network in the wireless communication system in accordance with the embodiment of the present invention.
FIGS. 9A to 9D are views for explaining a relay determination when establishing the ad hoc network in the wireless communication system in accordance with the embodiment of the present invention.
FIGS. 10A and 10B are a view for explaining relay communication using the adaptive address code in the wireless communication system in accordance with the embodiment of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings.
FIG. 4 is a view showing a concept of relay in a wireless communication system. In FIG. 4 , a communication device ‘A’ 410 cannot directly communicate with a communication device ‘C’ 430 , but communicates with the communication device ‘C’ 430 through the relay of a communication device ‘B’ 420 . First, the communication device ‘A’ 410 exchanges ad hoc network information with the communication device ‘B’ 420 . At the same time, the communication device ‘C’ 430 exchanges the ad hoc network information with the communication device ‘B’ 420 . Since a message needs to be broadcasted to all, the IP layer processing unit 206 instructs the MAC layer processing unit 205 at a code that does not require ACK communication, e.g., an address code ‘0’ and performs a wireless transmission.
In the above, if information has been successfully exchanged, it becomes possible that the communication device ‘A’ 410 communicates with the communication device ‘C’ 430 through the relay of the communication device ‘B’ 420 . At this time, since the communication device ‘A’ 410 , communication device ‘C’ 430 , and communication device ‘B’ 420 come to join to the same network, as shown in FIG. 6 , they have unique IP addresses within the same network.
FIG. 6 is a view for explaining an IP address when establishing an ad hoc network in the wireless communication system. As to the IP address, the IP layer processing unit 206 determines an address code by, e.g., the combination of final numbers. The address codes generated by combining unique IP addresses become also unique on the ad hoc network. Here, a participation number of the generated address codes are set to 2 and a response order is determined by ascending order of IP addresses. This information is defined as adaptive address code information. The adaptive address code is also set in the MAC processing unit 205 .
Next, the operation of the wireless communication system in accordance with the embodiment of the present invention will be described with reference to FIGS. 7 and 8 . FIGS. 7A to 7D are views for explaining adaptive address code information when establishing the ad hoc network in the wireless communication system in accordance with the embodiment of the present invention. FIG. 8 is a view for explaining an ARP information update when establishing the ad hoc network in the wireless communication system in accordance with the embodiment of the present invention. In FIG. 8 , an ARP information storage unit 826 stores adaptive address code information tables of FIGS. 7B to 7D . When IP layer processing units 513 and 823 exchange the ad hoc network information, the exchange is performed by assigning a MAC address and an IP address of the communication device.
By using them, when receiving the ad hoc network information, the IP layer processing units 513 and 823 updates ARP (Address Resolution Protocol) information having combination of the MAC address and the IP address. Up to this point, it is a pre-process to be executed until a terminal such as a PC transmits an IP packet.
Next, a process when an IP packet is inputted from a terminal such as a PC to a communication device will be described. When an IP packet is inputted from a terminal such as a PC to a communication device, the IP layer processing units 513 and 823 in the communication device determines whether or not there is relay transmission from the information exchanged on the ad hoc network. The determination of relay transmission is shown in FIG. 9 .
FIGS. 9A to 9D are views for explaining relay determination when establishing the ad hoc network in the wireless communication system in accordance with the embodiment of the present invention. For the relay determination, connection information of a wireless section (hereinafter, referred to as “link information”) is used as the content of the ad hoc network information. In this embodiment, since it is known that the communication device ‘B’ 420 is connected to the communication device ‘C’ 430 as the destination, the communication device ‘A’ 410 designates the communication device ‘B’ 420 as a relay device.
When outputting an IP packet to the MAC layer processing unit, a MAC address of the destination is set in a case that there is no relay device, and in a case that there is a relay device, a MAC address of the relay device is set. At this time, an IP address corresponding to the MAC address is extracted from the ARP information. The extracted IP address and an IP address of its own communication device are used as search keys to extract a matched address code from the adaptive address code information. The address code is given when the IP packet is inputted to the MAC layer processing unit. The MAC layer processing unit generates a MAC frame based on the given address code and the IP packet, outputs the MAC frame to the physical layer processing unit, and performs wireless communication.
Since the communication device as the destination also holds the adaptive address code information, when the communication device as the destination receives the MAC frame, the device determines that the received information is addressed to itself, and transmits ACK to the transmission destination, and then sends the received information to the IP layer processing unit. This case is shown in FIGS. 10A and 10B .
FIGS. 10A and 10B are a view for explaining relay communication using the adaptive address code in the wireless communication system in accordance with the embodiment of the present invention. In FIGS. 10A and 10B , the ARP information storage units 826 and 1016 store the adaptive address code information tables of FIGS. 7B to 7D . Relay information storage units 1017 and 1027 store relay information tables of FIGS. 9B to 9D . The communication device ‘A’ 410 uses the adaptive address code information shown in FIGS. 7B to 7D and the relay information shown in FIGS. 9B to 9D . From the relay information, it is seen that the communication device ‘B’ 420 is used as the relay device to send an IP packet to a terminal #2. Therefore, the communication device ‘A’ 410 selects adaptive address code information (address code “0x0102”) constructed between itself and the communication device ‘B’ 420 , outputs the selected information to a MAC layer processing unit 512 , and wirelessly transmits a MAC frame.
Upon receiving the wireless information, the communication device ‘B’ 420 also refers to the adaptive address code information and the relay information, and transmits an IP packet to the communication device ‘C’ 430 to send data to the terminal #2. At this time, the communication device ‘B’ 420 selects adaptive address code information (address code “0x0203”) constructed between itself and the communication device ‘C’ 430 , outputs the selected information to a MAC layer processing unit 522 , and wirelessly transmits a MAC frame. Then, the communication device ‘C’ 430 receives the wireless information. As described above, optimum address code information is constructed and an address code is selected at the time of communication.
The wireless communication system in accordance with the embodiment of the present invention can generate address code information with a minimum delay when establishing the ad hoc network.
INDUSTRIAL APPLICABILITY
As described above about the present invention in detail, the present invention is useful and available in a wireless communication system. Further, it goes without saying that the present invention is not limited to the wireless communication system described herein but can be widely applied to other wireless communication systems. The present application claims priority based on Japanese Patent Application No. 2014-244896 filed on Dec. 3, 2014, the entire contents of which are incorporated herein by reference.
DESCRIPTION OF REFERENCE NUMERALS
101 , 102 , 103 : transmitting and receiving stations
200 : wireless communication device
201 : antenna
202 : transmitting unit
203 : receiving unit
204 : physical layer processing unit
205 , 512 , 522 : MAC layer processing unit
206 , 513 , 523 , 1013 , 1023 , 1033 : IP layer processing unit
210 : router
410 : communication device ‘A’
420 : communication device ‘B’
430 : communication device ‘C’
511 , 521 : signal processing unit/transmitting unit
514 , 523 , 1034 : ad hoc network processing unit
515 , 525 , 1035 : address code information management unit
826 , 1016 : ARP information storage unit
1017 , 1027 : relay information storage unit | In a wireless communication system, a plurality of communication devices performs transmission and reception, each communication device including a signal processing unit/transmitting unit, a MAC layer processing unit and an IP layer processing unit. The IP layer processing unit includes an ad hoc network processing unit, an address information management unit, a relay information storage unit and an ARP information storage unit. The ARP information storage unit stores an adaptive address code information table and the relay information storage unit stores a relay information table. | 7 |
FIELD OF INVENTION
[0001] The embodiments of the present invention relate to semiconductor device packaging and, more particularly, to packaging having modifications that enhance the manufacturability and quality of products.
BACKGROUND
[0002] The electronics industry continues to rely upon advances in semiconductor technology to realize higher-function devices in more compact areas. For many applications realizing higher-functioning devices requires integrating a large number of electronic devices into a single silicon wafer. As the number of electronic devices per given area of the silicon wafer increases, the manufacturing process becomes more difficult.
[0003] Many varieties of semiconductor devices have been manufactured having various applications in numerous disciplines. Such silicon-based semiconductor devices often include metal-oxide-semiconductor field-effect transistors (MOSFET), such as p-channel MOS (PMOS), n-channel MOS (NMOS) and complementary MOS (CMOS) transistors, bipolar transistors, BiCMOS transistors. Such MOSFET devices include an insulating material between a conductive gate and silicon-like substrate; therefore, these devices are generally referred to as IGFETs (insulated-gate FET).
[0004] Each of these semiconductor devices generally includes a semiconductor substrate on which a number of active devices are formed. The particular structure of a given active device can vary between device types. For example, in MOS transistors, an active device generally includes source and drain regions and a gate electrode that modulates current between the source and drain regions.
[0005] Furthermore, such devices may be digital or analog devices produced in a number of wafer fabrication processes, for example, CMOS, BiCMOS, Bipolar, etc. The substrates may be silicon, gallium arsenide (GaAs) or other substrate suitable for building microelectronic circuits thereon.
[0006] The packaging of an IC devices is increasingly playing a role in its ultimate performance. Shortcomings in a particular package configuration may challenge the mounting process. For example, an IC component is placed onto to printed circuit board (PCB) and soldered on. The soldering process or package may cause the package not to lie flat on the PCB, the mounted package has substantial tilt. Furthermore, the quality of the soldering may not be visible on the finished populated PCB. Sending a PCB out into the field without the assurance of well-soldered (and well-observed) joint may pose a significant risk. This is of particular concern for IC devices subjected to harsh environmental conditions such as automotive or military applications in which extremes in temperature, humidity, mechanical stress are the norm. Field failure of a solder joint is not acceptable.
[0007] There is exists a need for a package with increased manufacturability and less susceptibility to tilting.
SUMMARY OF INVENTION
[0008] In the soldering of leadless chip carriers onto printed circuit boards, is necessary that the quality of the soldering be observable at the package terminals and that the carrier lie sufficiently flat. The present disclosure addresses these matters.
[0009] In an example embodiment, there is surface-mountable non-leaded chip carrier for a semiconductor device. The device comprises a first contact. A second contact is relative to the first contact; the second contact has a split therein to provide first and second portions of the second contact arranged relative to one another to lessen tilting of a soldering condition involving attachment of the chip carrier to a printed circuit board (PCB).
[0010] In another example embodiment, there is a small outline diode (SOD) package for surface mounting on a printed circuit board (PCB). The package comprises a first contact of a first length and width, having a bonding surface, a bottom mounting surface and a side mounting surface, the bonding surface having an area to which a diode die is attached; there is a second contact of a second length and width; the second contact is relative to the first contact, the second contact having a bonding surface, a bottom mounting surface, and a side mounting surface; the bonding surface has an area to which a bond wire is attached, the bond wire electrically coupling the diode die to the second contact. The second contact has a split therein to provide first and second portions of the second contact arranged relative to one another to lessen tilting of a soldering condition involving attachment of the chip carrier to the PCB. An encapsulation of molding compound envelopes the first contact and second contact, the side mounting surfaces of the first contact and second contact remain exposed, and the side mounting surfaces provides a visual indication of a the soldering condition.
[0011] In another example embodiment, semiconductor diode device is packaged in a small outline diode (SOD) package. the device comprises, a lead frame arranged in an array of die locations, each one of the die locations having, a first contact of a first length and width, having a bonding surface, a bottom mounting surface and a side mounting surface, the bonding surface having an area to which a diode die is attached; a second contact of a second length and width; the second contact is opposite to the first contact, the second contact has a bonding surface, a bottom mounting surface, and a side mounting surface, the bonding surface has an area to which a bond wire is attached; the bond wire electrically couples the diode die to the second contact; the second contact has a split therein to provide first and second portions of the second contact arranged relative to one another to lessen tilting of a soldering condition involving attachment of the chip carrier to the PCB. An encapsulation of molding compound envelopes the array of diode die locations. The lead frame is sawn between each die location in a first direction revealing a side mounting surface on the first contact and a side mounting surface of the second contact, the side mounting surface of the second contact having a corresponding split therein, the side mounting surfaces being flush with the encapsulation. Furthermore, the lead frame is electroplated with tin. The lead frame is sawn in a second direction, thereby separating the array of diode die locations into discrete diode devices. During installation onto a PCB, the side mounting surfaces of the discrete diode device provide an indication of the soldering condition.
[0012] In another example embodiment, there is a method for manufacturing small outline diode (SOD) package, the SOD package having a lead frame including, a first contact and a second contact opposite to the first contact, the second contact having a split therein to provide first and second portions of the second contact arranged relative to one another to lessen tilting of a soldering condition involving attachment of the chip carrier to a printed circuit board (PCB). The method comprises, providing a plurality of product die having a substrate connection and a wire bond connection; providing a plurality of lead frames; bonding the product die at the substrate connection onto the first contact of each lead frame and wire bonding the product die from wire bond connection to the second contact; encapsulating the plurality of product die and the plurality of lead frames in a molding compound; partially cutting the plurality of lead frames between each of the encapsulated product die; tin plating the exposed metal of the each lead frame of each product die; separating each encapsulated product die from one another; and testing each product die.
[0013] The above summaries of the present disclosure are not intended to represent each disclosed embodiment, or every aspect, of the present invention. Other aspects and example embodiments are provided in the figures and the detailed description that follow.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] The invention may be more completely understood in consideration of the following detailed description of various embodiments of the invention in connection with the accompanying drawings, in which:
[0015] FIG. 1 (Prior Art) depicts several packages having substantial tilting after mounting;
[0016] FIG. 2 is a line drawing of an example embodiment of a package according to the present disclosure
[0017] FIGS. 3A-3D depict an application of the package of FIG. 2 ;
[0018] FIGS. 4A-4D depicts an example component encapsulated with black molding compound in the package of FIG. 2 ; and
[0019] FIG. 5 depicts a flow diagram of an example assembly process for leadless packages according to an embodiment of the present disclosure; and
[0020] FIGS. 6A-6C depicts the sawing of an example lead frame undergoing the assembly process outlined in FIG. 5 .
[0021] While the invention is amenable to various modifications and alternative forms, specifics thereof have been shown by way of example in the drawings and will be described in detail. It should be understood, however, that the intention is not to limit the invention to the particular embodiments described. On the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the appended claims.
DETAILED DESCRIPTION
[0022] The disclosed embodiments have been found useful in the surface mounting of leadless chip carriers onto printed circuit board (PCB) apparatus. During surface mounting it is desirable for the components to lie flat upon the PCB and the combination of the chip carrier and PCB be of a certain height profile. However, imperfections in the wetting of the solder may cause the leadless chip carriers to be tilted, resulting in a too high profile. Refer to FIG. 1 . A group 100 of four devices 110 have been soldered onto a printed circuit board 120 and their solder profiles 130 have resulted in tilting and an uneven profile.
[0023] During a solder reflow process, when the solder melts, the solder heaps up under the package shown in FIG. 1 , the component slides to one side and the solder hardens, resulting in tilting. In one embodiment, the potential for tilting is inhibited by a double lead (i.e., one with two pads separated). In this embodiment the solder is pulling at the sides, which reduces the amount of solder under the component. The pulling force enhances the anti-tilting effect of the side contacts. The remainder of the solder is divided between the two pads at the bottom. The surface tension of at both sides prevents the component from sliding in one direction
[0024] With reference FIG. 2 , in a dimensioned drawing, a package 200 according to an embodiment to the present disclosure is presented. On the underside of the package is a first contact 215 and a second contact 225 split into a first portion and a second portion 225 a and 225 b on the side mounted to a printed circuit board. On an opposite side the first portion 225 a and second portion 225 b are electrically coupled. Upon this opposite side an attachment area for wire bonding is provided. The boundary 205 (represents the encapsulation) such that a package height of <0.4mm is attained. From a side view, contacts 225 a and 225 b are separated and visible. During attachment to the printed circuit board, the solder will wick from the bottom of the contacts 225 a ′ and 225 b ′ to the sides; likewise the solder will wick from the bottom of contact 215 to the side. Thus, the quality of the solder joints will be readily apparent from simple visual inspection. Note that in an example production process the package 200 would be in the form of a lead frame and be in quantities arranged in “tape and reel.” Tabs 240 , during assembly keep the contacts 215 and 225 in position for affixing a semiconductor die onto an attachment area on first contact 215 . The semiconductor die is wire bonded from a die pad region on the die and coupled to the attachment area of contact 225 . The assembled die is encapsulated. After encapsulation the lead frame is separated at tabs 240 (as shown by the dashed lines and spaces 245 . These show up as on the packaged die at contacts 215 ′ and 225 .′
[0025] Refer to FIGS. 3A-3D . In an example embodiment according to the present disclosure, a small outline diode (SOD) package 300 is depicted in four perspectives. FIG. 3A depicts the SOD in a perspective view. A first contact 325 and a second contact 315 electrically couple the diode die 330 with a bond wire 335 and through direct connection (at a defined area 330 ) at the underside of diode die 310 . Within an envelope 305 of molding compound the mounted diode die 310 , and contacts 325 , 315 , are encapsulated. Refer to FIG. 3B . note the second contact 320 is split into two portions 320 ′. This feature reduces the likelihood of tilting when the SOD device is soldered onto a printed circuit board. Further note that the first contact 325 and second contact 320 have flanges that allow the molding compound to flow about them so as to increase the mechanical strength of the envelope 305 . These SOD packages are arranged in lead frame arrays holding more than 8000 devices, divided over four areas (i.e., “mold caps’). Thus, during encapsulation, 8000 devices are enveloped in molding compound simultaneously.
[0026] Refer to FIG. 3C . The first contact 315 as viewed from a first short side of the package 300 , extends from the bottom of the package 300 partially upward on the side, flush with the encapsulation 305 . Likewise, in FIG. 3D , the second contact 325 , as viewed from a second short side, extends partially upward and flush with the encapsulation 305 , as well. Note at the dashed line 340 , the second contact has a first portion 325 a and a second portion 325 b.
[0027] So as to provide a solderable surface, the contacts are plated with tin or other suitable metal. When the SOD package is soldered to a PCB, during inspection one can easily see whether the quality of the soldering is sufficient. Previous packages in which the contacts were not visible from the sides would require complex X-ray scanning to evaluate the soldering.
[0028] The first contact and second contact during the mounting and encapsulation of a diode die 310 would be part of a lead frame assembly supplied to the user in the form of tape and reel. The cathode is on the underside of the diode die 310 and the anode is on the topside of the diode die 310 . Each lead frame assembly would be joined to another at tabs which had previously joined contact 315 ′ and 325 ′. After die mounting and encapsulation, the lead frame assembly would be “singulated,” that is separated into separate SOD product.
[0029] In an example embodiment according to the present invention, a diode die had been assembled in an SOD package. Refer to FIGS. 4A-4D . The long side view of FIG. 4A shows the areas 415 ′ and 425 ′ in which the lead frame (as mentioned in discussion with FIG. 2 ) and contacts 415 a contact portion 425 a. The underside view of FIG. 4B depicts the contact 415 and contacts 425 a and 425 b. Short side views FIG. 4C and FIG. 4D show the contacts 415 and contacts 425 a and 425 b, respectively. These contacts extend upwards for a portion of the finished vertical height of the encapsulation 405 . Furthermore, these contacts are flush with the encapsulation 405 .
[0030] In manufacturing the embodiments according to the present invention, an example process may be described in reference to FIG. 5 . The process will often begin with the making of inventory of materials, such as lead frames (such as those described in reference to FIG. 2 ), epoxy glue for die attaching, gold wire for wire bonding, and molding compound for encapsulating. As with many modern manufacturing processes, these materials are inspected to see whether they meet vendor/manufacturer agreed upon quality standards. In an example process, the lead frames are delivered as strips having four frames per strip. Within each frame there are greater than 800 locations to which diodes can be mounted. Depending on process specifics, the strips may be combined to make a tape and reel with a plurality of frames.
[0031] The wafers of a product die, for example, diodes is received by the manufacturing line. Wafers undergo dicing 510 in which functional die are separated out from the duds. The diode dice are die bonded 520 to the lead frame. Incidentally, the lead frame may be delivered in a tape and reel format that holds thousands of individual lead frames (i.e., analogous to the single frames of motion picture film). The lead frame is made of a suitable metal. For example, copper is often used, but particular applications may use other metals and alloys. A bonding compound of a conductive epoxy may be used, but it is not limited to this particular type of attachment. In other processes, a eutectic die attach may be used. After die bonding 520 , the epoxy glue is cured. After curing, the assembly is cleaned in a plasma. The die is wire bonded 530 to the lead frame from a defined bond pad on the diode die (bonding the diode cathode) to a defined bond pad on the lead frame (bonding the diode anode). After wire bonding 530 , the assembly is again cleaned in a plasma. The die having been attached to the lead frame and wire bonded, the assembly is encapsulated in a molding compound 540 . Tape on the contact side (underside) of the package keeps the molding compound from flowing onto the contacts. Therefore the leads are flush with the mold compound at the bottom. The molding compound undergoes a curing process.
[0032] In an example process, after the molding 540 , there is a plurality of devices on a strip of lead frames. Refer to FIGS. 6A-6C . To maintain stability of the lead frames during handling, a support tape 640 is applied to the plurality of devices after encapsulation 620 on the topside of the package. Prior to tin plating, the plurality of devices are prepared in a “partial cut” process 545 . Between each device a saw 630 makes cut into the boundaries separating a first lead frame 610 adjacent to an additional lead frame in a first direction. The saw cuts completely through the contacts and just slightly into the molding compound 620 . After sawing, a de-flashing process removes metal fragments, etc. from the lead frames. The underside surfaces and vertical surfaces of the first and second contacts are exposed for plating 650 with tin or other suitable metal which has soldering characteristics more suitable than that of bare copper. The encapsulated assembly's leads are plated with tin 550 . Since only one cut had been made, the devices are still connected electrically with the neighbors and the complete lead frame in the other direction, and therefore electroplating of tin is possible. Furthermore, the structural integrity of the lead frames is maintained so that prior to electroplating, the support tape can be removed.
[0033] The leads having been plated, the devices are given a final lead cut 555 in both directions, the second cut to complete the partial cut and then a third cut in the perpendicular direction to the first and second cuts, as illustrated in FIG. 6C . The dice are then separated in a singulation process 560 . The partial cut previously applied to the plurality of devices is finished off with a second cut 635 which completely passes through the devices' encapsulation and partially into the supporting tape 640 . The singulated devices are sorted visually to cull those devices damaged during separation. Electrical testing and marking 570 of the assembled devices assures that devices shipped to an end user function.
[0034] Numerous other embodiments of the invention will be apparent to persons skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims. | Consistent with an example embodiment, there is surface-mountable non-leaded chip carrier for a semiconductor device. The device comprises a first contact. A second contact is relative to the first contact; the second contact has a split therein to provide first and second portions of the second contact arranged relative to one another to lessen tilting of a soldering condition involving attachment of the chip carrier to a printed circuit board. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of applications Ser. Nos. 552,996 and 552,997, both filed Nov. 17, 1983, both now abandoned.
BACKGROUND OF THE INVENTION
The present invention relates to novel compositions of matter. These novel compositions are to be used in the treatment of conditions or symptoms due to certain disease conditions in mammals. In particular this invention relates to novel compounds which are useful in inhibiting the formation of products of the "aracidonic acid cascade" in such pathological states. This inhibition is accomplished by inhibiting the action of the enzyme phospholipase A 2 , an important mediator in the cascade, by administering certain novel 4,1-benzoxazepin-2(3H)-ones.
The important role of phospholipase A 2 in mammalian metabolism through the formation of prostaglandins is now well known. See W. Vogt, Advances in Prostaglandins and Thromboxane Research, Vol. 3, page 89 (1978); P. C. Isakson, et al., Advances in Prostaglandin and Thromboxane Research, Vol. 3, page 113, (1978). Phospholipase A 2 is responsible for the hydrolysis of arachidonic acid-containing phospholipids, thereby providing substrate for the multiple enzymes of the arachidonic acid cascade.
The products of the arachidonic acid cascade are varied. These products include prostaglandins, thromboxanes, leukotrienes, and other hydroxylated derivatives of arachidonic acid, which are referred to as "eicosanoids." While generally the products of the cascade are beneficial, in certain disease processes and other conditions the excessive production of eicosanoids induces deleterious consequences such as inflammation (see paper by N. A. Plummer, et al.; abstracted in Journal of Investigative Dermatology, Vol. 68, No. 4, p. 246 (1977)); erythema (N. A. Plummer, supra); platelet aggregation (B. B. Vargaftig, J. Pharm. Pharmacol., Vol. 29, p. 222-228 (1977)); and the release of SRS-A (slow reacting substance-anaphylaxis), a known mediator of allergenic responses. The inhibition of phospholipase A 2 prevents these and similar conditions mediated by the action of this enzyme.
Some inhibitors of phospholipase A 2 are known. R. J. Flower and G. J. Blackwell have shown that certain anti-inflammatory steroids induce biosynthesis of a phospholipase A 2 inhibitor which prevents prostaglandin generation. See Nature, Vol. 278, p. 456 (1979). These steroids are not direct inhibitors of phospholipase A 2 , but rather stimulate the synthesis of a phospholipase inhibiting factor called lipocortin, lipomodulin, or macrocortin.
Some examples of direct phospholipase A 2 inhibition are known. Indomethacin, a drug with anti-inflammatory properties, has been shown to inhibit at least one phospholipase A 2 enzyme. See K. L. Kaplan, et al., Proc. Natl. Acad. Sci., Vol. 75, No. 6, pp. 2955-2988 (1978). The compound has been shown to inhibit phospholipase A 2 enzymes, isolated respectively from the venoms of Russel Viper, Crotalus adamanteus, and bee, and from pig pancreas. Certain local anesthetics have been shown to inhibit phospholipase A 2 activity by competing with calcium ion, which appears to be a requirement for phospholipase activity. See W. Vogt, Advances in Prostaglandin and Thromboxane Research, Vol. 3 p. 89 (1978). Bromphenacyl bromide has been shown to inhibit phospholipase A 2 by acylating a histadine residue which is the active site of the molecule. See M. Roberts, et al., Journal of Biological Chemistry, Vol. 252, pp. 2405-2411 (1977). R. Blackwell, et al., in British Journal of Pharmacy, Vol. 62, p. 79-89 (1978) has disclosed that mepacrine inhibits the activity of phospholipase A 2 derived from perfused guinea pig lung. Certain butyrophenones are disclosed as phospholipase A 2 inhibitors in U.S. Pat. No. 4,239,780.
PRIOR ART
U.S. Pat. No. 3,122,554 discloses certain 1,5-dihydro-5-phenyl-4,1-benzoxazepin-2(3H)-ones which are optionally substituted at the nitrogen by a lower alkyl group. These compounds are stated to be useful as central nervous system depressants, as tranquilizers, and as muscle relaxants. Similarly, U.S. Pat. No. 3,346,565 discloses certain 1,2,3,5-tetrahydro- and 3,5-dihydro-4,1-benzoxazepines having alkyl, aralkyl, acyl, and amine substituents on the nitrogen. These compounds are stated to be useful as sedatives, tranquilizers, and hypnotics. Derwent Farmdoc 27355E, abstracting Japanese application No. 35576/82 (J5 7035-576) discloses certain 4,1-benzoxazepine-3-acetic acid derivatives which are stated to be useful as minor tranquilizers. U.S. Pat. No. 4,307,091 discloses certain 4H-1,4-benzoxazin-2,3-diones which are stated to be useful as antiallergic agents. Derwent Farmdoc 25429C, which abstracts Belgian application No. 880,282, discloses certain 4,1-benzoxazepine derivatives which are stated to be useful as CNS depressants. U.S. Pat. No. 3,598,808 discloses certain perhydro-5-substituted-phenyl-cycloalkapolyene-4,1-oxazepines as useful in the treatment of respiratory disorders, e.g., asthma. U.S. Pat. Nos. 4,341,704 and 4,297,280 disclose certain 4,1-benzoxazepines having (C 7 -C 9 )aralkyl substituents on the nitrogen. These compounds are stated to be useful as antidepressants. U.S. Pat. No. 3,346,565 discloses certain 4,1-benzoxazepin-2(3H)-ones having sedative, tranquilizing, and antidepressant activity.
SUMMARY OF THE INVENTION
The present invention particularly provides a compound of the Formula I wherein R 1 is
(a) cyclopropylmethyl,
(b) 2-phenylethyl,
(c) --(CH 2 ) n --NR 4 R 5 , or
(d) --CH 2 --CH 2 --(CH 2 ) m --R 11 ,
wherein R 11 is
(a) --O--PhX,
(b) --S(O) p --PhX,
(c) --O--Z,
(d) --PhX,
(e) --OR 2 , or
(f) phthalimido;
wherein PhX is
(a) phenyl, or
(b) phenyl substituted by X 1 ;
wherein X 1 is
(a) chloro
(b) bromo,
(c) fluoro,
(d) nitro,
(e) trifluoromethyl,
(f) methoxy,
(g) hydroxy,
(h) (C 1 -C 3 )alkyl,
(i) --SCH 3 , or
(j) --CO 2 M, wherein M is hydrogen, (C 1 -C 3 )alkyl, or a pharmacologically acceptable cation; wherein n is 2 or 3, wherein m is an integer from zero to 4, inclusive, with the proviso that m is not zero when R 11 is phenyl; wherein p is an integer from zero to 2, inclusive, and wherein R 4 and R 5 are the same or different and are (C 1 -C 3 ) alkyl or R 4 amd R 5 together with the nitrogen atom to which they are attached form 1-azetidinyl, 1-pyrrolidinyl, 1-piperidinyl, or 4-morpholinyl; wherein R 2 is
(a) hydrogen,
(b) (C 1 -C 2 )alkyl, or
(c) phenyl;
wherein Z is (C 3 -C 6 )cycloalkyl; wherein Y 1 is
(a) hydrogen,
(b) chloro,
(c) bromo,
(d) fluoro,
(e) nitro, or
(f) trifluoromethyl,
including the acid addition salts thereof when R 1 is --(CH 2 ) n --NR 4 R 5 ; with the following provisos:
(1) when R 1 is cyclopropylmethyl and R 2 is methyl or when R 1 is --CH 2 --CH 2 --(CH 2 ) m --R 11 , Y 1 is not hydrogen;
(2) when R 1 is cyclopropylmethyl, 2-phenylethyl, or --(CH 2 ) n --NR 4 R 5 , Y 1 is not nitro;
(3) R 2 is hydrogen or (C 2 -C 3 )alkyl only when R 1 is --CH 2 --CH 2 --(CH 2 ) m --R 11 .
The carbon atom content of various hydrocarbon-containing moieties is indicated by a prefix designating the minimum and maximum number of carbon atoms in the moiety, i.e., the prefix (C i -C j ) indicates a moiety of the integer "i" to the integer "j" carbon atoms, inclusive. Thus (C 1 -C 3 )alkyl refers to alkyl of one to 3 carbon atoms, inclusive, or methyl, ethyl, propyl, and isopropyl.
Examples of cycloalkyl of 3 to 6 carbon atoms, inclusive, are cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
Examples of substituted phenyl within the scope of PhX are p-chlorophenyl, m-chlorophenyl, p-tolyl, m-tolyl, o-tolyl, p-ethylphenyl, 5-methylphenyl, 4-bromophenyl, and the like.
Phthalimido means 1,3-dihydro-1,3-dioxo-2H-isoindol-2-yl.
The compounds of the present invention may be in the form of pharmacologically acceptable salts. These salts are formed when M is a pharmacologically acceptable cation. Such cations include: pharmacologically acceptable metal cations, ammonium, amine cations, or quaternary ammonium cations.
Especially preferred metal cations are those derived from the alkali metals, e.g., lithium, sodium, and potassium, and from the alkaline earth metals, e.g., magnesium and calcium, although cationic forms of other metals, e.g., aluminum, zinc, and iron are within the scope of this invention.
Pharmacologically acceptable amine cations are those derived from primary, secondary, or tertiary amines. Examples of suitable amines are methylamine, dimethylamine, trimethylamine, ethylamine, dibutylamine, triisopropylamine, N-methylhexylamine, decylamine, dodecylamine, allylamine, crotylamine, cyclopentylamine, dicyclohexylamine, benzylamine, dibenzylamine, α-phenylethylamine, β-phenylethylamine, ethylenediamine, diethylenetriamine, and the like aliphatic, cycloaliphatic, araliphatic amines containing up to and including about 18 carbon atoms, as well as heterocyclic amines, e.g., piperidine, morpholine, pyrrolidine, piperazine, and lower-alkyl derivatives thereof, e.g.,
1-methylpiperidine,
4-ethylmorpholine,
1-isopropylpyrrolidine,
2-methylpyrrolidine,
1,4-dimethylpiperazine,
2-methylpiperidine,
and the like, as well as amines containing water-solubilizing or hydrophilic groups, e.g.,
mono-, di-, and triethanolamine,
ethyldiethanolamine,
N-butylethanolamine,
2-amino-1-butanol,
2-amino-2-ethyl-1,3-propanediol,
2-amino-2-methyl-1-propanol,
tris(hydroxymethyl)aminomethane,
N-phenylethanolamine,
N-(p-tert-amylphenyl)diethanolamine,
glactamine,
N-methylglycamine,
N-methylglucosamine,
ephedrine,
phenylephrine,
epinephrine,
procaine,
and the like. Further useful amine salts are the basic amino acid salts, e.g.,
lysine and
arginine.
Examples of suitable pharmacologically acceptable quaternary ammonium cations are
tetramethylammonium,
tetraethylammonium,
benzyltrimethylammonium,
phenyltriethylammonium, and the like.
Compounds of the present invention have been tested in standard laboratory tests to evaluate their ability to inhibit phospholipase A 2 . In the perfused guinea pig lung, 1-(3-phenoxypropyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepine-2(3H)-one (Example 2) has been shown to be preferred, exhibiting complete inhibition of the enzyme at 1.8×10 -6 Molar.
Thus, the compounds of the present invention are useful whenever it is medically necessary or desirable to inhibit phospholipase A 2 in a mammalian system. They are particularly useful in treating symptoms or conditions resulting from the action of the arachidonic acid cascade.
The symptoms or conditions treated or prevented by the compounds of this invention are those which are produced as a result of the excessive stimulation of the arachidonic acid cascade during certain disease processes or conditions. The multiple enzymes of the cascade act upon 5,8,11,14-eicosotetraenoic acid to produce prostaglandins, leukotrienes, and hydroxylated derivatives. At certain times during these disease processes or conditions, some of these products are responsible for the symptoms or conditions noted above, e.g., inflammation, erythema, allergic responses, and similar conditions. Phospholipase A 2 provides the substrate for these enzymes of the cascade by hydrolysis of arachidonate rich phospholipids. Thus, phospholipase A 2 is an important mediator in these conditions. Inhibition of this enzyme by the method of this invention is thus effective to treat or prevent the symptoms or conditions, which are designated as PMC's (phospholipase A 2 mediated conditions).
The precise mechanisms of the disease processes or conditions which stimulate the arachidonic acid cascade are not clearly understood. The essential prerequisite, however, is enhanced activity of the phospholipases which provide arachidonate to the series of reactions designated as the arachidonic acid cascade. The method of this invention is simply to block the action of the phospholipases and cut off the flow of arachidonate into the cascade, irrespective of the stimulus or stimuli which may be present. This is accomplished with the compounds of the present invention. Thus, the method of this invention is suitable for treating seemingly unrelated diseases whose common element is the stimulation of the arachidonic acid cascade. The term "phospholipase A 2 mediated conditions" (PMC) includes all untoward conditions or symptoms which are the result of the excessive stimulation of the arachidonic acid cascade. These conditions encompass allergenic diseases, inflammatory conditions (including chronic inflammatory conditions such as rheumatoid arthritis), burns, and hypoxic conditions at the cellular level such as coronary infarcts, or infarcts of other tissues. In these latter infarct conditions it is desirable to block phospholipase activity to prevent the destruction of phospholipids which are substrates for phospholipases, and are integral structural components of cellular membranes.
The method of this invention could be used on any mammal whose metabolic system includes the phospholipase induced arachidonic acid cascade. The mammals which are preferred are generally domesticated animals and humans. Humans are the most preferred mammals to be treated by the method of this invention.
The degradation of cell membranes by phospholipase A 2 , hydrolyzing the phospholipid components of the membrane, is believed to be a component in the cellular death resulting from hypoxic states such as coronary infarcts, ligation of the aorta during surgery for aortic aneurysms (resulting in kidney damage), and the like. Inhibition of phospholipase A 2 by these compounds could greatly ameliorate the cellular damage resulting from such causes. See Zalewski, et al., Clinical Research 31:227 (1983). This is a preferred use of these compounds.
Asthma is a disease of the lungs in which a wide variety of stimuli can result in an asthmatic attack. These stimuli range from damp cold air to allergens in the environment. The asthmatic response is characterized by constriction of the bronchioles leading to increased airway resistance. There is an early constrictive phase due to histamine release from mast cells, as well as other modulators, e.g., peptides. A late sustained phase then occurs which, in human beings may reach a maximum in 6-8 hours. This phase is slower in onset and disappearance, and is due to a complex of products of the arachidonic acid cascade. These include thromboxanes, prostaglandins, and leukotrienes. The precursor for all of these eicosanoids is arachidonate which is released from esterified forms in membranes to the appropriate enzymes by the action of phospholipase A 2 . See, e.g., "Corticosteroid Treatment in Allergic Airway Diseases," Proceedings of a Symposium in Copenhagen Oct. 1-2, 1981 (Editors: T. H. Clark, N. Myginfd, and O. Selroos, Munksgaard/Copenhagen 1982). Thus, a block of the phospholipase A 2 , which is physiologically acceptable, will prevent release of eicosanoids in the lung, thought to be responsible for the "2nd wave" of airway resistance. This is a preferred use of the compounds of this invention.
Increased phospholipase activity has been observed after central nervous system (CNS) trauma, e.g., brain and spinal cord injury. See, E. P. Wei, et al., J. Neurosurg. 56:695-698 (1982) and E. D. Hall and J. M. Braughler, Surgical Neurology 18:320-327 (1982). Thus, phospholipase inhibitors, such as the compounds of the present invention, would be useful in the treatment or prevention of such conditions.
The method of this invention is useful both in treating a phospholipase A 2 mediated condition (PMC) or symptoms which has already manifested itself in the mammal as well as the prevention of these conditions or symptoms in mammals including those particularly susceptible to them. Employment of the method of this invention prior to the development of a PMC would prevent the formation of the prostaglandins and similar products necessary for such conditions. Thus, the method of this invention can be used to prevent edema and erythema from sunburn by administering these compounds prior to exposure to sunlight. The compounds of this invention could be administered to persons suffering from hayfever or similar allergies prior to exposure to allergenic substances which are particularly hard on hayfever suffers. In a like manner, a physician or veterinarian could readily determine other mammals or persons susceptible to a PMC.
It is most preferred to use the compounds of this invention in the treatment or prevention of asthma and in the treatment or prevention of cellular death resulting from hypoxic states.
Once a PMC has manifested itself a physician or verterinarian could readily determine the necessity of employing the process of this invention.
The actual inhibition of phospholipase A 2 by the method of this invention takes place on a cellular level. Administration of the compound of this invention can thus be by any manner which will allow for phospholipase A 2 inhibition in the affected tissues or organs. The preferred route in most cases would be to systemically administer the compounds, i.e., to allow them to enter the mammal's bloodstream and thus be distributed throughout the mammal's system. In certain cases, where the PMC is of a localized nature (e.g., sunburn), topical administration (e.g., transdermal) may be employed in order that the phospholipase A 2 inhibition is confined to the afflicted area.
Since the diseases or conditions resulting from the arachidonic acid cascade are varied, methods of administering these compounds must depend on the particular phospholipase mediated condition (PMC) sought to be treated. Regardless of the route of administration selected the compounds used in the process of the present invention are formulated into pharmaceutically acceptable dosage form by conventional methods known to the pharmaceutical art.
Thus, the compounds can be administered orally in forms such as pills, capsules, solutions or suspensions. They may also be administered rectally or vaginally in forms such as suppositories or bougies. They may also be introduced parenterally, e.g., subcutaneously, intravenously, or intramuscularly using sterile injectable forms known to the pharmaceutical art. For treatment of conditions such as erythema the compounds of this invention may also be administered topically in the form of ointments, creams, gels, or the like.
In general the preferred route of administration is oral.
The dosage regimen for preventing or treating phospholipase mediated conditions (PMC) by the compounds of this invention is selected in accordance with a variety of factors., including the type, age, weight, sex and medical condition of the mammal, the severity of the PMC and the particular compound employed. An ordinarily skilled physician or veterinarian will readily determine and prescribe the effective amount of the anti-PMC agent to prevent or arrest the progress of the condition. In so proceeding the physician or veterinarian could employ relatively low dosages at first, subsequently increasing the dose until a desired or maximum response is obtained.
Initial dosages of the compounds of this invention can be from about 0.003 to 4.0 g per 70 kg mammal per 8 hours orally. When other forms of administration are employed, equivalent doses are administered. When dosages beyond 2.0 g per 70 kg mammal per 8 hours are employed, care should be taken with each subsequent dose to monitor possible toxic effects.
Most importantly, these novel compounds are useful as antiinflammatory agents in mammals and especially humans, and for this purpose, are administered systemically and preferably orally. For oral administration, a dose range of 0.05 to 50 mg per kg of human body weight is used to give relief from pain associated with inflammatory disorders such as rheumatoid arthritis. They are also administered intravenously in aggravated cases of inflammation, preferably in a dose range of 0.01 to 100 μg per kg per minute until relief from pain is attained. When used for these purposes, these novel compounds cause fewer and less severe undesirable side effects than do the known synthetase inhibitors used to treat inflammation, for example, aspirin and indomethacin. When these novel compounds are administered orally, they are formulated as tablets, capsules, or as liquid preparations, with the usual pharmaceutical carriers, binders, and the like. For intravenous use, sterile isotonic solutions, are preferred.
The compounds of this invention can also be administered as pharmacologically acceptable acid addition salts such as the hydrochloride, hydrobromide, hydroiodide, sulfate, phosphate, acetate, propionate, lactate, maleate, malate, succinate, tartrate, methanesulfonate, p-toluenesulfonate, β-naphthalenesulfonate, fumarate, citrate, and the like. These salts may also be in hydrated or solvated form.
The compounds of the present invention are prepared by the methods depicted in Charts A and B.
In Chart A, Y 1 , R 1 , R 2 , and n are as defined above. The starting 2-aminobenzophenones of the Formula A-1 are well known in the art, particularly because of their usefulness in the preparation of 1,4-benzodiazepine compounds. See for example L. H. Sternbach, Progress in Drug Research, Vol. 22, page 229 (1978). A 2-aminobenzophenone of the Formula A-1 is reacted with an appropriate Grignard reagent, for example, R 2 MgBr, or with a suitable organolithium reagent, for example R 2 Li, in a suitable solvent, for example diethyl ether and the like to produce the R 2 -substituted amino-alcohol of the Formula A-2. The amino-alcohol of the Formula A-2 is chloroacetylated by reaction with chloroacetyl chloride at about 0° to 30° C. in a suitable solvent such as diethyl ether in the presence of a suitable acid scavenger, for example a teritary amine such as triethylamine, to produce an amide of the Formula A-3. An amide of the Formula A-3 is reacted with a suitable base such as sodium hydride in a suitable solvent such as tetrahydrofuran (THF), at about 10° to 30° C. for up to 20 hours and then at the reflux temperature of the mixture for up to four hours to produce a ring-closed 4,1-benzoxazepine-2(3H)-one of the Formula A-4. A Formula A-4 amide is alkylated on nitrogen by reaction with a suitable base such as sodium hydride in a suitable solvent such as dimethylformamide (DMF) for up to three hours at about 10° to 95° C. Lower temperatures are preferred for this reaction when R 2 is phenyl. To the reaction mixture thus obtained (after cooling if desired) is added the appropriate alkyl halide of the formula R 1 CH 2 CH 2 (CH 2 ) n Cl or R 1 CH 2 CH 2 (CH 2 ) n Br either without a solvent or in a suitable solvent such as xylene or DMF, and this mixture is then reacted at up to 100° C. for up to 24 hours to produce a compound of this invention of the Formula A-5.
Similarly, in Chart B, Y 1 , R 1 , R 2 and n are as defined above and Z is either chloro or bromo. The starting 2-aminobenzophenones of the Formula B-1 are well known in the art, particularly because of their usefulness in the preparation of 1,4-benzodiazepine compounds. See for example L. H. Sternbach, Progress in Drug Research, Vol. 22, page 229 (1978). A 2-aminobenzophenone of the Formula B-1 is reacted with an appropriate Grignard reagent, for example, R 2 MgBr, or with a suitable organolithium reagent, for example R 2 Li, in a suitable solvent, for example diethyl ether and the like to produce the R 2 -substituted amino-alcohol of the Formula B-2. The amino-alcohol of the Formula B-2 is chloroacetylated by reaction with chloroacetyl chloride at about 0° to 30° C. in a suitable solvent such as diethyl ether in the presence of a suitable acid scavenger, for example a tertiary amine such as triethylamine, to produce an amide of the Formula B-3. An amide of the Formula B-3 is reacted with a suitable base such as sodium hydride in a suitable solvent such as tetrahydrofuran (THF), at about 10° to 30° C. for up to 20 hours and then at the reflux temperature of the mixture for up to four hours to produce a ring-closed 4,1-benzoxazepine-2(3H)-one of the Formula B-4. A Formula B-4 amide is alkylated on nitrogen by reaction with a suitable base such as sodium hydride in a suitable solvent such as dimethylformamide (DMF) for up to three hours at about 10° to 95° C. Lower temperatures are preferred for this reaction when R 2 is phenyl. To the reaction mixture thus obtained (after cooling if desired) is added the appropriate alkyl halide of the formula R 1 Cl or R 1 Br either without a solvent or in a suitable solvent such as xylene or DMF, and this mixture is then reacted at up to 100° C. for up to 24 hours to produce a compound of this invention of the Formula A-5.
As an alternative for making compounds of the Formula I wherein R 1 is --(CH 2 ) n --NR 4 R 5 an amide of the Formula B-4 is reacted with a suitable base as described above, and the resulting reaction mixture is reacted with an appropriate alkyl halide of the Formula Z--(CH 2 ) n --Z, wherein each occurrence of Z is the same or different and is chloride or bromine, to produce a haloalkyl intermediate of the Formula B-6. A haloalkyl compound of the Formula B-6 is reacted with an amine of the Formula NHR 4 R 5 in a suitable solvent, for example a mixture of chloroform, 2-propanol, and acetonitrile, at a temperature from 25° C. to the reflux temperature of the mixture, for a time sufficient to form the corresponding compound of the Formula B-5. The Formula HNR 4 R 5 amines are known or can be prepared by known methods.
In compounds of the Formula I carbon atom number five (C 5 ) bears phenyl and R 2 as substituents, and when these C 5 substituents are different, C 5 is thus asymmetrically substituted and can possess either the R- or the S-configuration. Thus these Formula I compounds can exist as the racemate ((+)-form) or as a single enantiomer ((+)- or (-)-form) substantially free of the other enantiomer or as varying mixtures of the enantiomers, and all such stereoisomers are included within the scope of this invention and are meant to be included within the scope of Formula I. The enantiomers of a particular compound are separated by known resolution methods. For example the Formula A-2 amino-tertiary alcohols are separated, i.e. resolved, into their respective optical isomers (enantiomers), as is standard in the isomer resolution art, by reacting the amine moiety with any of the known resolving agents such as optically active camphorsulfonic acid, bis-o-toluoyltartaric acid, tartaric acid, diacetyl tartaric acid, and the like, which are generally commercially available and which are used for the resolution of amines (bases), as for example in Organic Synthesis, Coll. Vol. V, page 932 (1973), resolution of R-(+) and S-(-)-α-phenylethylamine with (-)-tartaric acid. The diastereomeric salts thus produced have different crystallization properties and are separated by conventional means including differential crystallization. On neutralization of each substantially separated diastereomeric salt with base in a suitable solvent, the corresponding optically active enantiomers of the Formula A-2 are obtained, each of which is purified by conventional means. The optically active Formula A-2 compounds are converted to optically active compounds of the Formula A-5 of this invention as described in Chart A, taking care that racemization does not occur.
Certain compounds of the present invention are preferred. Thus, compounds of the Formula I wherein R 1 is --OPhX, --OZ, --OH, --OCH 3 , --OC 2 H 5 , phthalimido, --SPhX or PhX; Z is cyclopentyl or cyclohexyl, R 3 is hydrogen, methyl or phenyl; n is zero, 1, or 2; and Y 1 is in the 7-position are preferred. 1-(3-phenoxypropyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one (Example 2) is most preferred.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In this specification ether refers to diethyl ether unless otherwise indicated. NaHCO 3 means sodium bicarbonate; MgSO 4 means magnesium sulfate; the phrase "dried (MgSO 4 )" generally means that a solution was dried by contacting with anhydrous magnesium sulfate followed by separation, usually filtration, of the liquid from the magnesium containing solids. THF means tetrahydrofuran; NaH means sodium hydride; MeOH means methanol; DMF means N,N-dimethylformamide; HCl means hydrogen chloride; CH 2 Cl 2 means methylene chloride; CHCl 3 means chloroform; SSB means Skellysolve B which is a trade name for a solvent which is essentially n-hexane, bp 60°-68° (Merck Index 9th Edition, page 1106).
Preparation 1
2,4'-Dichloro-α-hydroxy-α,α-diphenyl-o-acetotoluidide
(2-amino-5-chlorophenyl)diphenylmethanol. Refer to Chart A (conversion of A-1 to A-2).
Phenylmagnesium bromide (267 ml of 3M solution in ether; 0.8 mole) is added during 35 minutes to a solution of 2-amino-5-chlorobenzophenone and the mixture is then refluxed for 4 hours. It is decomposed with 400 ml of water and stirred for 30 minutes. The ether layer is decanted, washed with 200 ml of water, and 200 ml of saturated salt solution, dried (MgSO 4 ) and evaporated. The residue is crystallized from 200 ml of ether and 200 ml of petroleum-ether (30°-60° C.) to give 31 g of yellow rods, mp 127°-128.5° C. The second crop: 15 g, mp 126°-28° C. Yield 73%. The analytical sample melted at 128°-129.5° C. Spectral data support the product structure.
Anal. Calcd. for C 19 H 16 ClNO: C, 73.66; H, 5.21; Cl, 11.45; N, 4.52.
Found: C, 73.31; H, 5.19; Cl, 11.45; N, 4.71.
This compound was reported in J. Gen. Chem. U.S.S.R. (Eng. Transl) 27, 539 (1957) by the reaction of methyl 5-chloroanthranilate with phenylmagnesium iodide; mp 123.5°-125° C.
(Conversion of A-2 to A-3).
Triethylamine (10.1 g; 0.1 mole) is added to a solution of (2-amino-5-chlorophenyl)diphenylmethanol (15.49 g; 0.05 mole) in 290 ml of ether, the solution is cooled to 5° C. and treated dropwise during one hour with a solution of chloroacetyl chloride (5.65 g; 0.05 mole) in 145 ml of ether keeping the temperature at 5° C. The mixture is then stirred at 5° C. for one hour, and at room temperature for 18 hours. It is cooled in ice, 290 ml of water is added, and the mixture stirred at room temperature for 30 minutes. The suspension is filtered, and the solid washed with water and ether to give 8.15 g of titled dichloro product with melting point of 185°-186.5° C. The filtrate is separated into layers and the aqueous layer is extracted once with ether. The combined ether extract is washed with cold solvents as follows: water (100 ml), 10% hydrogen chloride (3×50 ml), water, NaHCO 3 solution (3×50 ml), saturated salt solution. It is dried (MgSO 4 ) and evaporated. Crystallization from ether gives 5.05 g of titled product with a melting point of 184°-185° C. The analytical sample has mp 186°-187° C. Spectral evidence supports the titled product structure.
Anal. Calcd. for C 21 H 17 Cl 2 NO 2 : C, 65.29; H, 4.44; Cl, 18.36; N, 3.63.
Found: C, 65.24; H, 4.61; Cl, 18.46; N, 3.60.
Preparation 2
7-Chloro-1,5-dihydro-5,5-diphenyl-4,1-benzoxazepin-2(3H)-one
Refer to Chart A (conversion of A-3 to A-4).
A solution of the dichloro compound of Preparation 1 (88.84 g, 0.230 mole) in 460 ml of THF is added during 15 minutes to a suspension of NaH (19.36 l g, 0.46 moles of 57% dispersion in mineral oil, washed with ether) in 2300 ml of THF. The mixture is stirred at room temperature for 20 hours, and then refluxed for 1.75 hours. It is evaporated, the residue is cooled in ice and stirred with 2 liters of water for 30 minutes (200 ml of ether is added to aid solidification). The suspension is filtered, and the solid washed with water and ether. Crystallization from MeOH gives 48.53 g as prisms with a melting point of 211.5°-212.5° C. Second crop, 11.1 g with a melting point of 197°-198° C. These two different crops are both the titled compound. Spectral evidence supports the titled product structure.
Anal. Calcd. for C 21 H 16 ClNO 2 : C. 72.10; H, 4.61; Cl, 10.13; N, 4.01.
Found: C, 71.95; H, 4.48; Cl, 10.22; N, 4.02.
Preparation 3
7-Chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
Refer to Chart A.
2-Amino-5-chloro-α-methylbenzhydrol (conversion of A-1 to A-2).
Methylmagnesium bromide (267 ml of 3M ether-solution; 0.8 mole) is added during 45 minutes to a solution of 2-amino-5-chlorobenzophenone (46.3 g; 0.2 mole) in 1 liter of ether. The mixture is refluxed for 5 hours and allowed to stand overnight. It is then cooled in ice and decomposed with 400 ml of water. The ether layer is decanted, washed with saturated salt solution dried (MgSO 4 ) and evaporated. The residue is crystallized from ether-Skellysolve B to give 37.1 g (75% yield), mp 93°-94° C., unchanged on recrystallization. Spectral data support the product structure.
Anal. Calcd. for C 14 H 14 ClNO: C, 67.88; H, 5.70; Cl, 14.32; N, 5.65.
Found: C, 67.65; H, 5.73; Cl, 14.49; N, 5.46.
This compound was reported in Helv. Chim. Acta, 48, 336 (1965), mp 93°-94° C.
2,4'-Dichloro-2'-(α-hydroxy-α-methylbenzyl)-acetanilide
(Conversion of A-2 to A-3).
A solution of chloroacetyl chloride (2.3 g; 0.02 mole) in 50 ml of ether is added during 40 minutes to a solution of 2-amino-5-chloro-α-methylbenzhydrol (4.95 g; 0.02 mole) and triethylamine (4.95 g; 0.02 mole) in 100 ml of ether keeping the temperature at 5° C. The mixture is stirred overnight at room temperature. Water (100 ml) is added at 5° C. and the mixture is stirred at room temperature for 30 minutes. The organic layer is separated, washed with 10% hydrochloric acid (3×20 ml), then with saturated sodium bicarbonate solution (2×50 ml), dried (MgSO 4 ) and concentrated. The residue is crystallizaed from ether to give 4.3 g (66% yield) of colorless needles, mp 161°-162° C. unchanged on recrystallization. Spectral data support the product structure.
Anal. Calcd. for C 16 H 15 Cl 2 NO 2 : C, 59.27; H, 4.66; Cl, 21.87; N, 4.32.
Found: C, 59.41; H, 4.54; Cl, 22.04; N, 4.10.
(Conversion of A-3 to A-4).
A solution of 2,4'-dichloro-2'-(α-hydroxy-α-methylbenzyl)acetanilide (73.1 g; 0.23 mole) in 500 ml THF is added to a stirred suspension of sodium hydride (19.8 g, 57% dispersion in mineral oil; 0.48 mole) in 5000 ml THF and the mixture is stirred overnight. The mixture is refluxed for 5 hours and evaporated to near dryness. The residue is treated with 2000 ml cold water, and the resulting precipitate is filtered. Trituration with methanol and ether gives 56.2 g (87% yield) of titled product with a melting point of 219°-222° C. Spectral evidence supports the titled product structure.
Anal. Calcd. for C 16 H 14 ClNO 2 : C, 66.78; H, 4.90; N, 4.87; Cl, 12.32.
Found: C, 67.04; H, 4.76; N, 4.75; Cl, 12.41.
Preparation 4
2-Amino-α-methylbenzhydrol
Refer to Chart B (conversion of B-1 to B-2).
The titled compound is prepared according to the procedure of M. Stiles and A. J. Sisti, J. Org. Chem. 26, 3639 (1961), m.p. 84°-85° C. reported m.p. 84°-85° C.; uv (EtOH) λmax 238, 288; IR yields peaks at 3520, 3460, 3370, 1620, 1600, 1575 1495, 1165, 1070, 760 and 700 cm -1 ; NMR in CDCl 3 is in accord; mass spectrum; M + 213.
Preparation 5
2-Chloro-2'-(α-hydroxy-α-methylbenzyl)-acetanilide
Refer to Chart B (conversion of B-2 to B-3).
A solution of chloroacetyl chloride (51.6 l g; 0.46 mole) in 1000 ml ether is added with cooling (<10°) to a solution of the compound of Preparation 3 (97.4 g; 0.46 mole) and triethylamine (50.5 g; 0.50 mole) in 2750 ml ether. The mixture is stirred at room temperature overnight and treated with 2500 ml cold water. The ether layer is separated, washed with 10% hydrochloric acid, water, and saturated sodium bicarbonate solution, dried over magnesium sulfate and concentrated to 1000 ml by distillation. On cooling, there is crystallized 67.3 g of the titled product, m.p. 147°-148° C. A second crop is obtained by concentration to 300 ml, 36.5 g, m.p. 146°-147° (78% total yield). uv (EtOH) λmax 205, 246; IR 3410, 3300, 1665, 1605, 1585, 1495, 1525, 1260, 770, 765, and 705; nmr in DMSO-d 6 is in accord; mass spectrum: M + , 289; M + +2, 291.
Anal. Calcd. for C 16 H 16 ClNO 2 : C, 66.32; H, 5.51; N, 4.84; Cl, 12.24.
Found: C, 66.50; H, 5.49; N, 5.25; Cl, 12.50.
Preparation 6
1,5-Dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
Refer to Chart B (conversion of B-3 to B-4)
A solution of the compound of Preparation 5 (98.0 g, 0.34 mole) in 500 ml. THF is added to a stirred suspension of sodium hydride (30.0 g, 57% dispersion in mineral oil; 0.71 mole) in 2000 ml. THF, and the mixture is stirred overnight. The mixture is refluxed for 2 hours and evaporated to near dryness. The residue is treated with 2500 ml water and the resulting precipitate is filtered and washed with Skellysolve B. Recrystallization from methanol gives 64.0 g (74% yield), m.p. 156°-158°; uv (EtOH) λmax 207, 246, 257, 276, and 286; IR 3200, 3160, 3070, 1665; 1605, 1585, 1525, 1495, 1410, 1130, 770, 775, and 705 cm -1 ; nmr in DMSO-d 6 is in accord; mass spectrum: M + , 253.
Anal. Calcd. for C 16 H 16 NO 2 : C, 75.86; H, 5.97; N, 5.53.
Found: C, 75.95; H, 6.06; N, 5.61.
Preparation 7
1-(3-Bromopropyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
(Conversion of B-4 to B-6).
A mixture of sodium hydride (1.32 g, 50% mineral oil) and 7.19 g of the compound of Preparation 3 in 100 ml of DMF is heated at 95° C. for 1 hour and then is cooled to 35° C. and 1,3-dibromopropane (4 ml) is added. The mixture is heated at 90° C. for 5 hours, is allowed to stir overnight at 25° C. and is then neutralized with acetic acid and concentrated (using a vacuum pump). The residue is partitioned between methylene chloride and water. The organic extract is filtered through anhydrous sodium sulfate and concentrated. The residue is chromatographed on silica gel and elution with 15-50% ethyl acetate--Skellysolve B gives 3.77 g of crude product as a brown oil which is rechromatographed on silica gel (350 g). Elution (100 ml fractions) with 1-4% acetone-CH 2 Cl 2 gives 1.79 g of titled product in fractions 20-26 as an oil; 1 H NMR: 7.8-6.8, 4.1, 3.1, 1.77, 1.4; 13 C NMR: 167.67, 147.23; 141.07, 136.97, 131.83, 129.82, 128.51, 128.26, 127.15, 124.37, 124.02, 80.95, 67.06, 46.64, 31.98, 30.92, 29.94; Anal. Calcd. for C 19 H 19 BrClNO 2 : C, 55.83; H, 4.69; N, 3.43. Found: C, 56.07; H, 4.40; N, 3.52.
This reaction is also carried out in DMSO with dimsyl sodium to give a 33% yield of the titled compound.
EXAMPLE 1
1-(3-Phenoxypropyl)-7-chloro-1,5-dihydro-5,5-diphenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: Y 1 is 7-chloro, R 3 is phenyl, R 1 is phenoxy, n is one). Refer to Chart A (conversion of A-4 to A-5).
Sodium hydride (700 mg, 50% mineral oil) is degreased (2×20 ml hexane), dried under vacuum, mixed with 100 ml of dry dimethyl formamide (DMF); 3.5 g of the compound of Preparation 2 is then added. The mixture is stirred for 2 hours at 25° C., then sodium iodide (150 mg) and 3 ml of 3-phenoxypropyl bromide is added. After stirring overnight, the reaction mixture is neutralized with acetic acid and evaporated (vacuum pump). The residue is partitioned (methylene chloride/water), the organic extract filtered through sodium sulfate and evaporated. The residue is chromatographed on 350 g of silica gel packed in 1% acetone-methylene chloride. Elution (100 ml fractions) with 500 ml of 1%, 2% and 3% and 1 liter of 4% acetone-methylene chloride gives 4.4 g (91%) of pure titled product as a white foam in fractions 13-17. 1 H NMR (δ): 7.6-6.7, 4.35, 3.82, 3.1, 1.9; 13 C NMR (δ); 167.52, 158.60, 144.19, 142.24, 137.60, 131.51, 129.89, 129.50, 128.12, 127.85, 127.40, 124.03, 120.91, 114.53, 86.40, 67.85, 65.33, 46.93 and 27.91.
EXAMPLE 2
1-(3-Phenoxypropyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: Y 1 is 7-chloro, R 3 is methyl, R 1 is phenoxy, n is one). Refer to Chart A (conversion of A-4 to A-5).
A mixture of sodium hydride (2.1 g, 50% mineral oil) and 8.61 g of the compound of Preparation 3 in 120 ml of DMF is stirred at 95° C. for 1 hour and then is cooled to room temperature. Sodium iodide (450 mg) and 3-phenoxypropyl bromide (15 ml) is added and the mixture is stirred overnight at 25° C. The reaction mixture is worked up as in the previous example and the crude product is chromatographed on silica gel. Elution with 1% and 2% methanol-methylene chloride and crystallization of pure fractions from ether gives 3.4 g of titled product. Mother liquors were rechromatographed on silica gel eluting with methanol-methylene chloride or 2% acetone-methylene chloride to give an additional 2.8 g of titled product. A sample of titled product from another run is crystallized from ether; mp 134°-136° C.; 1 H NMR: 7.6-6.7, 4.1. 3.7, 3.1, 1.77, 1.7δ; 13 C NMR: 167.65, 158.59, 147.29, 141.55, 136.91, 131.67, 129.78, 129.73, 128.21, 127.10, 124.36, 120.83, 114.50, 80.95, 67.22, 65.30, 45.65, 31.92, 27.24 δ. Anal. Calcd. for C 25 H 24 ClNO 3 : C, 71.17; H, 5.73; N, 3.32; Cl, 8.4. Found: C, 71.42; H, 5.70; N, 3.36; Cl, 8.23.
EXAMPLE 3
1-(2-Phenoxyethyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: Y 1 is 7-chloro, R 3 is methyl, R 1 is phenoxy, n is zero) refer to Chart A (conversion of A-4 to A-5).
A 2.87 g sample of the compound of Preparation 3 is allowed to react with 4 g of β-bromophenetole (2-bromoethyl phenyl ether) essentially as described in Example 2 except that sodium iodide (150 mg) is added to the reaction mixture. The crude product is chromatographed on silica gel. Elution with 2% and 3% methanol-methylene chloride gives 3.29 g (81%) of titled product as a colorless glass; 1 H NMR (δ): 7.9-6.7, 4.1, 3.5, 3.0, 1.78; 13 C NMR: 167.96, 158.28, 147.42, 141.60, 136.95, 132.10, 129.91, 129.49, 128.25, 128.11, 127.17, 126.27, 124.31, 121.10, 114.44, 80.95, 67.07, 64.61, 48.87, and 31.72 δ.
EXAMPLE 4
1-(4-Phenoxybutyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: (Formula I: Y 1 is 7-chloro, R 3 is methyl, R 1 L is phenoxy, n is 2). Refer to Chart A (conversion of A-4 to A-5).
A 2.87 g sample of the compound of Preparation 3 is allowed to react with 4.6 g of 4-phenoxybutyl-bromide essentially as described above. Chromatography of the crude product on silica gel and elution with 2% and 3% methanol-methylene chloride gives 2.8 g (65%) of titled product as a colorless glass; 1 H NMR: 7.9-6.8, 4.1, 3.75, 3.05, 1.77, 1.7-0.8 δ; 13 C NMR: 167.34, 158.83, 147.26, 141.29, 137.03, 131.57, 129.64, 129.39, 128.38, 128.15, 126.99, 124.37, 124.08, 120.60, 114.41, 80.90, 67.09, 47.61, 31.92, 26.70 and 24.05 δ.
EXAMPLE 5
1-(3-Phenylpropyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: Y 1 is 7-chloro, R 3 is methyl, R 1 is phenyl, n is one). Refer to Chart A (conversion of A-4 to A-5).
A 2.87 g sample of the compound of Preparation 3 is allowed to react with 3 ml of 1-bromo-3-phenylpropane essentially as described above. Chromatography of the crude product on silica gel and elution with 2% and 3% methanol-methylene chloride gives 3.3 g (85%) of titled product as a colorless glass; 1 H NMR: 7.8-6.8, 4.1, 3.0, 2.35, 1.72 and 1.4 δ; 13 C NMR: 167.39, 147.19, 141.22, 141.03, 137.09, 131.57, 129.60, 128.23, 127.07, 125.91, 124.39, 123.99, 80.92, 67.19, 47.36, 33.21, 31.92, and 28.53 δ.
EXAMPLE 6
1-(3-Phthalimidopropyl)-7-chloro-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: R 1 is phthalimido, n is 1, Y 1 is 7-chloro, R 3 is methyl). Refer to Chart A (conversion of A-4 to A-5)
A 2.87 g sample of the compound of Preparation 3 is allowed to react with 4 g of N-(3-bromopropyl)phthalimide essentially as described above. The product obtained by chromatography on silica gel and elution with 3% and 5% methanol --CH 2 Cl 2 is crystallized twice from acetone-ether to give 1.38 g (29%) of titled product.
M.P. 151°-153° C.; 1 H NMR: 8.0-6.7, 4.1, 3.4, 3.0, 1.78, 1.3 δ; 13 C NMR (δ): 167.96, 167.41, 147.19, 141.10, 137.19, 133.97, 132.07, 131.83, 129.81, 128.44, 128.23, 127.12, 124.35, 123.19, 80.93, 67.06, 53.47, 45.54, 35.66, 31.88, 26.39; Anal. Calcd. for C 27 H 23 ClN 2 O 4 : C, 68.28; H, 4.88; N, 5.9; Cl, 7.46; Found: C, 68.32; H, 5.03; N, 5.91; Cl, 7.42.
EXAMPLE 8
7-Chloro-1-(cyclopropylmethyl)-1,5-dihydro-5,5-diphenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: R 1 is cyclopropylmethyl, Y 1 is 7-chloro, R 2 is phenyl). Refer to Chart B (conversion of B-4 to B-5).
The compound of Preparation 2 (3.49 g; 0.01 mole) is added to a suspension of NaH (0.421 l g, 0.01 mole of 57% dispersion in mineral oil washed with petroleum ether 30°-60° C.) in 100 ml of DMF. After 2 hours the resulting solution is treated during 2 minutes with a solution of (bromomethyl)cyclopropane (2.7 g; 0.02 mole) in 5 ml of DMF, and stirred at room temperature for 23 hours. It is evaporated and the residue is crystallized from ether to give 2.356 g of colorless rods, melting point 147°-148° C. The second crop: 0.72 g with melting point of 136°-148° C. contains some starting material by tlc. The analytical sample melted at 148°-149° C. Spectral evidence supports the titled product structure.
Anal. Calcd. for C 25 H 22 ClNO 2 : C, 74.34; H, 5.49; Cl, 8.78; N, 3.47.
Found: C, 74.45; H, 5.54; Cl, 8.79; N, 3.53.
EXAMPLE 9
7-Chloro-1-(cyclopropylmethyl)-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: R 1 is cyclopropylmethyl, R 2 is methyl, Y 1 is 7-chloro). Refer to Chart B (conversion of B-4 and B-5)
A mixture of sodium hydride (0.44 g, 57% dispersion in mineral oil; 0.01 mole) and the compound of Preparation 3 (2.87 g; 0.01 mole) in 100 ml DMF is stirred at room temperature for 2 hours. Cyclopropylmethyl bromide (2.70 g; 0.02 mole) is added in one portion, and the mixture kept overnight. The mixture is evaporated at reduced pressure and the residue treated with water and methylene chloride. The organic phase is washed with water and saturated salt solution, dried (MgSO 4 ) and evaporated. The residue is chromatographed on silica gel (200 g) eluting with chloroform in 25 ml fractions. Fractions 1-30 contain no material; fractions 31-79 contain the titled product, recrystallized from ether-petroleum ether (30°-60° C.), 2.0 g (59% yield) with a melting point of 87°-88° C.; succeeding fractions contain the titled product of Preparation 3 (based on tlc). Spectral evidence supports the titled product structure.
Anal. Calcd. for C 20 H 20 ClNO 2 : C, 70.26; H, 5.90 N, 4.09; Cl, 10.37.
Found: C, 69.98; H, 6.01; N, 4.08; Cl, 10.36.
EXAMPLE 10
7-Chloro-1-[2-(dimethylamino)ethyl]-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one and its hydrochloride
(Formula I: R 1 is dimethylaminoethyl, R 2 is methyl, Y 1 is 7-chloro). Refer to Chart B (conversion of B-4 to B-5).
A mixture of sodium hydride (0.67 g, 57% dispersion in mineral oil; 0.016 mole) and the compound of Preparation 3 (4.32 g; 0.015 mole) in 100 DMF is heated at 95° C. for one hour. A solution of 1-chloro-2-(dimethylamino)ethane (3.44 g, 50% solution in xylene; 0.015 mole) (obtained by neutralization of the hydrochloride and distillation) in 50 ml DMF is added dropwise in 20 minutes and heating continued for 5 hours. The mixture is evaporated at reduced pressure and the residue treated with water and methylene chloride. The organic phase is washed with water, 10% HCl, and saturated salt solution, dried (MgSO 4 ), and evaporated. Recrystallization from ethanol-ether gives 3.6 g (61% yield) of the titled product with a melting point of 236°-238° C. Spectral evidence supports the titled product structure.
Anal. Calcd. for C 20 H 23 ClN 2 O.HCl: C, 60.76; H, 6.12; N, 7.09; Cl, 17.94.
Found: C, 60.44; H, 6.15; N, 7.11; Cl, 17.60.
EXAMPLE 11
7-Chloro-1-[3-(dimethylamino)propyl]-1,5-dihydro-5-methyl-5-phenyl-4,1-benzoxazepin-2(3H)-one and its maleate
(Formula I: R 1 is 3-(dimethylamino)propyl, R 2 is methyl, Y 1 is 7-chloro). Refer to Chart B (conversion of B-4 to B-5).
A mixture of sodium hydride (0.67 g, 57% dispersion in mineral oil; 0.016 mole) and the compound of Preparation 3 (4.32 g; 0.015 mole) in 100 ml DMF is heated at 95° C. for 30 minutes. A solution of 1-chloro-3-(dimethylamino)propane (3.22 g, 50% solution in xylene; 0.015 mole) (obtained by neutralization of the hydrochloride and distillation) in 50 ml DMF is added dropwise in 30 minutes and heating continued for 5 hours. The mixture is evaporated at reduced pressure and the residue treated with water and methylene chloride. The organic phase is washed with water and saturated salt solution and extracted with 10% HCl. The aqueous extract is neutralized with 40% sodium hydroxide and extracted with ether. The organic phase is dried (MgSO 4 ) and evaporated to give 3.1 g of the titled free base, a yellow oil (single component by tlc; 9:1 CHCl 3 :MeOH, silica gel). The oil is treated with maleic acid (1.00 g; 0.0086 mole) in 100 ml ether. Recrystallization gives 3.1 g (42% yield) of titled maleate product with a melting point of 142° C. Spectral evidence supports the titled product structure.
Anal. Calcd. for C 21 H 25 ClN 2 O 2 .C 4 H 4 O 4 : C, 61.41; H, 5.98; N, 5.73; Cl, 7.25.
Found: C, 61.51; H, 6.40; N, 5.86; Cl, 7.24.
EXAMPLE 12
1,5-dihydro-1-[3-(dimethylamino)propyl]-5-methyl-5-phenyl-4,1-Benzoxazepin-2(3H)-one, hydrochloride
(Formula I: R 1 is -(dimethylamino)propyl, R 2 is methyl, Y 1 is hydrogen). Refer to Chart B (conversion of B-4 to B-5).
A solution of 2.53 g (10.0 mmol) of the compound of Preparation 6 in 50 ml of dimethylformamide is treated with 0.53 g of 50% sodium hydride in oil (11.0 mmol) until dissolved. The reaction is heated (steam bath) for one hour then cooled slightly. Meanwhile, a solution of 5 g of 3-(dimethylamino)propyl chloride hydrochloride in water is saturated with sodium chloride, covered with ether and made basic with 5% sodium hydroxide solution. The mixture is extracted three times with ether which is washed with saline, dried and carefully evaporated. The residue remaining, 2.77 g (22.8 mmol) is dissolved in 5 ml of dimethyl formamide and added to the hydride reaction. The mixture is stirred well, heated (steam bath) for one hour then allowed to stir at ambient overnight. Further heating does not increase the amount of product (TLC 8% methanol-methylene chloride). Solvent is removed by rota-vac and the residue diluted with water and extracted with methylene chloride. After washing with water, the free amine is converted to the hydrochloride by washing well with 10% hydrochloric acid solution. After washing with saturated saline the solution is dried, evaporated and the residue crystallized from acetone-SSB to give 0.95 g. Chromatography of mother liquors over 10 g of silica gel with 2-10% methanol-methylene chloride gives an additional 0.70 g. Combining and recrystallization from acetone-SSB gives 1.12 g.
Anal. Calcd. for C 21 H 27 N 2 O 2 Cl.H 2 O: C, 64.19; H, 7.44; N, 7.13; Cl, 9.02.
Found: C, 63.86; H, 7.18; N, 7.05; Cl, 9.60.
IR (thin film) peaks at 3495, 3391, 3074, 3064, 3038, 3013, 2636, 2615, 2520, 2481, 1659, 1642, 1602, 1581, 1497, 1109, 1091, 768, and 702.
Mass spectrum peaks at 338, 280, and 58.
EXAMPLE 13
7-chloro-1,5-dihydro-5-methyl-5-phenyl-1-[3-(1-pyrrolidinyl)propyl]-4,1-benzoxazepin-2(3H)-one, hydrochloride
(Formula I: R 1 is 3-(1-pyrrolidinyl)propyl, R 2 is methyl, Y 1 is 7-chloro). Refer to Chart B (conversion of B-6 to B-5).
A mixture of 1.6 g of the compound of Preparation 7 and pyrrolidine (4.5 ml) in chloroform (9.5 ml), 2-propanol (15 ml) and acetonitrile (15 ml) is stirred at 50° C. for 3 days. The mixture is evaporated and the residue partitioned between CH 2 Cl 2 (30 ml) and 50 ml of water containing 2 ml of 6N HCl.
The aqueous phase is reextracted with CH 2 Cl 2 (30 ml) and the combined extracts are washed with brine, dried over sodium sulfate and evaporated. The residue is crystallized from ether-methanol to give 1.19 g of a pale brown solid, mp 194°-198° C. Chromatography on silica gel and elution with 20% methanol-CH 2 Cl 2 does not remove the color.
The column eluates are partitioned between CH 2 Cl 2 and aqueous HCl as described and the residue is crystallized from methanol-ether to give the titled product; m.p. 196°-198° C.; 13 C NMR: 167.94, 147.54, 140.75, 136.64, 132.23, 130.27, 128.29, 127.09, 124.94, 124.34, 80.90, 66.87, 53.88, 52.77, 45.36, 31.89, 24.06, 23.32. Anal. Calcd. for C 23 H 28 Cl 2 N 2 O 2 : C, 63.44; H, 6.48; N, 6.44; Cl, 16.29. Found: C, 63.31; H, 6.72; N, 6.38; Cl, 16.29.
EXAMPLE 14
7-Chloro-1-[3-(dimethylamino)propyl]-1,5-dihydro-5,5-diphenyl-4,1-benzoxazepin-2(3H)-one
(Formula I: R 1 is 3-(dimethylamino)propyl, R 2 is phenyl, Y 1 is 7-chloro).
Refer to Chart B (conversion of B-4 to B-5).
Sodium hydride (0.421 g; 0.01 mole of 57% dispersion in mineral oil) is added to a solution of the compound of Preparation 2 (3.49 g; 0.01 mole) in 100 ml of DMF and the mixture is stirred for 2.5 hours. The resulting solution is treated with a solution of 3-(dimethylamino)propyl chloride (2.42 g, 0.02 mole, two equivalents) in 2.42 g of xylene and the mixture is heated at 95° C. for 23 hours. It is evaporated and the residue taken up in 100 ml each of water and CH 2 Cl 2 . The organic layer is dried (MgSO 4 ) and evaporated. The residue (3 g) is chromatographed on 300 g of silica gel using CHCl 3 (1% Et 3 N). Fractions 1-90 (25 ml each) give no material. With 1% MeOH--CHCl 3 (1% Et 3 N) fractions 91-137 give no material. Fractions 138- 152 give (0.335 g (single spot) that is crystallized from MeOH to give 0.128 g of starting material, m.p. 209°-210° C. Fractions 153-165 give 0.318 g (two spots) which is crystallized from ether to give 22 mg of starting material.
With 2% MeOH--CHCl 3 (1% Et 3 N) fractions 181-223 give no material. Fractions 224-249 give 1.601 g (2 spots) which is crystallized from ether (save filtrate) to give 0.501 g of titled product; m.p. 134.5°-137° C. raised to 138°-139° C. on recrystallization, uv λmax 204, 253, 257, 264, 271. IR 3060, 2780, 2760, 2720, 1645, 1595, 1565, 1485, 1415, 1170, 1100, 1080, 820, 750 and 700 cm -1 . NMR in CDCl 3 and 100 MHz is in accord.
EXAMPLE 15
7-Chloro-1-[2-(dimethylamino)ethyl]-1,5-dihydro-5,5-diphenyl-4,1-benzoxazepin-2(3H)-one hydrochloride
(Formula I: R 1 is 2-(dimethylamino)ethyl, R 2 is phenyl, Y 1 is 7-chloro). Refer to Chart B (conversion of B-4 to B-5).
Sodium hydride (0.421 g; 0.01 mole of 57% dispersion in mineral oil; washed with petroleum-ether 30°-60° C.) is added to a solution of the compound of Preparation 2 (3.49 g; 0.01 mole) in 100 ml of DMF, and the mixture is stirred for 2.5 hr. The resulting solution is treated with a solution of 2-(dimethylamino)ethyl chloride (1.07 g; 0.01 mole) in xylene and heated at 95° for 19 hr. It was evaporated and the residue taken up in 25 ml of water and 50 ml of CH 2 Cl 2 . The aqueous layer is extracted once with CH 2 Cl 2 . Extraction of the CH 2 Cl 2 solution with 10% of HCl caused a distribution of the hydrochloride between the organic and the aqueous layers. Therefore, a solution of the product as the free base (4.05 g) in 10 ml of CHCl 3 is chromatographed on 405 g silica gel using 2% MeOH--CHCl 3 (1% Et 3 N). Fractions 1-10 (925 ml total) gives some mineral oil. Fractions 11-12 (25 ml from now on) give 0.361 g of starting material. Fractions 14-17 (2.68 g) give the desired product which is converted to the hydrochloride in ether with ethereal HCl. Crystallization from MeOH-ether gives colorless needles: 1.832 g, m.p. 260°-261° C. The analytical sample melts at 261°-262° C. UV λmax 253, 257, 264, 271; IR 3270, 2560, 2380, 1685, 1595, 1565, 1485, 1445, 1420, 1320, 1150, 885, 795, 765, 755 and 705. NMR in d 6 DMSO indicates some enolic form to be present. Mass spectrum peak at 420.
Anal. Calcd. for C 25 H 25 ClN 2 O 2 .HCl: C, 65.65; H, 5.73; Cl, 15.50; N, 6.13. Found: C, 65.46; H, 5.93; Cl, 15.37; N, 5.85.
EXAMPLE 16
Following the procedures of the preceding Examples, and using the appropriate starting materials, all of the other compounds within the scope of this application are prepared. ##STR1## | The present invention provides certain novel 4,1-benzoxazepin-2(3H)-ones which are useful as inhibitors of phospholipase A 2 and thus as inhibitors of arachidonate mobilization. These compounds are thus useful whenever it is medically necessary or desirable to inhibit the biosynthesis of the products of the arachidonic acid cascade. | 2 |
This is a continuation application of application Ser. No. 07/449,966 filed Dec. 12, 1989 now abandoned.
FIELD OF THE INVENTION
The invention relates to an exhaust gas cleaning device for diesel engines, comprising an exhaust gas soot filter having a filter body supported in a housing. The filter body being regenerated by combustion of the soot when its temperature rises above the middle operating exhaust gas temperature range.
BACKGROUND OF THE INVENTION
The exhaust gas of diesel engines contains more or less high concentrations of soot particles which are pollutive or even are rated as being a potential hazard to health when present in the breathing air in higher concentrations. This is the reason why endeavors have been made for some time to decontaminate the exhaust gases of diesel engines by removing the soot particles at least to a large extent. As technically most promising measure in the respect, exhaust gas soot filters have been conceived which are designed in their porosity such that they largely retain the soot particles from the exhaust gas flowing therethrough. These soot filters often consist of ceramic material because of the required temperature and strength needed with respect to the usual exhaust gas temperatures of diesel engines. These soot filters also have the tendency of becoming clogged with prolonged time of operation. It was hoped that the soot particles caught in the soot filter would be burnt off virtually to the same extent in which new particles accumulate, and in particular in relation with higher output conditions of the respective diesel engine. However, it has become evident that this hope is not fulfilled at least with a multiplicity of diesel engines. In particular such engines which are not often enough operated in operating conditions with relatively high exhaust gas temperatures. Instead, a constantly increasing accumulation of soot particles in the soot filter takes place which, thus, reaches in increasing manner a condition of undesirably high exhaust gas flow resistance.
SUMMARY AND OBJECTS OF THE PRESENT INVENTION
It is the object of the invention to provide an exhaust gas cleaning device of the type indicated at the outset, which provides more effective regeneration, i.e. more effective soot decomposition, of the exhaust gas soot filter.
For meeting this object it is provided according to the invention that a burner with a combustion air fan is provided whose hot gas side is in flow communication with the exhaust gas soot filter, and that the filter body is supported in its housing such that at least a large part of its outer surface is heated externally during operation of the burner.
Thus, according to the invention care is taken that temperature allowing soot combustion, which are higher than the normal operational exhaust gas temperatures, are present at the soot filter for regeneration thereof, and that the edge portions of the soot filter, which are particularly critical as regards regeneration, are (additionally) heated from the outer surface thereof.
The middle, i.e. operationally normal, exhaust gas temperature range of diesel engines is approximately 200° to 400° C., with temperature peaks during operation in the maximum output range being left unconsidered. The term "outer surface" designates that portion of the outside surface of the soot filter which is not the exhaust gas entry side or the exhaust gas exit side. It may be that, by means of the filter body support according to the invention, almost this entire outer surface of the filter body is heated from the outside. This external heating usually takes place indirectly through a filter body enclosure provided there. The burner usually is in flow communication with the inflow side of the exhaust gas soot filter. By the design of the exhaust gas soot filter according to the invention, a unit having the combined effect of a sound absorber and a soot filter can be made available.
Exhaust gas soot filters often have a substantially prismatic configuration with an exhaust gas entry side and an exhaust gas exit side and a cross-section, transversely of the exhaust gas flow direction, of circular, elliptical, oval, rectangular, square or the like configuration. The term "prismatic configuration" is to cover also such geometries in which the exhaust gas entry side and/or the exhaust gas exit side are not at right angles to the direction of flow through the soot filter and/or in which the outer (circumferential) surface of the soot filter varies progressively within certain limits in the direction of flow therethrough.
For supporting the filter body in the housing of the exhaust gas soot filter, especially with the aforementioned geometries, there are quite a number of possibilities which, according to the invention, permit heating of the outer surface or outer circumference, however care has to be taken in this respect that a flow of the exhaust gases externally past the filter body is to be avoided at least preferably, for ensuring the effective separation of the soot particles from the entire exhaust gas stream. For instance, it would be possible to support the filter body by strut-like supporting parts in its housing in circumferentially spaced manner, and to provide at one location a flow-preventing barrier in the annular gap between the filter body and the housing. Especially preferred is the support of the filter body by means of several ring-like holders which are spaced in the direction of flow and which have perforations in such a number and size that gas can flow therethrough, however, one thereof being closed so as to prevent the afore-mentioned free flow of exhaust gas around the annular gap. It is to be noted that the terms "ring-like" and "annular gap" by no means are supposed to mean "ring-shaped in circular manner", but are to be understood in their comprehensive sense and comprise in particular also oval, elliptical and angular configurations which as a whole are closed in ring-like or annular manner.
The exhaust gas cleaning device according to the invention preferably comprises as filter body a ceramic monolith having discontinuous flow channels, as it is known per se. The most frequent configuration resides in that the flow channels extending substantially in the overall flow direction through the filter body are alternatingly closed at the entry side of the filter body and at the exit side of the filter body, so that the exhaust gas entering a flow channel on the entry side cogently must pass through the porous wall of the particular flow channel into one or several adjacent flow channels in order to be able to leave the filter body on the flow exit side.
The burner preferably is a burner composed in accordance with the principle of a vaporizing burner.
In accordance with a particularly preferred embodiment of the invention the burner is provided for regenerative operation in operational pauses of the diesel engine after a longer diesel engine operational phase each. Thus, according to this embodiment, the burner is not constantly kept in operation in order to sufficiently increase the exhaust gas temperature at the entry to the filter body, but rather one prefers intermittent operation in which the soot filter is regenerated within a quite short period of time during a standstill phase of the diesel engine. In this respect, operation of the burner with excess air is favorable in order to have available in the soot filter oxygen for burning the soot deposited there. The embodiment mentioned renders the combustion of soot especially effective since the hot gases of the burner are not mixed with colder diesel engine exhaust gas.
The exhaust gas cleaning device preferably comprises a control means of the burner which at the beginning of the regenerative operation turns on the combustion air fan and a flow plug for igniting the fuel for the burner, additionally turns on a fuel pump of the burner in time-delayed manner, turns off the glow plug after ignition of the burner since the latter now burns on without aid of the glow plug, and, after a certain time, turns off the fuel pump and allows the combustion air fan to still remain in operation for a short or a longer period of time. This control means controls the said phases of the regenerative operation preferably automatically.
Preferably, a sensor is provided which directly or indirectly detects the amount of clogging of the filter body with soot and which either delivers a signal that new regeneration is necessary, and/or which suitably triggers regeneration on its own, preferably during the next standstill of the diesel engine. The sensor, for instance, can be responsive to the pressure increase in front of the soot filter caused by increased clogging, can operate on the basis of the measurement of gas flow velocities, or the like. It is also possible to employ a device for determining the operating time of the diesel engine since the last regeneration.
The burner preferably is designed such that it brings the filter body to a regeneration temperature of more than 500° C., most preferably of more than 600° C. or even more than 700° C. The burner need not be in operation for the entire regeneration period, since the once ignited soot still burns down also without the aid from the burner and since heat is released in doing so. The burner, furthermore, is preferably designed such that a relatively short regeneration time of some minutes to approx. thirty minutes, depending on the size of the filter body, is sufficient. During combustion of the soot, temperatures in the range of 850° C. may occur.
Preferably, a burner and a combustion air fan for the burner are used as they are already commercially available, especially with respect to motor vehicle heating devices that are independent of the engine.
A particularly preferred field of use of the exhaust gas cleaning device according to the invention are vehicles, in particular fork lifters, which are used in at least largely closed buildings, such as for instance fabrication shops, storehouses or the like. In case of such conditions of use, the exhaust of soot is particularly annoying, and regeneration can be carried out in convenient manner for instance at the end of a shift.
The features of some of the dependent claims, are of inventive significance also without the particular dependence of the claim or in combination with only part of the features of superior claims.
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 specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which preferred embodiments of the invention are illustrated.
BRIEF DESCRIPTION OF THE DRAWINGS
In the drawings:
The invention and further developments thereof will now be elucidated in more detail by way of a preferred embodiment shown in the drawing. The sole drawing shows a longitudinal sectional view of an exhaust gas soot filter and a burner connected thereto.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The exhaust gas soot filter 2 consists essentially of a housing 4 of sheet steel having a ceramic monolithic filter body 6 supported therein. The housing 4 is cylindrical in its central portion and conically tapers on its left-hand and right-hand sides to the diameter of an exhaust gas line 8. The exhaust gas flow direction through the soot filter 2 in the drawing is from right to left, as indicated by arrow P. The exhaust gas line section incoming from the right-hand side comes from a diesel engine and the exhaust gas line section outgoing to the left-hand side leads to the end of the exhaust system. The filter body 6 also is cylindrical and has flow channels 10 which extend substantially parallel to the common longitudinal axis 12 of the filter body 6 and the housing 4. The flow channels 10 are closed in alternating manner on the right-hand side and on the left-hand side.
Furthermore, it is possible to see an intermediate carrier 14 of sheet steel which is substantially cylindrical and has flange portions 16 drawn inwardly at the left-hand and right-hand ends thereof. The filter body 6 is held axially between the two flange portions 16 by means of resilient intermediate rings 18 of sufficiently temperature-resistant material. For reasons of thermal expansion, a narrow gap is present in the radial direction between the filter body 6 and the intermediate carrier 14. The intermediate carrier 14 in turn is welded by means of two annular holders 20 to the interior of the cylindrical portion of the housing 4 so that a circular, annular gap 22 is present between the filter body 6 or the intermediate carrier 14 and the housing 4. The annular gap 22 has a radial width of 5 to 20 mm. the two holders 20 are spaced in an axial direction and are each located closer to an axial end of the intermediate carrier 14 than to the center thereof.
The left-hand, i.e. downstream holder 20 as shown in the drawing is provided across the entire circumference thereof with, for instance, circular openings or perforations 24. These perforations would instead also be provided in the right-hand holder 20 in the drawing. It would also be possible to provide in the left-hand holder larger and numerous perforations 24, while the right-hand holder 20 is provided only with few and small perforations, or vice versa, so that a very small amount of exhaust gas can flow through the annular gap 22 from the front to the rear. The annular gap 22 axially between the two holders 20 may also be filled with a sufficiently temperature-resistant insulating material, for instance basalt wool. The soot filter 2 shown in the drawing and described thus far at the same time serves as an exhaust sound absorber, with the annular space 22 constituting a resonance space.
The conical portion of the housing 4 shown on the right-hand side in the drawing, i.e. the portion on the inflow side, has a burner 26 connected thereto which has a combustion air fan 28. In addition thereto it is possible to see a fuel pump 30 for the fuel of the burner 26, which is for instance diesel oil, and a glow plug 32 for igniting the fuel-air mixture formed in the burner. Finally, one can see a control unit 34 for the burner 26 or the unit formed by the burner 26 and the combustion air fan 28.
When the soot filter 6 is clogged with soot particles to a considerable extend especially after operation of the diesel engine for several hours, regeneration of the filter body 6 is carried out preferably in an operational pause of the diesel engine. For doing so, the combustion air fan 28 and the glow plug 32 are first turned on by means of the control unit 34. After approx. 30 to 60 sec. the fuel metering pump 30 is turned on as well, which feeds fuel into the combustion chamber of the burner 26. When combustion has properly started therein, which can be determined by flame monitoring, the glow plug 32 is turned off, and the combustion air fan 28 continues its operation. The combustion operation of the burner goes on, depending on the size of the soot filter 2, for approx. 2 to 10 min., and a temperature in the order of magnitude of 600° to 750° C. is reached at the filter body 6 within this "activation time". The burner 26 can be turned off now since at this temperature combustion of the soot at the filter body 6 has started and continues also without the aid of the burner. The oxygen necessary therefor can either be taken from the exhaust system (which, as is known, still contains residual oxygen in case of diesel engines), or it can be taken in through the combustion air fan 28 and the burner 26. It is also possible to have the combustion air fan 28 continue its operation, for instance also at a lower level. This combustion of soot takes approx. 5 to 30 minutes depending on the size of the soot filter 2, and during this time the temperature at the filter body 6 may still slightly increase due to the soot combustion, or may remain essentially the same or may drop slightly. After the afore-described turning-off of the burner 27 by turning off the fuel metering pump 30, the combustion air fan 28 definitely is still kept in operation for a certain time, for instance 2 to 4 min., so that no more combustible fuel-air mixture is left in the burner 26.
Reference numeral 36 designates a pressure probe in the space in front of the filter body 6. The pressure probe 36 is responsive to increased pressure caused by increasing clogging of the filter body 6 and indicates the necessity of new regeneration and/or automatically triggers such new regeneration via the control unit 34. This regeneration occurs preferably in a subsequent operational pause of the diesel engine.
Due to the perforations 24 in the left-hand holder 20 the hot gases of the burner 26, after flowing through the filter body 6, can enter into the annular gap 22 and also heat the filter body 6 externally by its outer surface or outer circumference. This heating becomes effective through the intermediate carrier 14. This outer circumference heating is essential for bringing especially the marginal portions of the filter body 6, which are hard to heat without the measure described, to a sufficiently high temperature. When more than two spaced holders 20 are provided, all of all but one thereof are provided with perforations 24.
The output of the burner is in the region of 2 to 15 kW, depending on the size of the soot filter 2.
The soot filter 2 may also have several filter bodies 6 in an axially successive arrangement, and in this case it will be sufficient--when an external flow of exhaust gas past all filter bodies is to be excluded--to provide a surrounding exhaust gas flow barrier at only one of the filter bodies. | An exhaust gas cleaning device for diesel engines has an exhaust gas soot filter (2) with a filter body (6) that is supported in a housing (4) and is regenerated by combustion of the soot when its temperature rises above the middle operating exhaust gas temperature range. A burner (26) is provided, having a combustion air fan (28) whose hot gas side is in flow communication with the exhaust gas soot filter (2), and the filter body (6) is supported in its housing in such a manner that at least a large part of its outer surface is heated externally during operation of the burner (26). | 8 |
This application claims benefit of U.S. Divisional Application No. 60/170,179, filed on Dec. 10, 1999.
BACKGROUND OF THE INVENTION
The present invention relates to pyrrolo[2,3-d]pyrimidine compounds which are inhibitors of protein kinases, such as the enzyme Janus Kinase 3 (hereinafter also referred to as JAK3) and as such are useful therapy as immunosuppressive agents for organ transplants, xeno transplation, lupus, multiple sclerosis, rheumatoid arthritis, psoriasis, Type I diabetes and complications from diabetes, cancer, asthma, atopic dermatitis, autoimmune thyroid disorders, ulcerative colitis, Crohn's disease, Alzheimer's disease, Leukemia and other indications where immunosuppression would be desirable.
This invention also relates to a method of using such compounds in the treatment of the above indications in mammals, especially humans, and the phamaceutical compositions useful therefor. JAK3 is a member of the Janus family of protein kinases. Although the other members of this family are expressed by essentially all tissues, JAK3 expression is limited to hematopoetic cells. This is consistent with its essential role in signaling through the receptors for IL-2, IL-4, IL-7, IL-9 and IL-15 by non-covalent association of JAK3 with the gamma chain common to these multichain receptors. XSCID patient populations have been identified with severely reduced levels of JAK3 protein or with genetic defects to the common gamma chain, suggesting that immunosuppression should result from blocking signaling through the JAK3 pathway. Animal studies have suggested that JAK3 not only plays a critical role in B and T lymphocyte maturation, but that JAK3 is constitutively required to maintain T cell function. Modulation of immune activity through this novel mechanism can prove useful in the treatment of T cell proliferative disorders such as transplant rejection and autoimmune diseases.
SUMMARY OF THE INVENTION
The present invention relates to a compound of the formula
or the pharmaceutically acceptable salt thereof; wherein
R 1 is a group of the formula
wherein y is 0, 1 or 2;
R 4 is selected from the group consisting of hydrogen, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkylsulfonyl, (C 2 -C 6 )alkenyl, and (C 2 -C 6 )alkynyl wherein the alkyl, alkenyl and alkynyl groups are optionally substituted by deuterium, hydroxy, amino, trifluoromethyl, (C 1 -C 4 )alkoxy, (C 1 -C 6 )acyloxy, (C 1 -C 6 )alkylamino, ((C 1 -C 6 )alkyl) 2 amino, cyano, nitro, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl or (C 1 -C 6 )acylamino or R 4 is (C 3 -C 10 )cycloalkyl wherein the cycloalkyl group is optionally substituted by deuterium, hydroxy, amino, trifluoromethyl, (C 1 -C 6 )acyloxy, (C 1 -C 6 )acylamino, (C 1 C 6 )alkylamino, ((C 1 -C 6 )alkyl) 2 amino, cyano, cyano(C 1 -C 6 )alkyl, trifluoromethyl(C 1 -C 6 )alkyl, nitro, nitro(C 1 -C 6 )alkyl or (C 1 -C 6 )alkylamino;
R 5 is (C 2 -C 9 )heterocycloalkyl wherein the heterocycloalkyl groups must be substituted by one to five carboxy, cyano, amino, deuterium, hydroxy, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, halo, (C 1 -C 6 )acyl, (C 1 C 6 )alkylamino, amino(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy-CO—NH, (C 1 -C 6 )alkylamino-CO—, (C 2 -C 6 )alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 )alkylamino, amino(C 1 -C 6 )alkyl, hydroxy(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy(C 1 -C 6 )alkyl, (C 1 -C 6 )acyloxy(C 1 -C 6 )alkyl, nitro, cyano(C 1 -C 6 )alkyl, halo(C 1 -C 6 )alkyl, nitro((C 1 -C 6 )alkyl, trifluoromethyl, trifluoromethyl((C 1 -C 6 )alkyl, (C 1 -C 6 )acylamino, (C 1 -C 6 )acylamino(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy(C 1 -C 6 )acylamino, amino(C 1 -C 6 )acyl, amino(C 1 -C 6 )acyl(C 1 -C 6 )alkyl, (C 1 -C 6 )alkylamino(C 1 -C 6 )acyl, ((C 1 -C 6 )alkyl) 2 amino(C 1 -C 6 )acyl, R 15 R 16 N—CO—O—, R 15 R 16 N—CO—(C 1 -C 6 )alkyl, (C 1 -C 6 )alkyl-S(O) m , R 5 R 16 NS(O) m , R 15 R 16 NS(O) m (C 1 -C 6 )alkyl, R 15 S(O) m R 16 N, R 15 S(O) m R 16 N(C 1 -C 6 )alkyl, wherein m is 0, 1 or 2 and R 15 and R 16 are each independently selected from hydrogen or (C 1 -C 6 )alkyl, or a group of the formula
wherein
a is 0, 1, 2, 3 or 4;
b, c, e, f and g are each independently 0 or 1;
d is 0, 1, 2, or 3;
X is S(O) n wherein n is 0, 1 or 2; oxygen, carbonyl or —C(═N-cyano)-;
Y is S(O) n wherein n is 0, 1 or 2; or carbonyl; and
Z is carbonyl, C(O)O—, or S(O) n wherein n is 0, 1 or 2;
R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are each independently selected from the group consisting of hydrogen and (C 1 -C 6 )alkyl optionally substituted by deuterium, hydroxy, amino, trifluoromethyl, (C 1 -C 6 )acyloxy, (C 1 -C 6 )acylamino, (C 1 -C 6 )alkylamino, ((C 1 -C 6 )alkyl) 2 amino, cyano, cyano((C 1 -C 6 )alkyl, trifluoromethyl((C 1 -C 6 )alkyl, nitro, nitro(C 1 -C 6 )alkyl or (C 1 -C 6 )acylamino;
R 12 is carboxy, cyano, amino, oxo, deuterium, hydroxy, trifluoromethyl, (C 1 -C 6 )alkyl, trifluoromethyl(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, halo, (C 1 -C 6 )acyl, (C 1 -C 6 )alkylamino, ((C 1 -C 6 )alkyl) 2 amino, amino(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy-CO—NH, (C 1 -C 6 )alkylamino-CO—, (C 2 -C 6 )alkenyl, (C 2 -C 6 ) alkynyl, (C 1 -C 6 )alkylamino, hydroxy(C 1 -C 6 )alkyl, ((C 1 -C 6 )alkoxy((C 1 -C 6 )alkyl, (C 1 -C 6 )acyloxy((C 1 -C 6 )alkyl, nitro, cyano(CH 1 -C 6 )alkyl, halo((C 1 -C 6 )alkyl, nitro((C 1 -C 6 )alkyl, trifluoromethyl, trifluoromethyl(C 1 -C 6 )alkyl, (C 1 -C 6 )acylamino, (C 1 -C 6 )acylamino((C 1 -C 6 )alkyl, (C 1 C 6 )alkoxy(C 1 -C 6 )acylamino, amino((C 1 -C 6 )acyl, amino((C 1 -C 6 )acyl((C 1 -C 6 )alkyl, (C 1 C 6 )alkylamino(C 1 -C 6 )acyl, ((C 1 -C 6 )alkyl) 2 amino((C 1 -C 6 )acyl, R 15 R 16 N—CO—O—, R 15 R 16 N—CO—(C 1 -C 6 )alkyl, R 15 C(O)NH, R 15 OC(O)NH, R 15 NHC(O)NH, (C 1 -C 6 )alkyl-S(O) m , (C 1 -C 6 )alkyl-S(O) m -(C 1 -C 6 )alkyl, R 15 R 16 NS(O) m , R 15 R 16 NS(O) m (C 1 -C 6 )alkyl, R 15 S(O) m R 16 N, or R 15 S(O) m R 16 N(C 1 -C 6 )alkyl, wherein m is 0, 1 or 2 and R 15 and R 16 are each independently selected from hydrogen or (C 1 -C 6 )alkyl;
R 2 and R 3 are each independently selected from the group consisting of hydrogen, deuterium, amino, halo, hydroxy, nitro, carboxy, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, trifluoromethyl, trifluoromethoxy, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy, and (C 3 -C 10 )cycloalkyl wherein the alkyl, alkoxy or cycloalkyl groups are optionally substituted by one to three groups selected from halo, hydroxy, carboxy, amino (C 1 -C 6 )alkylthio, (C 1 -C 6 )alkylamino, ((C 1 -C 6 )alkyl) 2 amino, (C 5 -C 9 )heteroaryl, (C 2 -C 9 )heterocycloalkyl, (C 3 -C 9 )cycloalkyl or (C 6 -C 10 )aryl; or R 2 and R 3 are each independently (C 3 -C 10 )cycloalkyl, (C 3 -C 10 )cycloalkoxy, (C 1 -C 6 )alkylamino, (C 1 -C 6 )alkyl) 2 amino, (C 6 -C 10 )arylamino, (C 1 -C 6 )alkylthio, (C 6 -C 10 )arylthio, (C 1 -C 6 )alkylsulfinyl, (C 6 -C 10 )arylsulfinyl, (C 1 -C 6 )alkylsulfonyl, (C 6 -C 10 )arylsulfonyl, (C 1 -C 6 )acyl, (C 1 -C 6 )alkoxy-CO—NH—, (C 1 -C 6 )alkyamino-CO—, (C 5 -C 9 )heteroaryl, (C 2 -C 9 )heterocycloalkyl or (C 6 -C 10 )aryl wherein the heteroaryl, heterocycloalkyl and aryl groups are optionally substituted by one to three halo, (C 1 -C 6 )alkyl, (C 1 -C 6 )alkyl-CO—NH—, (C 1 -C 6 )alkoxy-CO—NH—, (C 1 -C 6 )alkyl-CO—NH—(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy-CO—NH—(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy-CO—NH—(C 1 -C 6 )alkoxy, carboxy, carboxy((C 1 -C 6 )alkyl, carboxy((C 1 -C 6 )alkoxy, benzyloxycarbonyl(C 1 -C 6 )alkoxy, (C 1 -C 6 )alkoxycarbonyl(C 1 -C 6 )alkoxy, (C 6 -C 10 )aryl, amino, amino(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxycarbonylamino, (C 6 -C 10 )aryl((C 1 -C 6 )alkoxycarbonylamino, (C 1 -C 6 )alkylamino, (C 1 -C 6 )alkyl) 2 amino, (C 1 -C 6 )alkylamino(C 1 -C 6 )alkyl, C 1 -C 6 )alkyl) 2 amino((C 1 -C 6 )alkyl, hydroxy, (C 1 -C 6 )alkoxy, carboxy, carboxy((C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxycarbonyl, (C 1 -C 6 )alkoxycarbonyl(C 1 -C 6 )alkyl, (C 1 -C 6 )alkoxy-CO—NH—, (C 1 -C 6 )alkyl-CO—NH—, cyano, (C 5 -C 9 )heterocycloalkyl, amino-CO—NH—, (C 1 -C 6 )alkylamino-CO—NH—, C 1 -C 6 )alkyl) 2 amino-CO—NH—, (C 6 -C 10 )arylamino-CO—NH—, (C 5 -C 9 )heteroarylamino-CO—NH—, (C 1 -C 6 )alkylamino-CO—NH—(C 1 -C 6 )alkyl, (C 1 -C 6 )alkyl) 2 amino-CO—NH—(C 1 -C 6 )alkyl, (C 6 -C 10 )arylamino-CO—NH—(C 1 -C 6 )alkyl, (C 5 -C 9 )heteroarylamino-CO—NH—(C 1 -C 6 )alkyl, (C 1 -C 6 )alkylsulfonyl, (C 1 -C 6 )alkylsulfonylamino, (C 1 -C 6 )alkylsulfonylamino((C 1 -C 6 )alkyl, (C 6 -C 10 )arylsulfonyl, (C 6 -C 10 )arylsulfonylamino, (C 6 -C 10 )arylsulfonylamino((C 1 -C 6 )alkyl, (C 1 -C 6 )alkylsulfonylamino, (C 1 -C 6 )alkylsulfonylamino(C 1 -C 6 )alkyl, (C 5 -C 9 )heteroaryl or (C 2 -C 9 )heterocycloalkyl.
The present invention also relates to the pharmaceutically acceptable acid addition salts of compounds of the formula I. The acids which are used to prepare the pharmaceutically acceptable acid addition salts of the aforementioned base compounds of this invention are those which form non-toxic acid addition salts, i.e., salts containing pharmacologically acceptable anions, such as the hydrochloride, hydrobromide, hydroiodide, nitrate, sulfate, bisulfate, phosphate, acid phosphate, acetate, lactate, citrate, acid citrate, tartrate, bitartrate, succinate, maleate, fumarate, gluconate, saccharate, benzoate, methanesulfonate, ethanesulfonate, benzenesulfonate, p-toluenesulfonate and pamoate [i.e., 1,1′-methylene-bis-(2-hydroxy-3-naphthoate)]salts.
The invention also relates to base addition salts of formula I. The chemical bases that may be used as reagents to prepare pharmaceutically acceptable base salts of those compounds of formula I that are acidic in nature are those that form non-toxic base salts with such compounds. Such non-toxic base salts include, but are not limited to those derived from such pharmacologically acceptable cations such as alkali metal cations (e.g., potassium and sodium) and alkaline earth metal cations (e.g., calcium and magnesium), ammonium or water-soluble amine addition salts such as N-methylglucamine-(meglumine), and the lower alkanolammonium and other base salts of pharmaceutically acceptable organic amines.
The term “alkyl”, as used herein, unless otherwise indicated, includes saturated monovalent hydrocarbon radicals having straight or branched moieties or combinations thereof.
The term “alkoxy”, as used herein, includes O-alkyl groups wherein “alkyl” is defined above.
The term “halo”, as used herein, unless otherwise indicated, includes fluoro, chloro, bromo or iodo.
The compounds of this invention may contain double bonds. When such bonds are present, the compounds of the invention exist as cis and trans configurations and as mixtures thereof.
Unless otherwise indicated, the alkyl and alkenyl groups referred to herein, as well as the alkyl moieties of other groups referred to herein (e.g., alkoxy), may be linear or branched, and they may also be cyclic (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl) or be linear or branched and contain cyclic moieties. Unless otherwise indicated, halogen includes fluorine, chlorine, bromine, and iodine.
(C 2 -C 9 ) Heterocycloalkyl when used herein refers to pyrrolidinyl, tetrahydrofuranyl, dihydrofuranyl, tetrahydropyranyl, pyranyl, thiopyranyl, aziridinyl, oxiranyl, methylenedioxyl, chromenyl, isoxazolidinyl, 1,3-oxazolidin-3-yl, isothiazolidinyl, 1,3-thiazolidin-3-yl, 1,2-pyrazolidin-2-yl, 1,3-pyrazolidin-1-yl, piperidinyl, thiomorpholinyl, 1,2-tetrahydrothiazin-2-yl, 1,3-tetrahydrothiazin-3-yl, tetrahydrothiadiazinyl, morpholinyl, 1,2-tetrahydrodiazin-2-yl, 1,3-tetrahydrodiazin-1-yl, tetrahydroazepinyl, piperazinyl, chromanyl, etc. One of ordinary skill in the art will understand that the connection of said (C 2 -C 9 ) heterocycloalkyl rings is through a carbon or a sp 3 hybridized nitrogen heteroatom.
(C 2 -C 9 ) Heteroaryl when used herein refers to furyl, thienyl, thiazolyl, pyrazolyl, isothiazolyl, oxazolyl, isoxazolyl, pyrrolyl, triazolyl, tetrazolyl, imidazolyl, 1,3,5-oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,3-oxadiazolyl, 1,3,5-thiadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, 1,3,5-triazinyl, pyrazolo[3,4-b]pyridinyl, cinnolinyl, pteridinyl, purinyl, 6,7-dihydro-5H-[1]pyrindinyl, benzo[b]thiophenyl, 5,6,7,8-tetrahydro-quinolin-3-yl, benzoxazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzimidazolyl, thianaphthenyl, isothianaphthenyl, benzofuranyl, isobenzofuranyl, isoindolyl, indolyl, indolizinyl, indazolyl, isoquinolyl, quinolyl, phthalazinyl, quinoxalinyl, quinazolinyl, benzoxazinyl, etc. One of ordinary skill in the art will understand that the connection of said (C 2 -C 9 )heteroaryl rings is through a carbon atom or a sp 3 hybridized nitrogen heteroatom.
(C 6 -C 10 )aryl when used herein refers to phenyl or naphthyl.
Compounds of formula (I) may be administered in a pharmaceutically acceptable form either alone or in combination with one or more additional agents which modulate a mammalian immune system or with antiinflammatory agents. These agents may include but are not limited to cyclosporin A (e.g. Sandimmune® or Neoral®, rapamycin, FK-506 (tacrolimus), leflunomide, deoxyspergualin, mycophenolate (e.g. Cellcept®), azathioprine (e.g. Imuran®), daclizumab (e.g. Zenapax®. OKT3 (e.g. Orthoclone®), AtGam, aspirin, acetaminophen, ibuprofen, naproxen, piroxicam, and antiinflammatory steroids (e.g. prednisolone or dexamethasone). These agents may be administered as part of the same or separate dosage forms, via the same or different routes of administration, and on the same or different administration schedules according to standard pharmaceutical practice.
The compounds of this invention include all conformational isomers (e.g., cis and trans isomers. The compounds of the present invention have asymmetric centers and therefore exist in different enantiomeric and diastereomeric forms. This invention relates to the use of all optical isomers and stereoisomers of the compounds of the present invention, and mixtures thereof, and to all pharmaceutical compositions and methods of treatment that may employ or contain them. In this regard, the invention includes both the E and Z configurations. The compounds of formula I may also exist as tautomers. This invention relates to the use of all such tautomers and mixtures thereof.
This invention also encompasses pharmaceutical compositions containing prodrugs of compounds of the formula I. This invention also encompasses methods of treating or preventing disorders that can be treated or prevented by the inhibition of protein kinases, such as the enzyme Janus Kinase 3 comprising administering prodrugs of compounds of the formula I. Compounds of formula I having free amino, amido, hydroxy or carboxylic groups can be converted into prodrugs. Prodrugs include compounds wherein an amino acid residue, or a polypeptide chain of two or more (e.g., two, three or four) amino acid residues which are covalently joined through peptide bonds to free amino, hydroxy or carboxylic acid groups of compounds of formula I. The amino acid residues include the 20 naturally occurring amino acids commonly designated by three letter symbols and also include, 4-hydroxyproline, hydroxylysine, demosine, isodemosine, 3-methylhistidine, norvlin, beta-alanine, gamma-aminobutyric acid, citrulline, homocysteine, homoserine, ornithine and methioine sulfone. Prodrugs also include compounds wherein carbonates, carbamates, amides and alkyl esters which are covalently bonded to the above substituents of formula I through the carbonyl carbon prodrug sidechain.
Preferred compounds of formula I include those wherein a is 0; b is 1; X is carbonyl; c is 0; d is 0; e is 0; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is carbonyl; c is 0; d is 1; e is 0; f is 0, and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is carbonyl; c is 1; d is 0; e is 0; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is —C(═N═cyano)-; c is 1; d is 0; e is 0; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 0; c is 0; d is 0; e is 0; f is 0; g is 1; and Z is —C(O)—O—.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is S(O) n ; n is 2; c is 0; d is 0; e is 0; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is S(O) n ; n is 2; c is 0; d is 2; e is 0; f is 1; g is 1; and Z is carbonyl.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is S(O) n ; n is 2; c is 0; d is 2; e is 0; f is 1; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is carbonyl; c is 1; d is 0; e is 1; Y is S(O) n ; n is 2; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is S(O) n ; n is 2; c is 1; d is 0; e is 0; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 1; b is 1; X is carbonyl; c is 1; d is 0; e is 0; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is S(O) n ; c is 0; d is 1; e is 1; Y is S(O) n ; n is 2; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is S(O) n ; c is 0; d is 1; e is 1; Y is S(O) n ; n is 2; f is 1; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is oxygen; c is 0; d is 1; e is 1; Y is S(O) n ; n is 2; f is 1; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is oxygen; c is 0; d is 1; e is 1; Y is S(O) n ; n is 2; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is carbonyl; c is 1; d is 1; e is 1; Y is S(O) n ; f is 0; and g is 0.
Other preferred compounds of formula I include those wherein a is 0; b is 1; X is carbonyl; c is 1; d is 1; e is 1; Y is S(O) n ; n is 2; f is 1; and g is 0.
Other preferred compounds of formula I include those wherein R 12 is cyano, trifluoromethyl, (C 1 -C 6 )alkyl, trifluoromethyl(C 1 -C 6 )alkyl, (C 1 -C 6 )alkylamino, ((C 1 -C 6 )alkyl) 2 amino, (C 2 -C 6 )alkynyl, cyano(C 1 -C 6 )alkyl, (C 1 -C 6 )alkyl-S(O) m wherein m is 0, 1 or 2.
Specific preferred compounds of formula I include those wherein said compound is selected from the group consisting of:
Methyl-[4-methyl-1-(propane-1-sulfonyl)-piperidin-3-yl]-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine;
4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-carboxylic acid methyl ester;
3,3,3-Trifluoro-1-{4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-propan-1-one;
4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-carboxylic acid dimethylamide;
({4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-carbonyl}-amino)-acetic acid ethyl ester;
3-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-3-oxo-propionitrile;
3,3,3-Trifluoro-1-{4-methyl-3-[methyl-(5-methyl-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-propan-1-one;
1-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-but-3-yn-1-one;
1-{3-[(5-Chloro-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-methyl-amino]-4-methylpiperidin-1-yl}-propan-1-one;
1-{3-[(5-Fluoro-7H-pyrrolo[2,3-d]pyrimidin-4-yl)-methyl-amino]-4-methylpiperidin-1-yl}-propan-1-one;
N-cyano-4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-N′-propyl-piperidine-1-carboxamidine; and
N-cyano-4,N′,N′-Trimethyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-carboxamidine.
The present invention also relates to a pharmaceutical composition for (a) treating or preventing a disorder or condition selected from organ transplant rejection, xeno transplation, lupus, multiple sclerosis, rheumatoid arthritis, psoriasis, Type I diabetes and complications from diabetes, cancer, asthma, atopic dermatitis, autoimmune thyroid disorders, ulcerative colitis, Crohn's disease, Alzheimer's disease, Leukemia, and other autoimmune diseases or (b) the inhibition of protein kinases or Janus Kinase 3 (JAK3) in a mammal, including a human, comprising an amount of a compound of formula I or a pharmaceutically acceptable salt thereof, effective in such disorders or conditions and a pharmaceutically acceptable carrier.
The present invention also relates to a method for the inhibition of protein typrosine kinases or Janus Kinase 3 (JAK3) in a mammal, including a human, comprising administering to said mammal an effective amount of a compound of formula I or a pharmaceutically acceptable salt thereof.
The present invention also relates to a method for treating or preventing a disorder or condition selected from organ transplant rejection, xeno transplation, lupus, multiple sclerosis, rheumatoid arthritis, psoriasis, Type I diabetes and complications from diabetes, cancer, asthma, atopic dermatitis, autoimmune thyroid disorders, ulcerative colitis, Crohn's disease, Alzheimer's disease, Leukemia, and other autoimmune diseases in a mammal, including a human, comprising administering to said mammal an amount of a compound of formula I or a pharmaceutically acceptable salt thereof, effective in treating such a condition.
DETAILED DESCRIPTION OF THE INVENTION
The following reaction Schemes illustrate the preparation of the compounds of the present invention. Unless otherwise indicated R 2 , R 3 , R 4 and R 5 in the reaction Schemes and the discussion that follow are defined as above.
In reaction 1 of Preparation A, the 4-chloropyrrolo[2,3-d]pyrimidine compound of formula XXI, wherein R is hydrogen or a protecting group such as benzenesulfonyl or benzyl, is converted to the 4-chloro-5-halopyrrolo[2,3-d]pyrimidine compound of formula XX, wherein Y is chloro, bromo or iodo, by reacting XXI with N-chlorosuccinimide, N-bromosuccinimide or N-iodosuccinimide. The reaction mixture is heated to reflux, in chloroform, for a time period between about 1 hour to about 3 hours, preferably about 1 hour. Alternatively, in reaction 1 of Preparation A, the 4-chloropyrrolo[2,3-d]pyrimidine of formula XXI, wherein R is hydrogen, is converted to the corresponding 4-chloro-5-nitropyrrolo[2,3-d]pyrimidine of formula XX, wherein Y is nitro, by reacting XXI with nitric acid in sulfuric acid at a temperature between about −10° C. to about 10° C., preferably about 0° C., for a time period between about 5 minutes to about 15 minutes, preferably about 10 minutes. The compound of formula XXI, wherein Y is nitro, is converted to the corresponding 4-chloro-5-aminopyrrolo[2,3-d]pyrimidine of the formula XX, wherein Y is amino, by reacting XXI under a variety of conditions known to one skilled in the art such as palladium hydrogenolysis or tin(IV)chloride and hydrochloric acid.
In reaction 2 of Preparation A, the 4-chloro-5-halopyrrolo[2,3-d]pyrimidine compound of formula XX, wherein R is hydrogen, is converted to the corresponding compound of formula XIX, wherein R 2 is (C 1 -C 6 )alkyl or benzyl, by treating XX with N-butyllithium, at a temperature of about −78° C., and reacting the dianion intermediate so formed with an alkylhalide or benzylhalide at a temperature between about −78° C. to room temperature, preferably room temperature. Alternatively, the dianion so formed is reacted with molecular oxygen to form the corresponding 4-chloro-5-hydroxypyrrolo[2,3-d]pyrimidine compound of formula XIX, wherein R 2 is hydroxy. The compound of formula XX, wherein Y is bromine or iodine and R is benzenesulfonate, is converted to the compound of formula XIX, wherein R 2 is (C 6 -C 12 )aryl or vinyl, by treating XX with N-butyllithium, at a temperature of about −78° C., followed by the addition of zinc chloride, at a temperature of about −78° C. The corresponding organo zinc intermediate so formed is then reacted with aryliodide or vinyl iodide in the presence of a catalytic quantity of palladium. The reaction mixture is stirred at a temperature between about 50° C. to about 80° C., preferably about 70° C., for a time period between about 1 hour to about 3 hours, preferably about 1 hour.
In reaction 3 of Preparation A, the compound of formula XIX is converted to the corresponding compound of formula XVI by treating XIX with N-butyllithium, lithium diisopropylamine or sodium hydride, at a temperature of about −78° C., in the presence of a polar aprotic solvent, such as tetrahydrofuran. The anionic intermediate so formed is further reacted with (a) alkylhalide or benzylhalide, at a temperature between about −78° C. to room temperature, preferably −78° C., when R 3 is alkyl or benzyl; (b) an aldehyde or ketone, at a temperature between about −78° C. to room temperature, preferably −78° C., when R 3 is alkoxy; and (c) zinc chloride, at a temperature between about −78° C. to room temperature, preferably −78° C., and the corresponding organozinc intermediate so formed is then reacted with aryliodide or vinyl iodide in the presence of a catalytic quantity of palladium. The resulting reaction mixture is stirred at a temperature between about 50° C. to about 80° C., preferably about 70° C., for a time period between about 1 hour to about 3 hours, preferably about 1 hour. Alternatively, the anion so formed is reacted with molecular oxygen to form the corresponding 4-chloro-6-hydroxypyrrolo[2,3-d]pyrimidine compound of formula XVI, wherein R 3 is hydroxy.
In reaction 1 of Preparation B, the 4-chloropyrrolo[2,3-d]pyrimidine compound of formula XXI is converted to the corresponding compound of formula XXII, according to the procedure described above in reaction 3 of Preparation A.
In reaction 2 of Preparation B, the compound of formula XXII is converted to the corresponding compound of formula XVI, according to the procedures described above in reactions 1 and 2 of Preparation A.
In reaction 1 of Scheme 1, the 4-chloropyrrolo[2,3-d]pyrimidine compound of formula XVII is converted to the corresponding compound of formula XVI, wherein R is benzenesulfonyl or benzyl, by treating XVII with benzenesulfonyl chloride, benzylchloride or benzylbromide in the presence of a base, such as sodium hydride or potassium carbonate, and a polar aprotic solvent, such as dimethylformamide or tetrahydrofuran. The reaction mixture is stirred at a temperature between about 0° C. to about 70° C., preferably about 30° C., for a time period between about 1 hour to about 3 hours, preferably about 2 hours.
In reaction 2 of Scheme 1, the 4-chloropyrrolo[2,3-d]pyrimidine compound of formula XVI is converted to the corresponding 4-aminopyrrolo[2,3-d]pyrimidine compound of formula XV by coupling XVI with an amine of the formula HNR 4 R 5 . The reaction is carried out in an alcohol solvent, such as tert-butanol, methanol or ethanol, or other high boiling organic solvents, such as dimethylformamide, triethylamine, 1,4-dioxane or 1,2-dichloroethane, at a temperature between about 60° C. to about 120° C., preferably about 80° C. Typical reaction times are between about 2 hours to about 48 hours, preferably about 16 hours. When R 5 is a nitrogen containing heterocycloalkyl group, each nitrogen must be protected by a protecting group, such a benzyl. Removal of the R 5 protecting group is carried out under conditions appropriate for that particular protecting group in use which will not affect the R protecting group on the pyrrolo[2,3-d]pyrimidine ring. Removal of the R 5 protecting group, when benzyl, is carried out in an alcohol solvent, such as ethanol, in the present of hydrogen and a catalyst, such as palladium hydroxide on carbon. The R 5 nitrogen containing hetrocycloalkyl group so formed may be further reacted with a variety of different electrophiles of formula II. For urea formation, electrophiles of formula II such as isocyanates, carbamates and carbamoyl chlorides are reacted with the R 5 nitrogen of the heteroalkyl group in a solvent, such as acetonitrile or dimethylformamide, in the presence of a base, such as sodium or potassium carbonate, at a temperature between about 20° C. to about 100° C. for a time period between about 24 hours to about 72 hours. For amide and sulfonamide formation, electrophiles of formula II, such as acylchlorides and sulfonyl chlorides, are reacted with the R 5 nitrogen of the heteroalkyl group in a solvent such as methylene chloride in the presence of a base such as pyridine at ambient temperatures for a time period between about 12 hours to about 24 hours. Amide formation may also be carried out by reacting a carboxylic acid with the heteroalkyl group in the presence of a carbodiimide such as 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide in a solvent such as methylene chloride at ambient temperatures for 12-24 hours. For alkyl formation, electrophiles of formula II, such as α,β-unsaturated amides, acids, nitriles, esters, and α-halo amides, are reacted with the R 5 nitrogen of the heteroalkyl group in a solvent such as methanol at ambient temperatures for a time period between about 12 hours to about 18 hours. Alkyl formation may also be carried out by reacting aldehydes with the heteroalkyl group in the presence of a reducing agent, such as sodium cyanoborohydride, in a solvent, such as methanol, at ambient temperature for a time period between about 12 hours to about 18 hours.
In reaction 3 of Scheme 1, removal of the protecting group from the compound of formula XV, wherein R is benzenesulfonyl, to give the corresponding compound of formula I, is carried out by treating XV with an alkali base, such as sodium hydroxide or potassium hydroxide, in an alcohol solvent, such as methanol or ethanol, or mixed solvents, such as alcohol/tetrahydrofuran or alcohol/water. The reaction is carried out at room temperature for a time period between about 15 minutes to about 1 hour, preferably 30 minutes. Removal of the protecting group from the compound of formula XV, wherein R is benzyl, is conducted by treating XV with sodium in ammonia at a temperature of about −78° C. for a time period between about 15 minutes to about 1 hour.
In reaction 1 of Scheme 2, the 4-chloropyrrolo[2,3-d]pyrimidine compound of formula XX is converted to the corresponding 4-aminopyrrolo[2,3-d]pyrimidine compound of formula XXIV, according to the procedure described above in reaction 2 of Scheme 1.
In reaction 2 of Scheme 2, the 4-amino-5-halopyrrolo[2,3-d]pyrimidine compound of formula XXIV, wherein R is benzenesulfonate and Z is bromine or iodine, is converted to the corresponding compound of formula XXIII by reacting XXIV with (a) arylboronic acid, when R 2 is aryl, in an aprotic solvent, such tetrahydrofuran or dioxane, in the presence of a catalytic quantity of palladium (0) at a temperature between about 50° C. to about 100° C., preferably about 70° C., for a time period between about 2 hours to about 48 hours, preferably about 12 hours; (b) alkynes, when R 2 is alkynyl, in the presence of a catalytic quantity of copper (I) iodide and palladium (0), and a polar solvent, such as dimethylformamide, at room temperature, for a time period between about 1 hour to about 5 hours, preferably about 3 hours; and (c) alkenes or styrenes, when R 2 is vinyl or styrenyl, in the presence of a catalytic quantity of palladium in dimethylformamide, dioxane or tetrahydrofuran, at a temperature between about 80° C. to about 100° C., preferably about 100° C., for a time period between about 2 hours to about 48 hours, preferably about 48 hours.
In reaction 3 of Scheme 2, the compound of formula XXIII is converted to the corresponding compound of formula XV, according to the procedure described above in reaction 3 of Preparation A.
In reaction 1 of Scheme 3, the compound of formula XVII is converted to the corresponding compound of formula 1, according to the procedure described above in reaction 2 of Scheme 1.
The compounds of the present invention that are basic in nature are capable of forming a wide variety of different salts with various inorganic and organic acids. Although such salts must be pharmaceutically acceptable for administration to animals, it is often desirable in practice to initially isolate the compound of the present invention from the reaction mixture as a pharmaceutically unacceptable salt and then simply convert the latter back to the free base compound by treatment with an alkaline reagent and subsequently convert the latter free base to a pharmaceutically acceptable acid addition salt. The acid addition salts of the base compounds of this invention are readily prepared by treating the base compound with a substantially equivalent amount of the chosen mineral or organic acid in an aqueous solvent medium or in a suitable organic solvent, such as methanol or ethanol. Upon careful evaporation of the solvent, the desired solid salt is readily obtained. The desired acid salt can also be precipitated from a solution of the free base in an organic solvent by adding to the solution an appropriate mineral or organic acid.
Those compounds of the present invention that are acidic in nature, are capable of forming base salts with various pharmacologically acceptable cations. Examples of such salts include the alkali metal or alkaline-earth metal salts and particularly, the sodium and potassium salts. These salts are all prepared by conventional techniques. The chemical bases which are used as reagents to prepare the pharmaceutically acceptable base salts of this invention are those which form non-toxic base salts with the acidic compounds of the present invention. Such non-toxic base salts include those derived from such pharmacologically acceptable cations as sodium, potassium calcium and magnesium, etc. These salts can easily be prepared by treating the corresponding acidic compounds with an aqueous solution containing the desired pharmacologically acceptable cations, and then evaporating the resulting solution to dryness, preferably under reduced pressure. Alternatively, they may also be prepared by mixing lower alkanolic solutions of the acidic compounds and the desired alkali metal alkoxide together, and then evaporating the resulting solution to dryness in the same manner as before. In either case, stoichiometric quantities of reagents are preferably employed in order to ensure completeness of reaction and maximum yields of the desired final product.
The compositions of the present invention may be formulated in a conventional manner using one or more pharmaceutically acceptable carriers. Thus, the active compounds of the invention may be formulated for oral, buccal, intranasal, parenteral (e.g, intravenous, intramuscular or subcutaneous) or rectal administration or in a form suitable for administration by inhalation or insufflation. The active compounds of the invention may also be formulated for sustained delivery.
For oral administration, the pharmaceutical compositions may take the form of, for example, tablets or capsules prepared by conventional means with pharmaceutically acceptable excipients such as binding agents (e.g., pregelatinized maize starch, polyvinylpyrrolidone or hydroxypropyl methylcellulose); fillers (e.g., lactose, microcrystalline cellulose or calcium phosphate); lubricants (e.g., magnesium stearate, talc or silica); disintegrants (e.g., potato starch or sodium starch glycolate); or wetting agents (e.g., sodium lauryl sulphate). The tablets may be coated by methods well known in the art. Liquid preparations for oral administration may take the form of, for example, solutions, syrups or suspensions, or they may be presented as a dry product for constitution with water or other suitable vehicle before use. Such liquid preparations may be prepared by conventional means with pharmaceutically acceptable additives such as suspending agents (e.g, sorbitol syrup, methyl cellulose or hydrogenated edible fats); emulsifying agents (e.g., lecithin or acacia); non-aqueous vehicles (e.g., almond oil, oily esters or ethyl alcohol); and preservatives (e.g., methyl or propyl p-hydroxybenzoates or sorbic acid).
For buccal administration, the composition may take the form of tablets or lozenges formulated in conventional manner.
The active compounds of the invention may be formulated for parenteral administration by injection, including using conventional catheterization techniques or infusion. Formulations for injection may be presented in unit dosage form, e.g., in ampules or in multi-dose containers, with an added preservative. The compositions may take such forms as suspensions, solutions or emulsions in oily or aqueous vehicles, and may contain formulating agents such as suspending, stabilizing and/or dispersing agents. Alternatively, the active ingredient may be in powder form for reconstitution with a suitable vehicle, e.g., sterile pyrogen-free water, before use. The active compounds of the invention may also be formulated in rectal compositions such as suppositories or retention enemas, e.g., containing conventional suppository bases such as cocoa butter or other glycerides.
For intranasal administration or administration by inhalation, the active compounds of the invention are conveniently delivered in the form of a solution or suspension from a pump spray container that is squeezed or pumped by the patient or as an aerosol spray presentation from a pressurized container or a nebulizer, with the use of a suitable propellant, e.g., dichlorodifluoromethane, trichlorofluoromethane, dichlorotetrafluoroethane, carbon dioxide or other suitable gas. In the case of a pressurized aerosol, the dosage unit may be determined by providing a valve to deliver a metered amount. The pressurized container or nebulizer may contain a solution or suspension of the active compound. Capsules and cartridges (made, for example, from gelatin) for use in an inhaler or insufflator may be formulated containing a powder mix of a compound of the invention and a suitable powder base such as lactose or starch.
A proposed dose of the active compounds of the invention for oral, parenteral or buccal administration to the average adult human for the treatment of the conditions referred to above (e.g., rheumatoid arthritis) is 0.1 to 1000 mg of the active ingredient per unit dose which could be administered, for example, 1 to 4 times per day.
Aerosol formulations for treatment of the conditions referred to above (e.g., asthma) in the average adult human are preferably arranged so that each metered dose or “puff” of aerosol contains 20 μg to 1000 μg of the compound of the invention. The overall daily dose with an aerosol will be within the range 0.1 mg to 1000 mg. Administration may be several times daily, for example 2, 3, 4 or 8 times, giving for example, 1, 2 or 3 doses each time.
A compound of formula (I) administered in a pharmaceutically acceptable form either alone or in combination with one or more additional agents which modulate a mammlian immune system or with antiinflammatory agents, agents which may include but are not limited to cyclosporin A (e.g. Sandimmune® or Neoral®, rapamycin, FK-506 (tacrolimus), leflunomide, deoxyspergualin, mycophenolate (e.g. Cellcept®, azathioprine (e.g. Imuran®), daclizumab (e.g. Zenapax®), OKT3 (e.g. Orthocolone®), AtGam, aspirin, acctaminophen, ibuprofen, naproxen, piroxicam, and antiinflmmatory steroids (e.g. prednisolone or dexamethasone); and such agents may be administered as part of the same or separate dosage forms, via the same or different routes of administration, and on the same or different administration schedules according to standard pharmaceutical practice.
FK506 (Tacrolimus) is given orally at 0.10-0.15 mg/kg body weight, every 12 hours, within first 48 hours postoperative. Does is monitored by serum Tacrolimus trough levels.
Cyclosporin A (Sandimmune oral or intravenous formulation, or Neoral®, oral solution or capsules) is given orally at 5 mg/kg body weight, every 12 hours within 48 hours postoperative. Dose is monitored by blood Cyclosporin A trough levels.
The active agents can be formulated for sustained delivery according to methods well known to those of ordinary skill in the art. Examples of such formulations can be found in U.S. Pat. Nos. 3,538,214, 4,060,598, 4,173,626, 3,119,742, and 3,492,397.
The ability of the compounds of formula I or their pharmaceutically acceptable salts to inhibit Janus Kinase 3 and, consequently, demonstrate their effectiveness for treating disorders or conditions characterized by Janus Kinase 3 is shown by the following in vitro assay tests.
Biological Assay
JAK3 (JH1:GST) Enzymatic Assay
The JAK3 kinase assay utilizes a protein expressed in baculovirus-infected SF9 cells (a fusion protein of GST and the catalytic domain of human JAK3) purified by affinity chromatography on glutathione-Sepaharose. The substrate for the reaction is poly-Glutamic acid-Tyrosine (PGT (4:1), Sigma catalog # P0275), coated onto Nunc Maxi Sorp plates at 100 μg/ml overnight at 37° C. The morning after coating, the plates are washed three times and JAK3 is added to the wells containing 100 μl of kinase buffer (50 mM HEPES, pH 7.3, 125 mM NaCl, 24 mM MgCl2)+0.2 uM ATP+1 mM Na orthovanadate.) The reaction proceeds for 30 minutes at room temperature and the plates is washed three more times. The level of phosphorylated tyrosine in a given well is quantitated by standard ELISA assay utilizing an anti-phosphotyrosine antibody (ICN PY20, cat. #69-151-1).
Inhibition of Human IL-2 Dependent T-Cell Blast Proliferation
This screen measures the inhibitory effect of compounds on IL-2 dependent T-Cell blast proliferation in vitro. Since signaling through the IL-2 receptor requires JAK-3, cell active inhibitors of JAK-3 should inhibit IL-2 dependent T-Cell blast proliferation.
The cells for this assay are isolated from fresh human blood. After separation of the mononuclear cells using Accuspin System-Histopaque-1077 (Sigma # A7054), primary human T-Cells are isolated by negative selection using Lympho-Kwik T (One Lambda, Inc., Cat # LK-50T). T-Cells are cultured at 1-2×10 6 /ml in Media (RPMI+10% heat-inactivated fetal calf serum (Hyclone Cat # A-1111-L)+1% Penicillin/Streptomycin (Gibco) and induce to proliferate by the addition of 10 ug/ml PHA (Murex Diagnostics, Cat # HA 16). After 3 days at 37° C. in 5% CO 2 , cells are washed 3 times in Media, resuspended to a density of 1-2×10 6 cells/ml in Media plus 100 Units/ml of human recombinant IL-2 (R&D Systems, Cat # 202-IL). After 1 week the cells are IL-2 dependent and can be maintained for up to 3 weeks by feeding twice weekly with equal volumes of Media+100 Units/ml of IL-2.
To assay for a test compounds ability to inhibit IL-2 dependent T-Cell proliferation, IL-2 dependent cells are washed 3 times, resuspended in media and then plated (50,000 cells/well/0.1 ml) in a Flat-bottom 96-well microtiter plate (Falcon # 353075). From a 10 mM stock of test compound in DMSO, serial 2-fold dilutions of compound are added in triplicate wells starting at 10 uM. After one hour, 10 Units/ml of IL-2 is added to each test well. Plates are then incubated at 37° C., 5% CO 2 for 72 hours. Plates are then pulsed with 3 H-thymidine (0.5 uCi/well) (NEN Cat # NET-027A), and incubated an additional 18 hours. Culture plates are then harvested with a 96-well plate harvester and the amount of 3 H-thymidine incorporated into proliferating cells is determined by counting on a Packard Top Count scintillation counter. Data is analyzed by plotting the % inhibition of proliferation verses the concentration of test compound. An IC 50 value (uM) is determined from this plot.
The following Examples illustrate the preparation of the compounds of the present invention but it is not limited to the details thereof. Melting points are uncorrected. NMR data are reported in parts per million (δ) and are referenced to the deuterium lock signal from the sample solvent (deuteriochloroform unless otherwise specified). Commercial reagents were utilized without further purification. THF refers to tetrahydrofuran. DMF refers to N,N-dimethylformamide. Low Resolution Mass Spectra (LRMS) were recorded on either a Hewlett Packard 59890®, utilizing chemical ionization (ammonium), or a Fisons (or Micro Mass) Atmospheric Pressure Chemical Ionization (APCI) platform which uses a 50/50 mixture of acetonitrile/water with 0.1% formic acid as the ionizing agent. Room or ambient temperature refers to 20-25° C.
EXAMPLE 1
1-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-ethanone
Method A
(1-Benzyl-4-methyl-piperidin-3-yl)-methyl-amine
To a stirred solution of 1-benzyl-4-methyl-piperidin-3-one (2.3 grams, 11.5 mmol), prepared by the methods of Iorio, M. A. and Damia, G., Tetrahedron, 26, 5519 (1970) and Grieco et al., Journal of the American Chemical Society, 107, 1768 (1985), (modified using 5% methanol as a co-solvent), both references are incorporated by reference in their entirety, dissolved in 23 mL of 2 M methylamine in tetrahydrofuran was added 1.4 mL (23 mmol) of acetic acid and the resulting mixture stirred in a sealed tube for 16 hours at room temperature. Triacetoxy sodium borohydride (4.9 grams, 23 mmol) was added and the new mixture stirred at room temperature in a sealed tube for 24 h, at which time, the reaction was quenched upon addition of 1 N sodium hydroxide (50 mL). The reaction mixture was then extracted 3×80 mL with ether, the combined ether layers dried over sodium sulfate (Na 2 SO 4 ) and concentrated to dryness in vacuo affording 1.7 grams (69%) of the title compound as a white solid. LRMS: 219.1 (M+1).
Method B
(1-Benzyl-4-methyl-piperidin-3-yl)-methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
A solution of 4-chloropyrrolo[2,3-d]pyrimidine (2.4 grams, 15.9 mmol), prepared by the method of Davoll, J. Am. Chem. Soc., 82, 131 (1960), which is incorporated by reference in its entirety, and the product from Method A (1.7 grams, 7.95 mmol) dissolved in 2 equivalents of triethylamine was heated in a sealed tube at 100° C. for 3 days. Following cooling to room temperature and concentration under reduced pressure, the residue was purified by flash chromatography (silica; 3% methanol in dichloromethane) affording 1.3 grams (50%) of the title compound as a colorless oil. LRMS: 336.1 (M+1).
Method C
Methyl-(4-methyl-piperidin-3-yl)-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
To the product from Method B (0.7 grams, 2.19 mmol) dissolved in 15 mL of ethanol was added 1.5 mL of 2 N hydrochloric acid and the reaction mixture degassed by nitrogen purge. To the reaction mixture was then added 0.5 grams of 20% palladium hydroxide on carbon (50% water) (Aldrich) and the resulting mixture shaken (Parr-Shaker) under a 50 psi atmosphere of hydrogen at room temperature for 2 days. The Celite filtered reaction mixture was concentrated to dryness in vacuo and the residue purified by flash chromatography (silica; 5% methanol in dichoromethane) affording 0.48 grams (90%) of the title compound. LRMS: 246.1 (M+1).
Method D
1-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-ethanone
To a stirred solution of the product from Method C (0.03 grams, 0.114 mmol) dissolved in 5 mL of 10:1 dichloromethane/pyridine was added (0.018 grams, 0.228 mmol) of acetylchloride and the resulting mixture stirred at room temperature for 18 hours. The reaction mixture was then partitioned between dichloromethane and saturated sodium bicarbonate (NaHCO 3 ). The organic layer was washed again with saturated NaHCO 3 , dried over sodium sulfate and concentrated to dryness in vacuo. The residue was purified by preparative thin layer chromatography (PTLC) (silica; 4% methanol in dichloromethane) affording 0.005 mg (15%) of the title compound as a colorless oil. LRMS: 288.1 (M+1).
The title compounds for examples 2-26 were prepared by a method analogous to that described in Example 1.
EXAMPLE 2
[1-(2-Amino-ethanesulfonyl)-4-methyl-piperidin-3-yl]-methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
[1-(2-Amino-ethanesulfonyl)-4-methyl-piperidin-3-yl]-methyl-amine. LRMS: 353.
EXAMPLE 3
(1-Ethanesulfonyl-4-methyl-piperidin-3-yl)-methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
(1-Ethanesulfonyl-4-methyl-piperidin-3-yl)-methyl-amine. LRMS: 338.
EXAMPLE 4
[1-(Butane-1-sulfonyl)-4-methyl-piperidin-3-yl]-methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
[1-(Butane-1-sulfonyl)-4-methyl-piperidin-3-yl]-methyl-amine. LRMS: 366.
EXAMPLE 5
4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-carboxylic Acid Isobutyl Ester
4-Methyl-3-methylamino-piperidine-1-carboxylic acid isobutyl ester. LRMS: 346.
EXAMPLE 6
N-(2-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-sulfonyl}-ethyl)-propionamide
N-[2-(4-Methyl-3-methylamino-piperidine-1-sulfonyl)-ethyl]-propionamide. LRMS: 409.
EXAMPLE 7
(2-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-sulfonyl}-ethyl)-carbamic Acid Methyl Ester
[2-(4-Methyl-3-methylamino-piperidine-1-sulfonyl)-ethyl]-carbamic acid methyl ester. LRMS: 411.
EXAMPLE 8
N-(2-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-sulfonyl}-ethyl)-isobutyramide
N-[2-(4-Methyl-3-methylamino-piperidine-1-sulfonyl)-ethyl]-isobutyramide. LRMS: 423.
EXAMPLE 9
(1-Methanesulfonyl-piperidin-3-yl)-methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
(1-Methanesulfonyl-piperidin-3-yl)-methyl-amine. LRMS: 310.
EXAMPLE 10
(1-Ethanesulfonyl-piperidin-3-yl)-methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
(1-Ethanesulfonyl-piperidin-3-yl)-methyl-amine. LRMS: 324.
EXAMPLE 11
Methyl-[1-(propane-1-sulfonyl)-piperidin-3-yl]-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
(1-Propylsulfonyl-piperidin-3-yl)-methyl-amine. LRMS: 338.
EXAMPLE 12
[1-(Butane-1-sulfonyl)-piperidin-3-yl]-methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
(1-Butylsulfonyl-piperidin-3-yl)-methyl-amine. LRMS: 352.
EXAMPLE 13
2,2-Dimethyl-N-(2-{4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-sulfonyl}-ethyl)-propionamide
2,2-Dimethyl-N-[2-(4-methyl-3-methylamino-piperidine-1-sulfonyl)-ethyl]-propionamide. LRMS: 437.
EXAMPLE 14
3-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)amino]-piperidin-1-yl}-3-oxo-propionitrile
3-(4-Methyl-3-methylamino-piperidin-1-yl)-3-oxo-propionitrile. LRMS: 313.
EXAMPLE 15
(3-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-3-oxo-propyl)-carbamic Acid Tert-Butyl Ester
[3-(4-Methyl-3-methylamino-piperidin-1-yl)-3-oxo-propyl]-carbamic acid tert-butyl ester. LRMS: 417.
EXAMPLE 16
Methyl-[4-methyl-1-(propane-1-sulfonyl)-piperidin-3-yl]-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
Methyl-[4-methyl-1-(propane-1-sulfonyl)-piperidin-3-yl]-amine. LRMS: 352.
EXAMPLE 17
3-Amino-1-{4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl-propan-1-one
3-Amino-1-(4-methyl-3-methylamino-piperidin-1-yl)-propan-1-one. LRMS: 317.
EXAMPLE 18
2-Methoxy-1-{4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-ethanone
2-Methoxy-1-(4-methyl-3-methylamino-piperidin-1-yl)-ethanone. LRMS: 318.
EXAMPLE 19
2-Dimethylamino-1-(4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-ethanone
2-Dimethylamino-1-(4-methyl-3-methylamino-piperidin-1-yl)-ethanone. LRMS: 331.
EXAMPLE 20
(3-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-3-oxo-propyl)-carbamic Acid Tert-Butyl Ester
[3-(4-Methyl-3-methylamino-piperidin-1-yl)-3-oxo-propyl]-carbamic acid tert-butyl ester. LRMS: 417.
EXAMPLE 21
3,3,3-Trifluoro-1-{4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-propan-1-one
3,3,3-Trifluoro-1-(4-methyl-3-methylamino-piperidin-1-yl)-propan-1-one.
EXAMPLE 22
N-(2-{4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl-}2-oxo-ethyl)-acetamide
N-[2-(4-Methyl-3-methylamino-piperidin-1-yl)-2-oxo-ethyl]-acetamide. LRMS: 345.
EXAMPLE 23
3-Ethoxy-1-{4-methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidin-1-yl}-propan-1-one
3-Ethoxy-1-(4-methyl-3-methylamino-piperidin-1-yl)-propan-1-one. LRMS: 346.
EXAMPLE 24
4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-carboxylic Acid Methylamide
4-Methyl-3-methylamino-piperidine-1-carboxylic acid methylamide. LRMS: 303.
EXAMPLE 25
4-Methyl-3-[methyl-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amino]-piperidine-1-carboxylic Acid Diethylamide
4-Methyl-3-methylamino-piperidine-1-carboxylic acid diethylamide. LRMS: 345.
EXAMPLE 26
Methyl-[4-methyl-1-(2-methylamino-ethanesulfonyl)-piperidin-3-yl]-(7H-pyrrolo[2,3-d]pyrimidin-4-yl)-amine
Methyl-[4-methyl-1-(2-methylamino-ethanesulfonyl)-piperidin-3-yl]-amine. LRMS: 367. | A compound of the formula
wherein R 1 , R 2 and R 3 are as defined above, which are inhibitors of the enzyme protein kinases such as Janus Kinase 3 and as such are useful therapy as immunosuppressive agents for organ transplants, xeno transplation, lupus, multiple sclerosis, rheumatoid arthritis, psoriasis, Type I diabetes and complications from diabetes, cancer, asthma, atopic dermatitis, autoimmune thyroid disorders, ulcerative colitis, Crohn's disease, Alzheimer's disease, Leukemia and other autoimmune diseases. | 2 |
BACKGROUND OF THE INVENTION
[0001] This invention relates generally to video surveillance systems and, more particularly, to assembling and disassembling camera pan, tilt, and zoom assemblies.
[0002] At least some known video surveillance systems include one or more video cameras mounted in a housing along with a pan, tilt, and zoom (PTZ) assembly. The PTZ permits controlling a movement of the camera to align a viewing area of the camera with an object of interest or location of interest. The zoom portion of the mechanism may be used to adjust a field of view of the camera. The housing protects the camera from the environment in the location where the camera and PTZ assembly are mounted.
[0003] During initial installation and periodically thereafter, the camera and/or PTZ assembly may need to be removed from it's mounted location. For example, over time, the camera and/or PTZ assembly may require maintenance to restore a damaged or worn camera or PTZ assembly to an operable condition. When installing, repairing, or replacing a PTZ assembly a maintenance person is frequently required to use two hands to unlatch the mechanism that supports the PTZ assembly and remove it from its housing. At least some known PTZ assemblies are positioned in an elevated location, therefore using two hands to remove the PTZ assembly creates a safety hazard. In addition, when installing, repairing, or replacing a PTZ assembly a maintenance person is frequently required to push and/or pull with a great amount of force to install or remove the PTZ assembly from its housing. Such actions can cause a safety hazard by unbalancing a person high in the air on a ladder or lifting mechanism. Requiring the use of a man-lift or other lifting mechanism, so that two hands may be used also increases the cost of removing and installing the camera and PTZ assembly.
[0004] At least some known PTZ assemblies are compact in size such that various hazards can arise from placing a hand into these mechanisms, for example, to loosen fasteners, catches, and/or latches, or during insertion and removal of the PTZ assembly. A part of the PTZ assembly falling from the elevated mounting position can create a safety hazard as well. A PTZ assembly falling from an elevated position could cause death or serious bodily injury such that positive control and installation of the PTZ assembly is required. At least some known PTZ attachment mechanisms create a “false positive” indication of attachment, such that the user believes the mechanism is securely attached in place when it is not.
[0005] A previous attempt to address the afore mentioned problems included a radial handle located inside the PTZ assembly housing. When pulled, the handle would engage symmetrical pawls on leaf springs releasing the PTZ mechanism. However, an uneven distribution of downward forces, sometimes caused binding between the engaged components and inserting a hand into the housing created a safety hazard for the user and limited the compactness of the design. A second attempt to address the problems described above included a toothed bracket that was constrained to linear motion tangent to a shroud of the PTZ assembly. The shroud was also toothed, and when engaged, the teeth would align and the bracket could be moved. The bracket included a wedge design that would move over a stubby nose spring plunger, creating the upward force necessary to hold the PTZ assembly in place. However, the linear motion of the bracket causes binding because the motion of the shroud was radial and the latching of the PTZ assembly is not positive such that the user is required to apply a force to engage the latch.
BRIEF DESCRIPTION OF THE INVENTION
[0006] In one embodiment, a support mechanism is provided. The support mechanism includes an engagement pin including an engagement surface and a latch surface wherein the engagement pin is coupled to a base. The support mechanism also includes a pawl including an engagement surface complementary to the pin engagement surface and a latch surface complementary to the pin latch surface wherein the pawl is biased toward engagement of the pawl latch surface with the pin latch surface. The support mechanism also includes a ring latch that includes an annular ring having a toothed edge, the ring latch is coupled to the pawl such that the pawl extends axially away from the ring latch in a direction opposite the toothed edge.
[0007] In another embodiment, a support mechanism is provided. The support mechanism includes a base, a pan motor having a longitudinal axis, and a removable unit. The pan motor includes a stationary member coupled to the base and a rotatable member rotatably coupled to the stationary member. The removable unit is configured to latchably couple to the base using a first axial force applied to the removable unit. The removable unit is also configured to release from the base using a second axial force and a rotational force in sequential combination.
[0008] In yet another embodiment, a method of operating a support mechanism is provided. The support mechanism includes a base and a removable unit latchably coupled to the base. The method includes engaging a rotatable toothed shroud to a toothed ring latch using a an axial force to reposition the shroud from a relaxed position to an engaged position, rotating the shroud and ring latch using a rotational force applied to the shroud to unlatch the removable unit from the base, and withdrawing the removable unit from the base using at least one of the weight of the removable unit and an ejection bias member.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] FIG. 1 is a perspective view of an exemplary video camera pan, tilt, and zoom assembly in accordance with an embodiment of the present invention;
[0010] FIG. 2 is an enlarged perspective view of a portion of the PTZ assembly shown in FIG. 1 ;
[0011] FIG. 3 is an enlarged perspective view of an alternative embodiment of a portion of the PTZ assembly shown in FIG. 1 ;
[0012] FIG. 4 is a perspective view of the exemplary PTZ assembly shown in FIG. 1 with parts removed;
[0013] FIG. 5 is a perspective view of the exemplary PTZ assembly shown in FIG. 1 with different parts removed than shown in FIG. 3 ; and
[0014] FIG. 6 is a flowchart of an exemplary method of operating a support mechanism that includes a base and a removable unit latchably coupled to the base.
DETAILED DESCRIPTION OF THE INVENTION
[0015] As used herein, an element or step recited in the singular and proceeded with the word “a” or “an” should be understood as not excluding plural elements or steps, unless such exclusion is explicitly recited. Furthermore, references to “one embodiment” of the present invention are not intended to be interpreted as excluding the existence of additional embodiments that also incorporate the recited features.
[0016] FIG. 1 is a perspective view of an exemplary video camera pan, tilt, and zoom assembly 100 in accordance with an embodiment of the present invention. PTZ assembly 100 includes an upper bracket or base 102 coupled to an interior portion of a housing. The housing is configured to be fixedly coupled to a structure such as a ceiling, stanchion, post, or other suitable mount able to support the weight of PTZ assembly 100 and is a stable platform to facilitate reducing jitter. Jitter may be apparent in the camera image due to vibration or swaying of PTZ assembly 100 .
[0017] Base 102 includes one or more locating rounds 104 that are complementary to locating slots 106 in a lower bracket 108 of a removable unit 110 . Locating rounds and locating slots 106 are used to align removable unit 110 and base prior to coupling removable unit 110 to base 102 . Base 102 also includes one or more guides 112 configured to receive a pawl 114 coupled to a ring latch 116 on removable unit 110 . In the exemplary embodiment, a second pawl (not shown) is oriented similarly to pawl 114 and spaced approximately 180 degrees from pawl 114 . In an alternative embodiment, a different number of pawls are used. A distal end 118 of guide 112 includes a pin 120 extending away from guide 112 in a radial direction with respect to a longitudinal axis 122 of PTZ assembly 100 . Pawl 114 and pin 120 are configured to engage to transfer the weight of removable unit 110 to base 102 to support removable unit 110 . In various embodiments of the present invention pin 120 is configured as a rotatable wheel.
[0018] Ring latch 116 is rotatably coupled to lower bracket 108 . The amount of rotation ring latch 116 is capable of is limited by a plurality of stops 123 and complementary grooves 124 that engage to limit the rotational travel of ring latch 116 with respect to lower bracket 108 . A stationary member 128 of pan motor 126 is fixedly coupled to lower bracket 108 . When pan motor 126 rotates, removable unit 110 rotates with the rotatable member and with respect to base 102 . A slip ring 130 permits removable unit 110 to rotate continuously in a first rotational direction 132 or a second opposite direction 134 .
[0019] Removable unit 110 includes a shroud 136 that is slidably coupled to a chassis 137 . Shroud 136 is configured to maintain a relaxed position (shown in FIG. 1 ) and an engaged position. In the engaged position, a plurality of teeth 138 arranged circumferentially about an outer periphery 140 of shroud 136 and extending axially toward ring latch 116 are configured to mesh with a complementary plurality of teeth 142 arranged circumferentially about an outer periphery 144 of ring latch 116 and extending axially toward teeth 138 . Shroud 136 is translated from the relaxed position to the engaged position by applying an upward axial force to a bottom side 146 of shroud 136 . The movement associated with positioning shroud 136 from the relaxed position to the engaged position compresses or tensions a plurality of bias members 148 coupled between shroud 136 and chassis 137 . A plurality of travel limiters 147 limit the upward movement of ring latch 116 with respect to lower bracket 108 . Bias members 148 are configured to return shroud 136 to the relaxed position when the axial force applied to shroud 136 is removed.
[0020] Ring latch 116 is configured to rotate at least partially about axis 122 and shroud 136 is configured to rotate freely about axis 122 with chassis 137 and the rotatable member of pan motor 128 . Accordingly, with teeth 138 and 142 engaged by an axial force applied to shroud 136 , an additional rotational force may be applied to shroud 136 to cause ring latch to rotate. Pawl 114 rotates with ring latch 116 toward or away from pin 120 . If pawl 114 rotates away from pin 120 , the weight of removable unit 110 will no longer be supported by the engagement of pawl 114 and pin 120 and removable unit 110 will be released from base 102 by its own weight. In an alternative embodiment, one or more ejection springs are configured to apply a bias force to removable unit 110 to assist in disengaging removable unit 100 from base 102 .
[0021] FIG. 2 is an enlarged perspective view of a portion of PTZ assembly 100 (shown in FIG. 1 ). Pawl 114 extends axially away from ring latch 116 toward guide 112 . Pawl 114 includes an engagement surface 202 and latch surface 204 . Pin 120 extends radially from guide 112 and includes an engagement surface 206 and a latch surface 208 . Engagement surface 206 is configured to engage engagement surface 202 during an installation procedure where removable unit 110 is coupled to base 102 . A tip 210 of pawl 114 has a width 212 that is less than a width 214 of a root end 216 of pawl 114 . As pawl 114 moves axially with respect to pin 120 during the installation procedure, engagement surface 206 engages engagement surface 202 and a rotational force generated by the inclined engagement surface 202 and stationary engagement surface 206 forces pawl 114 to move away from pin 120 , which compresses a bias member 218 . In the exemplary embodiment, bias member 218 is a coil spring. In various alternative embodiments, bias member 218 is a leaf spring, an extension spring, a constant force spring, or a resilient material.
[0022] Latch surface 208 is configured to engage latch surface 204 after engagement surface 202 clears engagement surface 206 . Bias member 218 provides a rotational force to slide latch surface 204 over latch surface 208 such that the weight of removable unit 110 is transferred to pin 120 from pawl 114 .
[0023] In FIG. 2 , pin 120 is illustrated as a wedge-shape pin, in various alternative embodiments, pin 120 is a rotatable wheel that rolls along engagement surface 202 rather than sliding across it. The wheel is configured to engage latch surface 204 after the wheel clears engagement surface 202 during an installation procedure. A radially outer periphery of the wheel corresponds to engagement surface 206 and latch surface 208 and engages engagement surface 202 and latch surface 204 .
[0024] FIG. 3 is an enlarged perspective view of an alternative embodiment of a portion of PTZ assembly 100 (shown in FIG. 1 ). In this embodiment, a pin 264 extends axially away from ring latch 266 toward a guide 268 . Pin 264 includes an engagement surface 270 and latch surface 272 . A pawl 274 extends from guide 268 and includes an engagement surface 276 and a latch surface 278 . Engagement surface 276 is configured to engage engagement surface 270 during an installation procedure where removable unit 110 is coupled to base 102 . A tip 280 of pawl 274 has a width 282 that is less than a width 284 of a root end 286 of pawl 274 . As pin 264 moves axially with respect to pawl 274 during the installation procedure, engagement surface 270 engages engagement surface 276 and a rotational force generated by the inclined engagement surface 270 and stationary engagement surface 276 forces pin 264 to move away from pawl 274 , which compresses a bias member 288 . In the exemplary embodiment, bias member 288 is a coil spring. In various alternative embodiments, bias member 288 is a leaf spring, an extension spring, a constant force spring, or a resilient material.
[0025] Latch surface 272 is configured to engage latch surface 278 after engagement surface 270 clears engagement surface 276 . Bias member 288 provides a rotational force to slide latch surface 272 over latch surface 278 such that the weight of removable unit 110 is transferred to pawl 274 from pin 264 .
[0026] In FIG. 3 , pin 264 is illustrated as a wedge-shape pin, in various alternative embodiments, pin 264 is a rotatable wheel that rolls along engagement surface 276 rather than sliding across it. The wheel is configured to engage latch surface 278 after the wheel clears engagement surface 276 during an installation procedure.
[0027] FIG. 4 is a perspective view of exemplary PTZ assembly 100 (shown in FIG. 1 ) with parts removed. Specifically, PTZ assembly 100 is illustrated with base 102 , shroud 136 , and ring latch 116 removed. PTZ assembly 100 includes a tilt motor 302 coupled to chassis 137 and to a video camera 304 such that a rotation of tilt motor 302 defines a tilt angle of camera 304 with respect to axis 122 . A plurality of tabs 306 extending radially away from lower bracket 108 support ring latch 116 in an axial direction and are configured to permit ring latch 116 to rotate.
[0028] FIG. 5 is a perspective view of exemplary PTZ assembly 100 (shown in FIG. 1 ) with different parts removed than shown in FIG. 3 . Specifically, PTZ assembly 100 is illustrated with base 102 , lower bracket 108 , and ring latch 116 removed. PTZ assembly 100 includes a rotatable member 402 of motor 128 coupled to chassis 137 such that a rotation of pan motor 128 defines a rotation of chassis 137 about axis 122 .
[0029] FIG. 6 is a flowchart of an exemplary method 500 of operating a support mechanism that includes a base and a removable unit latchably coupled to the base. In the exemplary embodiment, the removable unit is a PTZ assembly configured to support a video camera and permit rotation of the camera field of view about a pan axis and a tilt axis. The removable unit includes a pawl and pin latch mechanism that permits attachment of the removable unit to the base using a force acting along the pan axis, such as by a user's hand supporting the removable unit and the user supplying an upward force from the bottom of the removable unit. To release the removable unit, an upward force is applied to the bottom of the removable unit to engage two sets of teeth. A rotation force is then applied to the removable unit to unlock the pawl and pin latch mechanism. The rotational force is transmitted through the meshed teeth to move the pawl from a latched position to an unlatched position with respect to the pin. The weight of the removable unit permits the removable unit to separate from the base with substantially no additional force required.
[0030] To release the removable unit of an assembled PTZ assembly, method 500 includes engaging 502 a rotatable toothed shroud to a toothed ring latch using a an axial force to reposition the shroud from a relaxed position to an engaged position, rotating 504 the shroud and ring latch using a rotational force applied to the shroud to unlatch the removable unit from the base, and withdrawing 506 the removable unit from the base using the weight of the removable unit.
[0031] To install the removable unit to the base, method 500 includes aligning 508 a locating round of the base with a complementary locating socket of the removable unit, and latchably coupling 510 the removable unit to the base using an axial force applied to the shroud on a side opposite the base.
[0032] Although the embodiments described herein are discussed with respect to a video surveillance system, it is understood that the coupling and release mechanism described herein may be used with other mechanical and electro-mechanical systems.
[0033] It will be appreciated that the use of first and second or other similar nomenclature for denoting similar items is not intended to specify or imply any particular order unless otherwise stated.
[0034] The above-described embodiments of a video surveillance system provide a cost-effective and reliable means for a latching mechanism that allows the PTZ assembly to be installed and removed using only one hand, thus allowing the user to keep one hand secured to a ladder or lifting mechanism, and that requires a relatively small amount of upward force to install and substantially zero downward force to remove. The latching mechanism also operates such that the user's hand only comes in contact with the shroud to facilitate reducing pinch points and crush points and does not create a false positive installation indication.
[0035] Exemplary embodiments of video surveillance systems and apparatus are described above in detail. The video surveillance system components illustrated are not limited to the specific embodiments described herein, but rather, components of each system may be utilized independently and separately from other components described herein. For example, the video surveillance system components described above may also be used in combination with different video surveillance system components. A technical effect of the various embodiments of the systems and methods described herein include facilitating operation and maintenance of video surveillance system by permitting relatively simple interchangeability and maintenance of cameras.
[0036] While the invention has been described in terms of various specific embodiments, those skilled in the art will recognize that the invention can be practiced with modification within the spirit and scope of the claims. | Methods and apparatus for a support mechanism are provided. The support mechanism includes an engagement pin including an engagement surface and a latch surface wherein the engagement pin is coupled to a base. The support mechanism also includes a pawl that includes an engagement surface complementary to the pin engagement surface and a latch surface complementary to the pin latch surface wherein the pawl is biased toward engagement of the pawl latch surface with the pin latch surface. The support mechanism also includes a ring latch that includes an annular ring having a toothed edge, the ring latch is coupled to the pawl such that the pawl extends axially away from the ring latch in a direction opposite the toothed edge. | 5 |
FIELD OF THE INVENTION
The field of the invention is that of formulations for the treatment of substrates for the purpose of conferring on them resistance to aqueous and fatty substances. More particularly, the invention relates to silicone compositions comprising perhalogenated, preferably perfluorinated, radicals which can be used in particular for the preparation of hydrophobic and/or oleophobic coatings and/or for carrying out hydrophobic and/or oleophobic impregnations of various substrates.
More particularly still, the invention relates to silicone compositions which can be employed as fluorinated finishing preparations in the textile field for rendering the treated fabrics impermeable and for contributing stain-resistant and/or soil-resistant properties, combined with ease of washing. Such properties are also advantageous for other fields of application than the textile field. Mention may be made, for example, of the construction field, in which coatings, paints, coats or other glazings of a water- and oil-repellent nature are employed which render resistant surfaces which are non-adhesive with respect to ice, biological fouling of the type of that which becomes attached to boat hulls, or graffiti, or with respect to other undesirable contaminants.
DESCRIPTION OF RELATED ART
Silicone oils grafted with fluorinated units can also be used as lubricant, as specific antiadhesive agent with respect to certain adhesives (silicones with a high adhesive power), as grease-resistant agent or alternatively as antifoaming agent. They can also be formulated with various thickeners in order to form mastics or any other leakproofing and/or pointing material.
The present invention is targeted at the use of functionalized silicone compositions comprising linear or cyclic perhalogenated, preferably perfluorinated, polyorganosiloxanes exhibiting at least one silicon atom substituted by at least one perfluorinated radical Rf for the preparation of hydrophobic and/or oleophobic coatings and/or for carrying out hydrophobic and/or oleophobic impregnations with a low surface energy (for example, soil-resistant coating on textile substrates).
The invention also comprises a selection of silicone compositions with given perfluorinated functional groups and with other specific functional groups, in particular for attachment.
The present invention also relates to a process for the preparation of a hydrophobic and/or oleophobic coating and/or for carrying out a hydrophobic and/or oleophobic impregnation employing said composition.
Finally, the invention is targeted at precursors of coatings, coats, paints or other glazings comprising this composition.
The role of halogens and in particular of fluorine and of the carbon/fluorine bond in contributing specific properties to organic polymer systems is a notion which is well known in polymer chemistry. In particular, it is known that fluorination and more specifically the introduction of perfluorinated units into polymers leads to a decrease in the surface energies, an improvement in the thermal and chemical stability and an improvement in the hydrophobicity, organophobicity and oleophobicity properties. It is thus known that, in order to resist aqueous and fatty substances, a coating must comprise a high density of perfluorinated end groups Rf at the surface. Since the 1970s, this type of functionalization by perfluorination has been applied to silicone polymers, in particular of the linear or cyclic, preferably linear, polyorganosiloxane (POS) type.
For more details on these fluorosilicones, reference may be made to the article by Ogden R. Pierce entitled “Fluorosilicons”, 1970, John Wiley & Sons Inc., pages 1 to 15.
A first known strategy for the industrial synthesis of silicones comprising perfluorinated units consists essentially in “hydrosilylating” a dihalohydroorganosilane, such as MeHSiCl 2 (Me=methyl), with an unsaturated compound carrying a perfluorinated unit with the general formula: CH 2 ═CH—Rf (Rf=perfluorinated unit). The addition of the silane to this olefin results in a perfluorinated dihalo-organosilane, which can be hydrolyzed so as to produce a functionalized silicone, which may, for example, be a cyclic tetramer. It is possible to subject the latter to a redistribution in order to obtain a perfluorinated linear polyorganosiloxane (POS). The hydrosilylation reactions which are involved in this type of synthesis and which employ various combinations of silicone hybrids and of perfluorinated olefins are known to be catalyzed by selected metal compounds and in particular certain metals from Group VIII, such as platinum. Pt/Sn complexes have thus been employed as hydrosilylation catalyst—cf. U.S. Pat. No. 4,089,882 (Shinetsu). This synthetic strategy appears to be relatively complex and therefore expensive.
For the sake of industrial simplification, a second synthetic strategy has been proposed based on the direct hydrosilylation of a silicone comprising an SiH unit using α-fluorinated olefin, e.g. of the CH 2 ═CH—Rf type, this perfluorinated unit Rf being directly attached to the olefinic CH via a carbon atom carrying at least one fluorine atom. Here again, various metal catalysts from Group VIII, in particular based on platinum, are used in the context of this hydrosilylation reaction. However, it turned out that these catalysts did not make it possible to achieve very high yields. In particular, conventional platinum-based industrial hydrosilylation catalysts (for example of the Karstedt type) are not very efficient. In addition, it could be observed that large amounts of by-product are generated, this very clearly being at the expense of the perfluorination of the silicones.
In U.S. Pat. No. 5,233,071, it is these linking units which are employed. They originate from the hydrosilylation of α-olefins. However, in order to overcome the shortcomings of the hydrosilylation catalysts used previously, the process disclosed in this patent resorts to cobalt-based organometallic complexes [(Co 2 CO 8 .Co 2 CO 6 ) (PR 3 ) 3 with R=alkyl, aryl]. It is apparent that such a technical proposal is unsatisfactory, as the reaction times obtained are of the order of a few days and it is essential to use a large amount of catalyst (1-2%), which is particularly penalizing to the economics of the process.
A not insignificant disadvantage of these cobalt-based complexes is that they catalyze other reactions than the hydrosilylation. In particular, they can participate in polymerization processes by cleavage of epoxy rings. This lack of specificity is a particular hindrance. In addition, these catalysts are not industrially usable.
U.S. Pat. No. 5,348,769 discloses linear or cyclic polyorganosiloxanes comprising D siloxyl units substituted by a first perfluorinated functional unit of formula —R 3 ZRf and other D siloxyl units carrying a second type of functional unit of the etherhydroxyl or alkylhydroxyl type. The linking unit or the bridge connecting Si to Rf of the first perfluorinated functional unit is composed in particular of: (CH 2 ) x Z, with x=2, 3 or 4 and Z=NHCO, NHSO 2 , O 2 C, O 3 S, OCH 2 CH 3 , NHCH 2 CH 2 or CH 2 CHOHCH 2 . The catalyst employed is preferably chloroplatinic acid.
Apart from these linking units, the precursors of which are perfluoroalkylated α-olefins of formula CH 2 ═CH—Rf, the prior technical literature also discloses bridges for which the olefinic precursors are of the CH 2 ═CH—L—Rf type; the chemical bond between L and Rf being an ester bond. The latter results from the reaction of a carboxyl functional group with a perhalogenated alcohol, preferably a perfluorinated alcohol. And generally, said carboxyl functional group is the product of the hydrolysis of an acid anhydride.
Thus it is that PCT Patent Application WO 94/12561 discloses POSs grafted with fluorinated units solely at the α- and ω-positions at the ends of the silicone chains. These α,ω-(alkyl ester perfluorinated) POSs do not exhibit optimum properties as regards the lowering in surface tension and the oleophobicity and the hydrophobicity.
European Patent Application No. 0 640 644 discloses, for its part, perfluorinated (Rf) silicone derivatives which can be used in cosmetic formulations. These perfluorinated silicone derivatives are characterized by D siloxyl units carrying perfluorinated grafts of three different types, namely:
with
R 2 and R 3 =alkyl, e.g. CH 3 ;
2≦l ≦16, e.g. l=3; 1≦m, n≦6; ≦p≦200; 0≦r≦50;
X and Y=single bond, —CO— or C 1 -C 6 alkylene.
These perfluorinated grafts (1) to (3) have in common the presence of ether bonds in the linking unit connecting the perfluorinated radical Rf to the silicon.
In order to overcome the absence of chemically stable perfluorinated POSs which can be obtained simply and economically, the Applicant Company has already provided novel linear or cyclic perfluorinated POSs corresponding to these specifications and comprising perfluorinated grafts Gf of formula: C m H 2m —Rf, in which m≧2 and Rf=perfluorinated residues; and optionally one or more other perfluorinated or nonperfluorinated grafts Gf with a first condition according to which at least 60% of the grafts Gf are perfluorinated and a second condition according to which, in the case where m=2, at least one other graft Gf is then provided which is different in nature from that defined in the above formula.
These POSs can correspond, e.g., to the following formula:
These POSs can be used in the formulation of lubricant antifoaming agents, of antiadhesive agents, of agents for lowering surface tension, of soil-resistant agents, of oleophobic and/or hydrophobic agents or of starting materials for the preparation of elastomers or of films which are resistant to chemical attacks and to solvents. These novel perfluorinated POSs and their production and their application are disclosed in French Patent Application No. 95 09 269.
French Patent Application No. 95 09 268 is a sister application of FR 95 09 269. This Application No. 95 09 268 discloses polyfunctional perfluorinated POSs comprising, on the one hand, fluorinated side grafts (Gf) resulting from the hydrosilylation of perfluorinated olefins by SiH groups and exhibiting alkyl and/or alkyl ester linking units, with the exception of ethers, and, on the other hand, other nonperfluorinated functional units (E) which can in particular be of the propylmalonyl type in the COOR or anhydride form or of the amine type.
These POSs can, e.g., be those of following formula:
These POSs have the same applications as those according to FR 95 09 629, including in particular textile soil resistance.
SUMMARY OF THE INVENTION
One of the essential objectives of the present invention is to select perfluorinated silicone compositions also possessing other functionalities very particularly suited to the preparation of hydrophobic and/or oleophobic coatings with a low surface energy (for example, soil-resistant coatings on textile substrates).
Another essential objective of the present invention is to improve the perfluorosilicone (co)polymers according to the prior art and in particular according to FR 95 09 269 and FR 95 09 268:
by providing them with better properties of attachment to the substrates, as regards the coating and/or impregnation applications,
and by improving their hydrophobic and oleophobic natures and their resistance to washing, to wear and to abrasion, in short by increasing their lifetime.
This is because it is important for perfluorosilicone systems to be insensitive to external attacks (solubilization/extraction due to washing or to the action of abrasives), so as to retain their desired properties of lowering the surface tension, which is the source of their impermeability, stain-resistance and soil-resistance functions. This is because the abovementioned external attacks have the direct repercussion of removing the surface perfluoro groups. In point of fact, it was seen above that this surface location of said Rf groups is essential for their effectiveness.
Having been set these objectives, among others, the Inventors have had the credit of demonstrating, after lengthy and laborious studies and experiments and in an entirely surprising and unexpected way:
on the one hand, that it is possible, advantageously, to use certain specific perfluorinated and functionalized silicone compositions for preparing hydrophobic and/or oleophobic coatings with a low surface energy (for example, soil-resistant coatings on textile substrates),
and, on the other hand, that it is possible to achieve the improvement by providing a silicone system comprising POSs carrying:
firstly, perhalogenated, preferably perfluorinated, grafts (Gf) carefully selected from perfluorinated esters of dicarboxylic acids capable of forming anhydrides (e.g. maleic acid); these Gf grafts being described as bifid Rf grafts;
secondly, attaching functional groups of HALS, epoxy or polyether type;
and optionally, thirdly, alkyl groups exhibiting more than 12 carbon atoms in substitution for a portion of the fluorinated grafts Gf.
It follows that the present invention relates first of all to the use of a silicone composition of the type of those comprising at least one perfluorinated POS A and optionally at least one functional additive B for the preparation of hydrophobic and/or oleophobic coatings and/or for carrying out hydrophobic and/or oleophobic impregnations with a low surface energy, characterized in that the POS A carries, per molecule:
one or more perfluorinated Gf grafts, which are identical to or different from one another, of formula:
in which:
the R 1 radicals independently represent hydrogen or a C 1 -C 6 alkyl
Rf 1 and Rf 2 are perhalogenated, preferably perfluorinated, radicals and more preferably still a linear or branched perf luoroalkyl radical of formula:
—CqF 2 q—CF 3 with q>/0; (II)
or
—CqF 2 q—H with q>/1; (III)
m=1 to 10;
n=0 to 4;
one or more attaching functional radicals F a , which are identical to or different from one another, chosen from the group of radicals carrying at least one amine functional group f a1 , preferably amine composed of a sterically hindered piperidinyl group and its derivatives; and/or at least one epoxy functional group f a2 and/or at least one (poly)ether functional group f a3 ; and/or at least one carboxyl functional group f a4 ;
and optionally one or more linear or branched (preferably linear) alkyl groups G alk comprising at least 6, preferably at least 8 and more preferably still between 10 and 20 carbon atoms.
It should be pointed out, as key for all the formulae given in the present description, that the free valencies represented in bold—are those which are attached directly or indirectly to the silicon of the molecule under consideration.
The term “low surface energy” is understood to mean, in accordance with the invention, values of total γ s ≦15 mJ/m 2 .
By choosing to use POSs substituted by Gf perfluorinated grafts of formula I of bisRf or Rf bifid type, by amine (preferably of the hindered piperidinyl type, e.g.: HALS), epoxy, polyether or carboxyl attaching functional groups f a , and optionally by long alkyls in place of the Gfs, the Inventors introduce an entirely satisfactory solution to the problem of the attachment of hydrophobic and oleophobic fluorinated coatings to substrates and of the increase in the resistance to aqueous and fatty substances. This makes it possible also to increase the durability of the effectiveness of the surface fluorine.
Furthermore, without wishing to be bound by theory, it would seem that the bifid structure of the Gf grafts selected according to the invention contributes to the achievement of an anisotropic arrangement, which promotes the hydrophobic and oleophobic effect of the perfluorinated units.
Within the meaning of the invention, the f a4 functional groups of carboxyl type are those corresponding to —COOR with R=hydrocarbonaceous radical or to COO − X + with X + =alkali metal or ammonium cation.
DETAILED DESCRIPTION OF THE INVENTION
Still as regards the Gf perfluorinated grafts, it should be noted that, according to the invention, the monovalent residues Rf 1 and Rf 2 in the formula I preferably correspond to —C p F 2p —CF 3 , with p between 3 and 20, preferably between 5 and 20 and more preferably still between 7 and 10.
In practice, it is also possible to employ, for example, mixtures of Rfs for which the indices p are equal to 7, 8 or 9.
According to an alternative form, the POS A carries, per molecule:
one or more perfluorinated Gfh grafts, which are identical to or different from one another, of formula (I.1):
in which:
R 11 , Rf 3 , m′ and n′ correspond to the same definitions as those given above for R 1 , Rf 1 , m and n;
Rh is a linear or branched, preferably linear, C 6 -C 40 and more preferably C 6 -C 20 alkyl radical.
As regards the attaching functional radicals F a of the POSs comprising Gf, indeed even Gfh, perfluorinated grafts used in accordance with the invention, these are hydrocarbonaceous radicals, identical to or different from one another, which can comprise one or more Hals, epoxy, ether or carboxyl functional groups f a1-4 .
F a can, for example, be composed of an f a1-4 functional group and of a linking unit which connects f a1-4 to a silicon of the siloxane chain. The linking units can be alkylenes, such as ethylenes, propylenes, butylenes. Thus, the functional group f a1 =amine, preferably hindered piperidinyl of HALS type, can form an F a functional radical in combination with a divalent propylene linking unit, and likewise for f a2 =epoxy, f a3 polyether or f a4 carboxyl.
As regards these f a4 functional groups of the carboxyl type, it may be envisaged, as an alternative form of the invention, that they are carried, in a molecule, by specific f a4 functional radicals corresponding to the following formula (IV):
in which:
R 13 , m′″ and n′″ correspond to the same definitions as those given above in the key to the formula (I.1) for R 11 , m′ and n′ respectively;
Z 1 and Z 2 correspond to —OH or together form an —O— bridge.
These attaching functional radicals Fa contribute to the permanence of the hydrophobicity and oleophobicity properties. In particular, they improve the resistance to washing.
The interactions between the substrates (e.g. textiles) and Fa, which are the cause of such results, can, if appropriate, be promoted by a catalyst.
According to an advantageous form, the POSs A employed in the use which is a subject matter of the invention comprise only a single type of f a1 or 2 or 3 or 4 functional group. Although an assortment of different f a S on the same POS A is not excluded, this single-f a alternative form is preferred for reasons of industrial simplification.
As regards the long alkyls G alk capable of forming pendant side groups for the POS A employed in the use according to the invention, it has appeared advantageous to choose them from alkylmalonate esters or analogous compounds.
It follows that the POS A advantageously carries, per molecule, one or more G alk group, which are identical to or different from one another, of formula (V):
in which:
R 12 , m″, n″ and Rh 1 correspond to the same definitions as those given above for R 11 , m′, n′ and Rh,
X corresponds to an Rh 2 radical corresponding to the same definition as Rh 1 or to hydrogen or alternatively to a hydrocarbonaceous radical other than Rh 1 and Rh 2 .
The G alk grafts of formula V in which Rh 1 and X are both long (e.g. C 12 -C 20 ) alkyls are particularly preferred.
The POS A is preferably linear and comprises, in addition to the siloxyl units substituted by Gf, F a and G alk , D siloxyl units of Si—H type and/or of —(R 2 ) 2 SiO— type.
Thus, in the case where the final application targeted is the soil-resistant coating for substrates (e.g. textiles), it is desirable for free D siloxyl units to exist.
According to an alternative form, the end M siloxyl units of the linear POSs A can be substituted by at least one group chosen from: Gf, F a and G alk .
Preferred POSs among which the POS A can be selected are in practice linear random POSs which can optionally exhibit up to 50% by weight of branchings (units other than D siloxyl units), cyclic polymers or three-dimensional polymers (resins comprising T and/or Q siloxyl units). (polymethylsiloxanes-polymethylhydrosiloxanes).
Thus, in a preferred embodiment of the invention, the composition comprises one or more POSs A corresponding to the following formula (VI):
with
Gf and F a representing, independently and respectively, perfluorinated grafts and radicals carrying F a functional groups, as defined above;
R 2 , which are identical to or different from one another, =methyl, propyl or butyl;
G alk , which are identical to or different from one another, =linear or branched alkyl, preferably C 6 -C 40 alkyl and more preferably C 6 -C 20 alkyl;
0<p i , preferably 1≦p i ≦100;
0≦p ii , preferably 0≦p ii ≦500;
0≦p iii , preferably 0≦p iii ≦10;
0≦p iv , preferably 0≦p iv ≦100;
0<p v , preferably 1≦p v ≦100;
Σp i to v +2=5 to 600, preferably 10 to 400.
In practice, it is possible to have:
1≦p i ≦50;
50≦p ii ≦300;
0≦p iii ≦5;
0≦p iv ≦50;
1≦p v ≦50;
Σp i to v +2=5 to 300.
According to an advantageous alternative form, the POS A used according to the invention comprises, in addition to the M and D siloxyl units, T and optionally Q siloxyl units.
The POS A of the composition according to the invention is also novel and advantageous because of the features relating to its production. It is preferably obtained from POSs chosen from polyalkylhydrosiloxanes, the SiH units of these POSs subsequently being at least partially used for the hydrosilylation of olefinic precursors of all or a portion of the Gf, Fa and optionally G alk grafts; in the presence of an effective amount of metal hydrosilylation catalyst, preferably based on platinum.
In the cases where first of all only a portion of the Gf, Fa or indeed even G alk grafts are grafted by hydrosilylation, the introduction of the missing part perhaps carried out in one or more graftings involving any chemical reaction mechanism.
This functionalization by segments can also be acceptable for the other Fr, Frc or alkyl substituents of the POS A.
In addition to the POS A, the perfluorosilicone composition employed in the context of the use according to the invention can comprise one or more functional additives B, such as surfactants, fillers, plasticizers, viscosifying agents, fluidizers, stabilizers, biocides or others.
As regards more specifically the soil-resistant coatings and/or impregnations for textile substrates application, the functional additives B are, for example:
thermocondensable resins for improving the dimensional strength or the behavior when washed or for introducing a degree of stiffness;
softeners which give a soft feel, which improve the behavior in the clothing industry and which favor the mechanical treatments (treatment with emery, napping, calendering);
antistatic agents which facilitate the flow of the electrostatic charges accumulated by the textiles during the various drying or polymerization operations and the like;
flame-retardant agents which decrease the flammability and prevent the propagation of the flame;
fungicidal and bactericidal agents which protect from molds and rots;
products which are commonly denoted under the name of extenders, which can, for example, be melamine resins modified by fatty acids or mixtures of waxes and of zirconium salts and which, in combination with fluororesins, substantially improve, in some cases, the properties thereof.
Insofar as it has been seen above that it is possible to envisage, according to a secondary alternative form, catalyzing the reactions which make possible bonding between the attaching functional groups F a1 to 4 of the F a radicals of the POS A and the substrate on which above said silicone composition can be applied, the silicone composition can optionally comprise at least one catalyst C capable of promoting the reactions under consideration.
According to another of its subject matters, the present invention relates to perhalosilicone, preferably perfluorosilicone, compositions as novel industrial products.
These novel compositions can in particular be employed in the use according to the invention.
A first family of these novel compositions is composed of those comprising at least one POS A of the type of that defined above, pages 7, line 10 to page 8, line 5, apart from the difference that F a corresponds to attaching functional radicals, which are identical to or different from one another, chosen from the group of radicals carrying at least one amine functional group F a1 , preferably sterically hindered piperidinyl, e.g.: HALS, and/or at least one epoxy functional group F a2 and/or at least one polyether functional group F a3 , with the exclusion of the carboxyl functional groups F a4 .
A second family of these novel compositions is composed of those comprising at least one POS A of the type of that defined above, page 7, line 10, page 8, line 5, apart from the difference
that F a corresponds to attaching functional radicals, which are identical to or different from one another, chosen from the group of radicals carrying at least one carboxyl functional group F a4
and that the POS A comprises, per molecule, at least one G alk group of formula V as defined above in which X=Rh 2 .
The novel compositions belonging to these two families can, following the example of all those employed in the context of the use according to the invention and defined above, optionally comprise functional additives B and/or at least one catalyst C as described above.
By virtue of the particular nature of the perfluorinated grafts G f , of the attaching functional radicals Fa and of the optional grafts G alk of the POS A, the compositions according to the invention make it possible to confer, in a lasting manner, a low surface tension on the solids to which they are applied or in which they are present. These compositions thus provide oleo- and/or hydrophobicity properties which are stable over time. This result is particularly advantageous and attractive for applications of the coating, finishing or impregnation type:
for textiles,
for buildings (coats, paints, graffiti-resistant paints, or glazes),
or for any other article to be protected against stains and dirt and to be rendered impermeable (e.g. antifouling paints for boats).
These fluorosilicone compositions according to the invention can also participate in the formulation of mastic, of pointing and leakproofing material, of lubricant, of antiadhesive agent, of antifoaming agent or of grease-resistant agent.
The lowering in the surface tension induced by the fluorosilicone compositions according to the invention, that is to say the oleo- and/or hydrophobicity properties, can be adjusted by controlling the proportions of D units grafted or not grafted by fluorinated and/or alkylated units. This corresponds to the variation in the indices p i to p v in the above formula (VI) of the POSs A.
Various functional additives D can be incorporated in the compositions of the invention according to the applications envisaged.
The compositions according to the invention are prepared by mixing the various constituents A and optionally B and/or C. Before being used or incorporated in operating formulations, these compositions can be in solution, in emulsion or in the form of a molten mass.
According to a characteristic of the invention, the POSs A according to the invention are obtained by hydrosilylation of olefinic precursors, comprising an end double bond (for example vinyl or allyl), of the various grafts or substituents envisaged for these POSs A, that is to say: Gf, Fa or G alk .
These hydrosilylations are carried out, in a way known per se, in the presence of an effective amount of industrial metal catalyst chosen from nickel-, palladium- or platinum-based compounds, preferably platinum-based compounds. This can be, for example, a Karstedt catalyst advantageously employed in a small amount, e.g. of the order of 10 to 50 ppm with respect to the POS compounds under consideration, before hydrosilylation (SiH oil). Hydrosilylation is a simple technique well known to a person skilled in the art. The kinetics thereof are fast and hydrosilylation makes it possible to achieve particularly high yields and degrees of conversion of the SiH units. The hydrosilylation conditions are conventional and can thus be easily determined by a person skilled in the art.
In practice, the hydrosilylation takes place in as many phases as there exist different olefinic reactants. The reaction medium is stirred and brought to a temperature of between 50 and 150° C. The reaction takes place at atmospheric pressure and generally over a period of several hours. The degree of conversion of the SiH units is greater than 90% by number.
It has been seen that the grafting of a specific substituent, for example: Gf, Fa, or G alk , can be broken down into several stages. The first of these stages is a hydrosilylation, by the SiH units of the POS, of a precursor of the substituent corresponding only to a portion of said substituent. To this first link, attached by hydrosilylation to the main chain of the POS, will subsequently be connected one or more other links or spacing compounds, until the graft or the substituent in its entirety is obtained.
The binding of the various links to one another can be carried out by various known chemical reaction mechanisms, e.g.: esterification, addition, substitution, and the like.
In the case of the Gf, Fa, or G alk grafts or radicals of formula I, I.1, IV, V or the like, it can be envisaged carrying out the grafting by first of all attaching to the POS, by hydrosilylation, a radical with one end comprising an ethylenic unsaturation and the other end exhibiting the two carboxyl functional groups in the form:
COOR′, with R′=hydrocarbonaceous radical,
COO − . . . X + , with X=alkali metal or ammonium cation.
These two carboxyl functional groups can also be provided in the anhydride form.
It is easy to react these carboxyl or anhydride reactive functional groups with interposed links or end links carrying the functionality or functionalities which it is desired to graft onto the POS. Thus, in the case where the operation has to be carried out on a first link comprising an anhydride end, it can be envisaged: subjecting at least a portion of the anhydride functional groups attached to the POS to hydrolysis, so as to generate free carboxyl ends, and subsequently esterifying at least a portion of said ends using reactants which make it possible to construct the graft in its entirety.
Mention may be made, among the POSs capable of being used as starting material for the preparation of the POSs A, of, by way of examples, linear POSs, such as polymethylhydrosiloxanes comprising from 10 to 100 D units of SiMeH or SiMeH and SiMe 2 type, or cyclic POSs such as tetramethylcyclosiloxane D′4.
The invention is also targeted, in another of these subject matters, at a process for the preparation of hydrophobic and/or oleophobic coatings and/or for carrying out hydrophobic and/or oleophobic impregnations on a substrate, this process being characterized in that it consists essentially:
in preparing and/or employing a composition as defined above,
in applying this composition to a substrate, so as to obtain a film and/or to impregnate it,
and in optionally evaporating the solvent, in the case where the composition is provided in the solution form.
The substrate under consideration can be a textile or any other solid material, such as, e.g.: metal, cement, concrete, wood, plastic, composite, and the like.
The applicational techniques come under the general knowledge of each specific field of use. The examples which follow give a few illustrations in this respect.
Industrial Application
The present invention also relates to the products or the formulations in which the composition to which it relates can be incorporated. They are, inter alia:
coating precursors,
coats,
paints (antifouling paints),
glazes,
lubricants,
agents for lowering the surface tension,
soil-resistant agents,
antiadhesive agents,
antifoaming agents,
oleophobic and/or hydrophobic agents,
starting materials for the preparation of elastomers or of films which are resistant to chemical attacks and to solvents,
textile finishing preparations.
The films and/or coatings prepared from the composition as defined above also come within the scope of the invention.
EXAMPLES
Example 1
Preparation of Silicone Compositions
1) Monomer Synthesis
Example 1
Synthesis of the Malonic Allyldiester of Hexadecanol
968 g (4 mol) of hexadecanol (Aldrich), 440 g of diethyl allylmalonate (2.2 mol) and 7.04 g of butyl titanate are introduced into a 2,000 cc reactor. The reaction mass is brought to 130° C. in order to remove the ethanol formed during the reaction. After reacting for 72 h, 95% of the expected ethanol has been removed (174.5 g) and the product is recovered by precipitating from methanol. NMR analysis confirms the purity of the product (cf. Example IX, EP No. 96 420 251.9). 2) Polymers Synthesis
The reaction is monitored by volumetric determination of the SiHs and the disappearance by IR of the peaks at 2,150 cm −1 corresponding to the SiH functional group and the peaks at 3,085 cm −1 and 1,645 cm −1 corresponding to the unsaturations.
Example 2
101.2 g of 1,2-dimethoxyethane (Prolabo) are introduced into a 500 cc reactor and and 3.7 mg of Pt are added in the form of an organometallic complex comprising 11.2% of platinum.
The temperature is brought to 90° C. and 29.64 g (0.05 mol) of the hydrocarbonaceous diester of example 1 (in the molten form, θ=60° C.) and 88.3 g of a fluid comprising SiH assaying 2.55 mol of SiH functional groups/kg (0.225 mol of SiH functional groups) with the formula: MD 50 D′ 50 M [M=(Me) 3 SiO 1/4 -/D=(Me) 2 SiO 2/4 /-D′=MeHSiO 2/4 ] are run in simultaneously over 1 hour.
After reacting for 3 hours, IR quantitative determination indicates that the unsaturations have disappeared and 84.6 g (0.075 mol) of the perfluorinated diester of diethyl allylmalonate (in the molten form, θ=60° C.) are run in over 30 minutes. After reacting for 16 hours, IR quantitative determination indicates that the unsaturations have disappeared and 19.7 g of 4-allyloxy-2,2,6,6-tetramethylpiperidine (0.1 mol) are added. After reaction for a total of 20 h, the degree of conversion of the SiH units is 95%.
The product is recovered by precipitating from methanol and is dried under vacuum in an oven at ambient temperature for 48 h.
Material balance=92%.
The product obtained is as follows:
Example 3
13.4 g of toluene (Prolabo) are introduced into a 150 cc reactor. Heating is carried out to 90° C. and 1.2 mg of Pt in the form of an organometallic complex comprising 11.2% of platinum are added.
A solution composed of 40 g of toluene (Prolabo), of 54 g (0.052 mol) of the perfluorinated diester of diethyl allylmalonate and 20 g of fluid comprising SiH of example 2 assaying 2.55 mol of SiH functional groups/kg (0.05 mol of SiH functional groups) is run in over 3 hours.
After reacting for 4 h 30, the degree of conversion of SiH units is 99.5%.
The product is recovered by precipitating from methanol and is dried under vacuum in an oven at ambient temperature for 48 h.
Material balance=91.8%.
The product obtained is as follows:
Example 4
70 g of hexamethyldisiloxane are introduced into a 500 cc reactor. Heating is carried out to 90° C. and 19 mg of Pt in the form of an organometallic complex comprising 11.2% of platinum are added.
A solution composed of 100 g of hexamethyldisiloxane, of 129.5 g (0.125 mol) of the perfluorinated diester of diethyl allylmalonate and and 82.9 g of a fluid comprising SiH assaying 1.64 mol of SiH functional group/kg (0.135 mol of SiH functional groups which is prepared as described in example 2) is run in over 3 hours. After reacting for 8 h, the degree of conversion of the SiH units is 92.6% and 1.98 g of 4-allyloxy-2,2,6,6-tetramethylpiperidine (0.01 mol) are added. After reacting for a total of 12 h, the degree of conversion of the SiH units by IR is 100%.
The product is recovered by devolatilization (3 h, 130° C., 2 mbar).
Material balance=95.7%.
Example 5
30 g of hexamethyldisiloxane are introduced into a 100 cc reactor and 0.9 mg of Pt in the form of an organometallic complex comprising 11.2% of platinum is added.
The temperature is brought to 90° C. and 25.07 g (0.04 mol) of the perfluorinated monoester of diethyl allylmalonate and 12.7 g of a fluid comprising SiH assaying 3.92 mol of SiH functional groups/kg (0.049 mol of SiH functional groups) prepared as described in example 2 are run in simultaneously over 1 h.
After reacting for 1 hour, the degree of conversion of the SiH units is 72.5% and 3.94 g (0.02 mol) of 4-allyloxy-2,2,6,6-tetramethylpiperidine are run in over 10 minutes. After reacting for a total of 8 h, the degree of conversion of the SiH units is 100%. The product is recovered by devolatilization (5 h, 150° C., 5 mbar).
Material balance=96%
Example 6
40 g of toluene (Prolabo) are introduced into a 250 cc reactor and 2.8 mg of Pt in the form of an organometallic complex comprising 11.2% of platinum are added.
The temperature is brought to 90° C. and 114.6 g (0.194 mol) of the hydrocarbonaceous diester of example 1 (in the molten form, θ=60° C.) and 17.52 g of a fluid comprising SiH assaying 15.8 mol of SiH functional groups/kg (0.276 mol of SiH functional groups) prepared as described in example 2 are run in simultaneously over 30 minutes.
After reacting for 19 hours, IR quantitative determination indicates that the unsaturations have disappeared and 62.3 g (0.055 mol) of the perfluorinated diester of diethyl allylmalonate (in the molten form, θ=60° C.) are run in over 30 minutes. After reacting for 36 hours, IR quantitative determination indicates that the unsaturations have disappeared and 5.42 g of 4-allyloxy-2,2,6,6-tetramethylpiperidine (0.0297 mol) and 2.8 mg of Pt are added. After reacting for a total of 192 h, the degree of conversion of SiH units is 98.8%.
The product is recovered by devolatilization (8 h, 160° C., 9 mbar).
Material balance=80%.
Example 7
55 g of toluene (Prolabo) are introduced into a 250 cc reactor and 1.8 mg of Pt are added in the form of an organometallic complex comprising 11.2% of platinum. The temperature is brought to 90° C and 22.8 g (0.136 mol) of 1-dodecene (Aldrich) and 17.6 g of a fluid comprising SiH assaying 15.8 mol of SiH functional groups/kg (0.279 mol of SiH functional groups) prepared as described in example 2 are run in simultaneously over 50 minutes.
After reacting for 4 hours, the degree of conversion of the SiH units is 55% and 54.7 g (0.109 mol) of the allyl ether of heptadecafluorodecanol are run in over 30 minutes. After reacting for 15 hours, the degree of conversion of the SiH units is 86% and 5.45 g of 4-allyloxy-2,2,6,6-tetramethylpiperidine (0.0297 mol) are added. After reacting for a total of 51 h, the degree of conversion of the SiH units is 98.3%.
The product is recovered by devolatilization (4 h, 140° C., 3 mbar).
Material balance=74.8%.
Evaluation of the Performances
The performances are evaluated from solutions of polymers in isopropyl acetate according to the standardized AATCC 118 (Oil Repellency-OR-) and EN 24920 (Spray Test) tests.
3.1 Application to Polyester/cotton Fabric at 20 g/l in Solution in Isopropyl Acetate
The results obtained are given in Table 1 below.
TABLE 1
Spray Test
OR
%
1 wash
5 wash
1 wash
5 wash
Exam-
fluo-
Ini-
1
+
5
+
Ini-
1
+
5
+
ples
rine
tial
wash
iron
wash
iron
tial
wash
iron
wash
iron
2
22
80
70
70
50
50
5
5
4
4
4
3
45
70
50
50
0
0
0
0
0
0
0
4
38
70
70
70
50
70
5
5
5
1
3
5
31.9
70
50
50
0
50
3
1
1
0
0
6
19.8
100
50
90
0
70
3
3
2
0
0
7
35.5
70
0
0
0
0
0
0
0
0
0
Key: iron = ironing − wash = washing.
The properties cannot be rendered permanent without interactions with the substrate (Example 3) despite a high fluorine content.
The presence of a perfluorinated diester linking unit also makes it possible to obtain properties which are substantially superior to those obtained with polymers based on perfluorinated allyl ether (Example 7) or on monoperfluorinated linking unit (Example 5), while the fluorine contents are lower (Examples 2 and 6).
The presence or absence of hydrocarbonaceous functional groups makes it possible to vary the oleophobic nature or the hydrophobic of the polymer (Example 6 and 4).
Application as an Emulsion at 20 g/l to Polyester Cotton
The results obtained are given in Table 2 below.
TABLE 2
Solids
Spray Test
OR
Exam-
content
%
Ini-
5
5 wash +
Ini-
5
5 wash +
ples
%
fluorine
tial
wash
iron
tial
wash
iron
2
15
22
80
70
70
5
5
5
3
45
70
50
50
3
0
0
4
38
80
70
70
5
4
5
503*
100
80
100
6
1
5
FC251**
100
70
80
5
1
2
*503 = Foraperle ® 503 from Atochem
**FC251 = Scotchguard ® from 3M.
4) Evaluation of Other Polymers
4.1. Preparation of POS A Polymers Substituted by Bifid Gfs and Fas=HALS in the Same Way as in Example 5
4.2. Oil Repellency (OR) and Water Repellency (WR) Tests in Various Solvents
The OR (AATCC 118 standard) and WR (ISO 4920 standard) tests are carried out as follows:
deposition of 700 ppm of fluorine (impregnation of a circular sample of polyamide carpet weighing 15 g) from various solutions of POS A comprising Gf grafts and comprising Fa=HALS,
drying for 6 min at 80° C.,
heat treatment for 4 min at 140° C.
4.3. Results
The results are given in Table 3 below.
TABLE 3
Ex. No.
POS A
Solvents
OR
WR
8 Comparative
MIBK Methyl isobutyl ketone
0
0
8
MIBK
4
3
9
MIBK
5
7
10
MIBK
6
7
11
MIBK
5
7
12
MIBK
6
7
The classification of these POSs A can be carried out as such:
O: poor performances
XX: good performances
The results obtained are given in Table 4 below.
TABLE 4
O
XX
9
8
10
11
8 Comp.
12
5) Application as an Emulsion
5.1. Methodology
The same substrate is used as for the application in a solvent and 700 ppm of fluorine are deposited (spraying a circular sample of polyamide carpet weighing 15 g using a spray gun) from emulsions. The carpet is subsequently subjected to drying for 6 minutes at 80° C. and then to a heat treatment for 4 minutes at 140° C. The emulsions are prepared from the POS A of Example 9 and two commercial products are tested under the same conditions as comparative examples. (They are the products AG 850 from Asahi and FC 396 from 3M, referenced respectively as Comp. Example 17 and Comp. Example 18).
5.2. Composition (as Weight %) for Examples 13 to 16
TABLE 5
Example No.
Constituents
13
14
15
16
POS A = fluorosilicone
19.9
13.6
25.1
13.6
Example No. 9
Methyl isobutyl ketone
14.9
28.9
22.3
10.2
Acetic acid
0.5
0.17
0.51
0.63
Water
64.7
41.8
50.2
41.8
Genapol X050
0.68
Genapol X080
1.25
0.68
5.3. Soil-resistance Results
TABLE 6
Example No.
OR
WR
13
4
4
14
4
4
15
4
5
16
4
4
Comp. 17
4
4
(Asahi)
Comp. 18
5
3
(3M)
5.4. Evaluation of the Permanency
The permanency nature of the coating is demonstrated by several techniques.
Characterization of the contact angles on a polyamide PA 6-6 film before and after extracting with a solvent
Evaluation of the soil-resistant properties before and after washing on various substrates.
5.4.1. Contact Angle Measurements
The process for the preparation of the samples is as follows:
extraction of the PA 66 films with MeOH in a Soxhlet
drying for 48 h at 80° C.
coating with 1% solutions in freon by spin coating
drying for 4′ at 140° C.
extraction with MeOH for 2 h in a Soxhlet (80° C.)
drying for 4′ at 140° C.
The values for surface energy, which is calculated from the angles formed with diodomethane and water, are presented in the following Table 7.
TABLE 7
Surface energy (mN/m)
Example No.
Before extraction
After extraction
9
11.2
14.6
10
11.4
13.9
Comp. 17
8
21
The values obtained before extraction correspond to surface energies for perfluorinated compounds. After extracting for 2 hours with methanol at 80° C., the coating is found to be permanent except in the case of Comp. Sample 17, which does not comprise acidic or HALS functional groups.
5.4.2. Evaluation of the Resistance to Washing
The evaluation is carried out on three types of substrate (polyamide microfibers, polyester or cotton). The application is carried out by spraying with a spray gun starting from the following emulsions, which are diluted, so as to deposit, in each case, 2 000 ppm of fluorine on the textile.
Comp. Example 21 and Comp. Example 22 are comparative examples of perfluorinated products for the treatment of textiles (3M). The emulsion is used as is (Comp. Example 21) and according to the recommendations of the supplier (Comp. Example 22).
The emulsion compositions for Example 19, Example 20, Comp. Example 21 and Comp. Example 22 are given in the following Table 8.
TABLE 8
Example No.
21,
22,
Emulsion composition
19
20
Comp.
Comp.
Fluorosilicone No. 8, Comp.
19
Fluorosilicone No. 9
19.7
Methyl isobutyl ketone
14.8
14.8
Acetic acid
0.5
0.12
Water
65.2
64
87.65
Genapol X080
1
1
FC251 (3M)
100
2.13
Quedocur FF (Thor)
8
Magnesium chloride
2
The performances on three types of fabrics:
cotton: Table 9
PET/cotton: Table 10
Polyamide μfibers: Table 11
and are evaluated in the initial state, after 5 washing operations at 40° C. for 40 minutes and then after ironing.
TABLE 9
COTTON
5 washing
5 washing
operations +
Initial
operations
ironing
Example
OR
spray test
OR
spray test
OR
spray test
19
2
50
0
0
0
0
20
5
70
2
50
4
50
21, Comp.
3
90
1
50
0
50
22, Comp.
6
90
0
50
0
50
TABLE 10
PET/COTTON
5 washing
5 washing
operations +
Initial
operations
ironing
Example
OR
spray test
OR
spray test
OR
spray test
19
3
70
0
50
0
50
20
5
70
4
50
5
70
21, Comp.
5
100
1
70
2
80
22, Comp.
6
80
0
70
4
70
TABLE 9
POLYAMIDE μFIBERS
5 washing
5 washing
operations +
Initial
operations
ironing
Example
OR
spray test
OR
spray test
OR
spray test
19
3
50
0
0
0
50
20
5
70
2
50
0
50
21, Comp.
6
100
3
70
6
100
22, Comp.
6
100
0
70
6
80 | A functionalized silicone with perfluorinated polyorganosiloxanes (POS) R f is used to produce coatings with low surface energy and improved adherence to supports. The compositions include a group POS A bearing, per molecule, bis-perfluoromalonate grafts Gf, functional radicals Fa of the amine (HALS) f a1 , epoxy f a2 , (poly)ether f a3 , carboxy f a4 type, and optionally alkyl groups G alk . The invention is useful for producing soil release coatings for textiles. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention:
The present invention relates to the field of spring energized gyros.
2. Prior Art:
Spring energized gyros are two axis free gyros having a rotor which, when the unit is fired, is spun up by a prewound spring. In a simplest form, a drive member is coaxial with and extends to engage the end of the rotor shaft. Upon firing of the device by squib or otherwise, a prewound spring spins the drive member, with the drive member, rotor shaft and either the drive spring or another spring then cooperating to disengage and withdraw the drive member. Once withdrawn the rotor in an instrument in use will coast at a relatively high speed throughout the relatively short duration of its use, or if in test, will coast to a stop after a few minutes. In general during testing, the rotor will not stop in a position aligned with the drive member, so that in order to re-engage the drive member with the rotor shaft and rewind the spring, access to the instrument interior is required to allow manual repositioning the gimbals of the gyro for re-engagement of the drive member. Since the purpose of testing normally is to verify that the instrument as closed and sealed has the full required freedom and accuracy of operation, the opening of the instrument to rearm the same negates a substantial purpose of the test, as it provides an opportunity for the entry of foreign matter, may result in repositioning or breaking of lead wires, etc., which can only be discovered by again retesting. Accordingly, it is the purpose of the present invention to provide for the caging and rearming of a spring wound gyro after testing without having to gain entry into the main instrument enclosure, thereby eliminating the opportunity for entry of foreign matter, etc., and making testing thereof prior to actual use much more meaningful and a much more valid verification of what the performance in use will be.
BRIEF SUMMARY OF THE INVENTION
A rearmable spring caged and energized free gyro which will allow repeated rearming for testing and use without requiring the opening of the main instrument enclosure, or requiring auxiliary sources of energy is disclosed. The gyro is housed in an approximately cylindrical enclosure with the spin axis perpendicular to the axis thereof. A helical spring substantially coaxial with the enclosure is positioned adjacent one end of the enclosure, and may be wound through that end of the enclosure by an appropriate winding tool. During the winding of the spring a cam moves substantially coaxially along the inside of the enclosure, engaging a roller adjacent the end of the pitch axis which rotates the gimbal assembly around the roll axis to the roll axis caged position, at which time the end of the inner gimbal cooperatively references to the cam to align the spin axis. At the same time an annular gear moves axially in the enclosure to engage a gear on the end of the spin axis, so that upon complete winding of the spring the gyro is caged ready for firing. Upon release of the spring, typically by firing a squib, the annular gear engaging the gear on the end of the spin axis rotates a fraction of a turn to run the rotor up to speed, with additional rotation of the spring drive resulting in retraction of the axially moveable cam and annular gear to release the inner gimbal and spin axis for free gyro operation of the system. The combined caging and arming of the spring wound gyro by a single winding device avoids intrusion into the main enclosure of the instrument for rearming for repetitive testing and subsequent use.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the preferred embodiment of the present invention.
FIG. 2a is an end view of the instrument of FIG. 1 with the cover 24 removed.
FIG. 2b is a side view of the rachet member 28 and lever 36 as illustrated in FIG. 2a.
FIG. 3 is a partial cross section taken along line 3--3 of FIG. 2a.
FIG. 4 is a partial cross section taken along line 4--4 of FIG. 3.
FIG. 5 is a partial cross section taken along line 5--5 of FIG. 4.
FIG. 6 is a partial cross section taken along line 6--6 of FIG. 3.
FIG. 7 is a partial cross section similar to FIG. 3 with the caging ring 122 in the uncaged position.
FIG. 8 is a graphic illustration of the cam slot 110 in the cam ring 106.
DETAILED DESCRIPTION OF THE INVENTION
First referring to FIG. 1, a perspective view of the preferred embodiment of the present invention may be seen. As shown, the instrument is comprised of a generally cylindrical enclosure 20, having three mounting holes on a flange 22 at one end of the housing and having a removable cover 24 on the flanged end of the instrument. For convenience of orientation with respect to the descriptions of the other figures to follow, the three major axes, specifically the roll axis, pitch axis and spin axis of the instrument, have been identified in this figure.
Now referring to FIG. 2a, an end view of the instrument of FIG. 1 with the cover 24 removed may be seen. It will be noted that the cover 24 merely covers a cavity at the flanged end of the instrument so that the removal thereof only exposes those few elements shown in the figure, with the main instrument assembly being separated therefrom by the interior wall 26.
As may be seen in the figure, located below cover 24 and accessible upon the removal thereof is a rachet member 28 having openings 29 therein for recaging the instrument and rewinding the re-energizing spring after firing the instrument for test purposes. The rachet member 28 as seen in a side view thereof in FIG. 2b is comprised of a toothed member 30 with a plate 32 on the back side thereof. The rachet member 28 is retained in the wound or partially wound positions by a pawl or dog 34 on arm 36 pivotally supported on pin 38 and yieldably encouraged to the dog 34 engaged position shown by spring 40 retained on pin 42. Mounted adjacent the opposite end of arm 36 is an electrically fireable squib 44 fastened to inner wall 26 through a mounting plate 46 and disposed so as to engage arm 36 to rotate the same about pin 38 to withdraw dog 34 from the rachet member 28 when fired. At the same time a finger 48 integral with arm 36 (see also FIG. 2b) is forced under plate 32 of the rachet member 28 to encourage the same upward for reasons which shall be subsequently described.
Also visible upon the removal of cover 24 is a pair of terminals 50 and 52 mounted on mounting block 54, the terminals 50 and 52 being leaf-like spring members extending through the block to positions adjacent the end of arm 36. In particular, end 56 of terminal 50 cooperates with a cam-like surface on the end of arm 36 to be deflectible upon rotation of the arm from the position shown to make electrical contact with the end 58 of terminal 52, thereby providing a switch closure signal indicative of the firing of the squib.
Now referring to FIG. 3, a partial cutaway view of the instrument of FIGS. 1 and 2 may be seen. In particular it will be noted that rachet member 28 is positioned somewhat above the inner wall 26, with a coil spring 60 yieldably encouraging the rachet member still further upward, the upward movement of the rachet member being inhibited when the instrument is armed by the engagement of dog 34 (FIG. 2a) with the plate 32 on the lower part of the rachet member. Other elements such as block 54, terminals 50 and 52, etc., are not shown in this region for purposes of clarity. As may be seen in this figure, the rachet member 28 is supported on pin 62 passing through a journal-like bearing formed as part of inner wall 26, the pin having a gear 64 on the inner end thereof. Cooperating with gear 64 is another gear 66 rigidly coupled to a spring housing 68 enclosed by a cover 70 fastened thereto. The assembly of gear 66, spring housing 68 and cover 70 is rotatably supported on a central pin 72 mounted to the inside surface of the inner wall 26 by a bolt 74 threaded thereinto, the inner diameters of the spring housing 68 and cover 70 having a freely rotatable fit on the pin 72. Locating within the enclosure defined by the spring cover 68 and cover plate 70 is a helical spring, not shown in FIG. 3, but visible in cross section as spring 176 in FIG. 7. The helical spring has its inner end anchored to pin 72, with the outer end thereof anchored to the spring housing 68. Accordingly, it may be seen that with the rachet member 28 and the gear 64 in the position shown in FIG. 3, the spring may be wound by turning the rachet member clockwise as viewed in FIG. 2a. It may also be seen that upon the firing of the squib 44, dog 34 (FIG. 2a) will be withdrawn from the rachet member 28, allowing the rachet member to start to spin as the helical spring starts to unwind with finger 48 on lever 36 in combination with coil spring 60 forcing the rachet member outward to withdraw gear 64 from engagement with gear 66, thereby allowing the spring to substantially immediately more freely unwind.
Mounted from pin 72 on a bearing 76 and from end wall 78 on bearing 80 is the outer or roll gimbal 82 having balance screws 84 therein for balancing the assembly about the roll gimbal axis. The inner or pitch gimbal 86 is mounted to the outer gimbal 82 on bearings 88. The pitch gimbal 86 is relatively flat to fit between rotor segments 90 of a dumbbell rotor configuration, the gimbal having a central hub 92 for supporting the spin bearings 94 therein. The two rotor segments 90 are supported on the bearings 94 by rotor shaft 96, one end of which has a pinion gear 98 thereon and the other end of which has a roller 100 thereon, the roller having a diameter substantially equal to the minor diameter of the pinion gear 98. Spin bearing end play is adjusted in the assembly by a pair of lock nuts 102.
The output of the instrument shown comprises a Hall effect sine-cosine generator of conventional construction on the outer or roll axis gimbal. The Hall effect generators 102 (only one being shown in FIG. 3) are mounted on the end 78 of the instrument enclosure with the permanent magnet 104 on the outer gimbal itself. Obviously if desired an appropriate pitch axis position pick off could also be used, and/or pickoffs of other construction could be used. Of course the single roll axis pick off of the type described coupled with the spring energized rotor avoids the need for any slip rings or other gimbal to gimbal and gimbal to case electrical contact. For purposes of clarity, electrical feedthroughs, pigtails, etc., for the pickoff outputs and the squib leads are not shown, though are of conventional construction for gyros and related instruments.
Referring again to FIG. 3, a cam ring 106 concentric to the spring housing 68 is rigidly mounted to the internal wall 26 by screws 108 (only one being shown in the figure). As shall subsequently be described in greater detail, the cam ring 106 has a slot 110 cut in its inner surface, the slot forming internal cam surfaces over approximately 720 degrees. Between the cam ring 106 and the spring housing 68 is a second ring, specifically a gear ring 112 effectively keyed to member 114 connected to the spring housing 68 so as to be slideable axially with respect thereto but not rotatable with respect thereto. The gear ring 112 has a flange 116 thereon captured between a shoulder 118 and a snap ring 120 on a caging ring 122 subsequently described. The gear ring 112 has gear teeth 124 cut in the end thereof which gear teeth cooperate with the pinion gear 98 when the gear ring 112 is in the position shown so that the instrument rotor will be spun by the rotation of the gear ring. This may be best seen in FIGS. 4 and 5. At the same time roller 100 will be supported by the tops of the gear teeth to help stabilize the inner rotor from deflecting about the pitch axis because of the component of force on the gear 98 parallel to the roll axis of the instrument.
The capturing of flange 116 on the gear ring 112 between the shoulder 118 and snap ring 120 on the caging ring 122 assures that the caging ring 122 and the gear ring 112 move in unison with respect to any axial movement thereof, though the gear ring 112 is free to rotate with respect to the cam ring because of the looseness of the fit of flange 116. To maintain the gear ring 112 coaxial with the caging ring 122, rollers 126 having their axes parallel to the roll axis of the instrument are positioned at 120 degree intervals in the space between the gear ring and the caging ring to ensure both accurate coaxial alignment and free rotation with respect thereto (only one of the rollers 126 being visible in FIG. 3). At the end of gear ring 112 opposite to the gear teeth 124 is a pin 128 projecting into slot 110 and thus acting as a cam follower for the cam effectively defined by the varying lead of the slot. Thus on rotation of the spring housing 68 the axial position of the gear ring 112 and the caging ring 122 will be determined by the cam arrangement defined by the slot 110 and pin 128.
The caging ring 122 itself is guided along the interior wall of enclosure 20 for motion along the roll axis by rollers 130 adjacent opposite ends of the caging ring and positioned at 120 degree increments around the circumference of the caging ring. In that regard it should be noted that the shafts on which the various rollers hereinbefore described operate need not be fully journaled or captured in the various parts to which they are mounted, but rather may be merely captured in appropriately disposed U shaped slots as desired, as such slots will more than adequately retain appropriately shaped shafts or axles in the final assembly. The rollers 130 at the two spaced apart axial positions on the caging ring provide for the axial concentricity of the caging ring, yet free axial motion thereof as dictated by the rotation of the spring housing 68, the caging ring being restricted from rotation by the key arrangement 132 (FIG. 3). The relative positions of the gear ring 112, the cam ring 106 and the caging ring 122 as well as other parts such as the key 128, etc. being shown in FIG. 6 in a cross section taken along lines 6--6 of FIG. 3.
Now referring to FIGS. 4 and 5, details of the gimbal structure and cam ring which allow the cam ring to cage the instrument may be seen. In particular, a roller 132 is positioned adjacent one end of the inner or pitch gimbal axis at a location to cooperate with the end of the caging ring 122 as shown in FIG. 5. As shown in FIG. 4 and perhaps better illustrated in FIG. 7, the roller 132 is supported in a U shaped structure 134 having a width as viewed in FIG. 4 substantially equal to the diameter of the roller. As shown in FIG. 4, the end 136 of the caging ring 122 is tapered in both directions starting from a high point at one point thereof and terminating in a U shaped slot 138 at the desired caging point 180 degrees therefrom. Thus it may be seen that in the state illustrated in FIG. 4, the roll gimbal has been rotated until roller 132 fell into slot 138 and the inner gimbal has been aligned thereby, while simultaneously the ring gear 112 has engaged the pinion 98 on the spin axis, with the other end of the spin axis being supported on roller 100 from the tops of the ring gear teeth.
In FIG. 7 on the other hand, the caging ring 122 as well as the gear ring 112 are shown in the withdrawn or retracted positions. As retracted, unless otherwise restricted, the outer gimbal will have full 360 degree rotation capabilities and the inner gimbal will enjoy substantial angular freedom, though in the embodiment shown, not a full 360 degree freedom. In that regard, instruments of this general type generally require full freedom about the roll axis, but only limited freedom about the pitch axis, the preferred embodiment disclosed herein having approximately ±40 degrees of freedom about the pitch axis. Thus as the caging ring 122 moves from the position shown in FIG. 7 toward the position shown in FIGS. 3 and 4, roller 32 will engage the cam surface defined by the end of the caging ring 122 to first rotate the outer gimbal about the roll axis until the roller 132 falls into slot 138 (FIG. 4), at which time rotation about the roll axis, having reached the caged position, will stop. Member 134 will then be intercepted by the walls of the slot to rotate the inner gimbal to the caged position well before the roller bottoms in the slot, thereby rotating the inner gimbal to the caged position, and as importantly, to align the spin axis so that gear 98 and roller 100 are rotated about the pitch axis so as to be properly engaged by the gear teeth 124 on the end of the gear ring 112 as the caging ring 122 moves to its final caged position.
Having completed the description of the structure of the present invention and the manner in which caging is accomplished by the motion of the caging ring 122, the overall operation of the instrument will now be described. The slot 110 (see particularly FIGS. 3 and 7) has the general shape illustrated in FIG. 3. In particular, as stated before, the slot extends over approximately 720 degrees or two full turns, with a substantially circular portion of approximately 270 degrees at each end thereof interconnected by an approximately 180 degree section of substantial lead. The left end of FIG. 8 represents the armed condition as illustrated in FIGS. 3 and 4, wherein the caging ring is extended to maintain the gimbals in the caged position and of course the helical spring 76 is fully wound, whereas the right end of FIG. 8 represents the condition existing before arming or rearming of the instrument (or even very shortly after firing of the squib) wherein the caging ring is in the withdrawn or uncaged position so as to not restrict the gimbal freedom, as illustrated in FIG. 7.
For purpose of explanation it will be assumed that the currently installed squib has not been fired, and that the instrument is otherwise in the condition illustrated in FIG. 7. In this condition the pin 128 (see FIG. 3) will be at the right hand end of the slot 110 of FIG. 8. The first step in arming the instrument is to rotate lever 36 clockwise against spring 40 (FIG. 2a) to allow rachet member 28 (FIG. 7) to be pushed inward against coil spring 60 until gear 64 is in engagement with gear 66 on the spring housing 68 and the plate 32 (FIG. 2b) has moved to a position below or behind lever 36, at which time lever 36 may be allowed to spring back to the position illustrated in FIG. 2b. Then with the winding key, rachet member 28 is rotated in a direction to rotate the spring housing 68 to wind up spring 76, the rotation of the spring housing causing the pin 128 to move to the left in slot 110 of FIG. 8. As the spring continues to be wound, the caging ring and the gear ring will both be extended as the pin moves into the inclined portion of the cam slot, the caging ring caging the instrument as hereinbefore described as it is being extended and the gear ring ultimately engaging the gear on one end of the spin axis and the roller on the other end of the spin axis as the caging ring 112 moves to its final caged position. Thereafter as winding continues the instrument remains in the caged condition, with the winding of course ultimately terminating as the pin 128 ultimately reaches the left end of slot 110 as illustrated in FIG. 8. Note that because the gear ring 112 rotates with the spring housing which in turn rotates during winding, the teeth on the gear ring 122 will first engage the teeth in pinion gear 98 at approximately location 140 illustrated in FIG. 8, with the instrument rotor thereafter rotating about the spin axis as driven by the gears as winding continues. Of course on firing the instrument as hereinbefore described, rachet member 28 is both released for rotation and forced outward by spring 60 and the action of the squib to disengage gear 64 from gear 66 to allow the tightly wound spring to rotate the spring housing 68 and ring gear 112 to spin up the rotor, and to then withdraw both the caging ring and gear ring to allow the operation of the two axis free gyro during at least the initial period of the rotor coast down. Note that upon firing, rotor spin up occurs essentially during the first 270 degrees of rotation of the gear ring, after which time the gear ring and caging ring move to their uncaged positions. In general the 270 degree rotation is ample rotation to spin the rotor up, prototypes of the present invention spinning up to approximately 12,000 rpm during that period. Also note that from the foregoing description and the structure illustrated, the gyro in essence remains caged during the initial withdrawal of the caging ring because of the shape of the caging slot, etc., which essentially keeps the gyro caged until after the gear ring disengages from the pinion on the end of the spin axis. This tends to minimize any kick or mutation which may be incurred upon the disengagement of the gears due to the spring putting either an accelerating or decelerating torque on the spin axis gear at the moment of disengagement.
There has been described herein a new and unique rearmable spring caged and energized free gyro which allows the repeated testing thereof without having to gain access to the main instrument enclosure and without having to provide electrical or other alternative energy sources for effecting the caging thereof. While the present invention has been disclosed and described with respect to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention. | A rearmable spring caged and energized free gyro which will allow repeated rearming for testing and use without requiring the opening of the main instrument enclosure, or requiring auxiliary sources of energy. The gyro is housed in an approximately cylindrical enclosure with the spin axis perpendicular to the axis thereof. A helical spring substantially coaxial with the enclosure is positioned adjacent one end of the enclosure, and may be wound through that end of the enclosure by an appropriate winding tool. During the winding of the spring a cam moves substantially coaxially along the inside of the enclosure, engaging a roller adjacent the end of the pitch axis which rotates the gimbal assembly around the roll axis to the roll axis caged position, at which time the end of the inner gimbal cooperatively references to the cam to align the spin axis. At the same time an annular gear moves axially in the enclosure to engage a gear on the end of the spin axis, so that upon complete winding of the spring the gyro is caged ready for firing. Upon release of the spring, typically by firing a squib, the annular gear engaging the gear on the end of the spin axis rotates a fraction of a turn to run the rotor up to speed, with additional rotation of the spring drive resulting in retraction of the axially moveable cam and annular gear to release the inner gimbal and spin axis for free gyro operation of the system. | 8 |
FIELD OF INVENTION
[0001] This invention relates to plumbing devices and is particularly directed to improved means for blocking floor sink drain openings to prevent passage of large objects, while allowing free flow of fluid therethrough.
[0002] As is well known, food preparation kitchens are usually provided with a floor sink having a drain opening which connects to a grease trap or sewer to allow disposal of indirect waste water and the like. Unfortunately, rags, napkins, silverware and other large objects are often washed into the floor sink along with the floor washing water and these objects often get carried into the drain and cause blockage, flooding and other problems. Moreover, the loss of napkins, silverware and the like add significant expense to the operation of the restaurant. Unfortunately, most floor sinks have open drains which are subject to the problems noted above. Some prior art drain grates or screens have been provided which are permanently installed in the drain opening. However, these often become clogged and simply add to the flooding problem. Thus, none of the prior art sink drain screens have been entirely satisfactory.
SUMMARY OF THE INVENTION
[0003] These disadvantages of the prior art are overcome with the present invention and an improved floor sink drain screen is provided which positively precludes passage of large objects, while permitting free passage of fluid and which can quickly and easily be removed for cleaning, when desired. In some embodiments, a special, tamperproof locking key may be used to prevent unauthorized disassembly of the installed floor drain screen.
[0004] These advantages of the present invention are preferably attained by providing an improved floor sink drain screen lock having expandable means for engaging the walls of a floor sink drain, yet being readily collapsible for quick and easy removal when desired.
[0005] Accordingly, it is an object of the present invention to provide an improved floor sink drain screen locking apparatus.
[0006] Another object of the present invention is to provide an improved floor sink drain screen lock which positively precludes passage of large objects.
[0007] A further object of the present invention is to provide an improved floor sink drain screen lock which positively precludes passage of large objects while permitting free passage of liquids.
[0008] An additional object of the present invention is to provide an improved floor sink drain screen lock which positively precludes passage of large objects while permitting free passage of liquids and which can quickly and easily be removed for cleaning, when desired.
[0009] Yet another object of the present invention is to provide improved floor sink drain screen locks having expandable means for sealingly engaging the walls of a floor sink drain, yet being readily collapsible for quick and easy removal when desired.
[0010] These and other objects and features of the present invention will be apparent from the following detailed description, taken with reference to the figures of the accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is an upper isometric view of a removable locking floor sink drain screen for enlarged opening embodying the invention.
[0012] FIG. 2 is a lower isometric view of an embodiment of the invention.
[0013] FIG. 3 is an exploded front view of an embodiment of the invention.
[0014] FIG. 4 a is a plan view of an embodiment of the center section of the locking floor sink drain screen.
[0015] FIG. 4 b is a plan view of another embodiment of the center section of the locking floor sink drain screen.
[0016] FIG. 5 is a plan view of the lower section of the locking floor sink drain screen.
DETAILED DESCRIPTION OF THE INVENTION
[0017] FIG. 1 depicts a locking floor sink drain for an enlarged opening, indicated generally at 10 . An upper grate 12 formed with a central opening 14 is surrounded by a plurality of additional openings 16 through which water or any other liquid can be drained. A middle section 18 has a non-expandable section 19 with an internal flange 32 that supports a plurality of vertical separators 22 . An expandable ring section consists of a number of panels 20 separated by a plurality of slits 21 that permit the panels 20 to be forcefully expanded against the inner surface of a drain pipe (not shown). The vertical separators 22 space the grate 12 from the flange 32 and are themselves spaced apart to permit draining liquid to flow into and through the center cavity of the device and down the drain pipe. Positioners 30 attached to the vertical separators 22 interface with the grate 12 to prevent substantial rotational or sliding movement between the grate 12 and the separators 22 . The separators 22 also position and secure the grate 12 above the middle section 18 .
[0018] A hollow tapered section 24 has an outer diameter 36 that is larger than the inner diameter of middle section 18 and incorporates internal structure to form a threaded hole 28 . Threaded hole 28 receives a threaded bolt 26 that extends through the central opening 14 of the grate 12 , through the middle section 18 , and secures the grate 12 to tapered section 24 . When tightened, the threaded bolt 26 pulls the tapered section 24 upward and into the middle section 18 , causing the panels 20 of the middle section to expand against the inner diameter of the drain pipe.
[0019] Although depicted as a square plate, the metal grate can be circular, rectangular, or of an irregular shape, depending upon the configuration of the installation environment.
[0020] FIG. 2 is a lower isometric view of the drain locking device for an enlarged drain. This view provides some detail of the tapered section 24 , and shows exemplary structure through which threaded hole 28 is formed.
[0021] FIG. 3 shows an exploded front view of the locking device of this invention. Threaded bolt 26 may have a head 40 which may be a slotted screw, a hexagonal head, a tamperproof head, or any other suitable means know in the art for tightening or loosening bolt 26 . In a preferred embodiment, grate 23 may be metallic, such as brass or stainless steel, although any suitable corrosion-resistant material of sufficient strength and flexibility will suffice, and will have an indented portion 38 to receive the head 40 of bolt 26 and position it flush with the upper grate surface. The grate 23 is supported by vertical separators 22 , and optionally may be secured by positioners 30 or, in some embodiments, suitable fastening means to hold middle section 18 in a fixed relationship with respect to grate 23 . Vertical separators 22 are supported by an internal flange 32 located within upper non-expandable portion 19 of middle section 18 . The lower portion of middle section 18 is a plurality of panels 20 being separated by slits 21 whereby the panels 20 may be forced apart and outwardly against the interior surface of a drain pipe (not shown).
[0022] A frusto-conical tapered section 24 of the device has a threaded through hole 28 that receives threaded bolt 26 . The upper diameter 34 of the tapered section 24 is smaller than the inner diameter of middle section 18 , while the lower diameter 36 of the tapered section is larger than the inner diameter of middle section 18 . As threaded bolt 26 is tightened, tapered section 24 is drawn up against the expandable section 20 of middle section 18 , causing the panels 20 to expand and press against the inner surface of a drain pipe and lock the device into the drain.
[0023] FIG. 4 a is a plan view of the middle section 18 of the device of this invention. As viewed from above in FIG. 4 a , vertical separators 22 may have a rectangular cross-section and a positioning knob or fastening means 30 to interface with the grate 12 . Fastening means 30 may assist in maintaining the physical relationship between grate 12 and middle section 18 , and may be positioning knobs, threaded screws, or any other suitable fastening means known in the art. An internal flange 32 supports vertical separators 22 within non-expandable portion 19 of middle section 18 . FIG. 4 b depicts the separators 22 as being curved, and permits flange 32 to have a smaller lip, thus increasing the size of the cavity through which liquid may flow. Although the embodiment depicted in FIGS. 4 a and 4 b shows four separators, the choice of configuration of separators 22 as rectangular or of some other shape, and of the number of separators, is not critical to the function of the invention and may be a matter of design choice.
[0024] FIG. 5 is a plan view of the tapered section 24 . Threaded through hole 28 receives the threaded bolt 26 , while the smaller upper diameter 34 and larger lower diameter 36 form a frusto-conical surface that will cause expandable panels 20 to be forced outwardly when the tapered section 24 is drawn upward as bolt 26 is tightened.
[0025] In use, the locking floor sink drain screen 10 is inserted into the mouth of a floor sink drain so that the grate 12 rests on the surface of the area being drained and, preferably, within an indented cavity that will support the grate flush with the surface to be drained. The middle portion 18 and tapered portion 24 of the device are attached to the grate with threaded bolt 26 , and extend downwardly to fit within the upper end of a drain pipe. The bolt 26 is then tightened which serves to draw the tapered section 24 toward the middle section 18 , which causes the expandable panels 20 to expand laterally to wedge against and frictionally engage the drain pipe opening. This ensures that the device 10 will not be displaced during use. Because the device of this invention is intended for use in drains where the drain pipe is smaller than the mouth of the floor sink drain, liquid can flow through openings 16 in the grate 12 and through spaces between vertical separators 22 , and further through the large opening in tapered section 24 , where it will be channeled into the drain pipe. However, any large objects will be blocked by the mesh-like structure of the grate 12 . If the openings 16 become clogged over time, bolt 26 can be loosened, allowing tapered section 24 to be forced downward, releasing friction on expandable panels 20 and allowing the floor sink drain 10 to be removed for cleaning. Subsequently, the drain screen lock 10 can be reinserted in the floor sink drain opening in the manner described above for further use.
[0026] Bolt 26 may be tamperproof such that special tools are required for installation or removal of the device from a drain. Because the drain pipe will be some distance below the grate and floor openings, the middle section 18 and tapered section 24 may be of any length, and will be sized to fit within a drain of corresponding size. Vertical separators may be of any height but, preferably, will be no longer than about one inch (2.54 cm).
[0027] Numerous variations and modifications can be made without departing from the spirit of the present invention. Therefore, it should be clearly understood that the forms of the present invention described above and shown in the accompanying drawing are illustrative only and are not intended to limit the scope of the present invention. | An improved locking floor sink drain screen for an enlarged drain is provided. The locking floor sink drain positively precludes passage of large objects, while permitting free passage of fluid and which can quickly and easily be removed for cleaning. Vertical separators provide spaces through which water can flow from the enlarged drain opening into a standard drain pipe. In some embodiments, a special, tamperproof locking key may be used to prevent unauthorized disassembly of the installed floor drain screen. | 4 |
BACKGROUND OF THE INVENTION
[0001] This application claims the benefit of prior filed co-pending U.S. provisional application Serial No. 60/334,049 filed Nov. 28, 2001 entitled “SWIMMING POOL LEAK STOP PLUMBING ADAPTER AND METHOD” by William C. Tarr.
[0002] The invention relates to improvements in the plumbing part of the construction of swimming pools. More particularly, the invention relates to a barrier device and method which (1) prevents leakage of pool water around plumbing, such as return pipes, extending through the gunite (i.e., shotcrete) layer of the wall of the partially constructed swimming pool or drain pipes extending through the gunite layer for connection to drain fixtures, and (2) also prevents leakage of plaster or other interior surface finishing material into open ends of any exposed plumbing extending through the gunite layer as the plaster or other finishing material is applied thereto.
[0003] A problem of the prior art is that the above described application of plaster or other interior surface finishing material results in leakage of some of the material into the open ends of the return water pipes or drain pipes as the material is being applied. The presence of plaster or the like in the open ends of the water return pipes or drain pipes may cause considerable difficulty, especially if slurry or plaster material hardens before being removed from the pipes.
[0004] In the past, pool construction workers have sometimes applied tape over, or inserted sponges into, the open ends of the return water pipes or drain pipes extending through and beyond the gunite layer of which the swimming pool wall and floor are constructed. However, that approach has been inadequate, because some of the plaster or slurry inevitably passes through the tape or sponge into the open end of the water return pipes and/or drain pipes.
[0005] Another problem of the prior art is that after the swimming pool construction has been completed and the pool has been filled with water, leakage of pool water occurs around the outside surfaces of the return water pipes and drain pipes through defective seals between the water pipes and the pool wall, because of the failure of pool wall materials to provide a reliable seal with the outside surfaces of the pipes. When gunite is applied to the interior of the pool, the nozzle usually is positioned higher than plumbing pipes that pass through the pool “shell” or wall. This often leaves a void underneath a protruding pipe. Also, the gunite material being applied can slump and create voids around plumbing that passes through the pool wall. Such voids can cause leakage of pool water if a good seal is not provided around the pipe during application of the interior surface plaster or other finish. Also, during temperature changes from summer to winter in warmer climates, the gunite and interior finish expands and contracts. This causes leakage of pool water around plumbing pipes that pass through the gunite structure. Such leakage can cause soil expansion problems and cracking of the swimming pool wall. Repairing such a defective seal after the pool has been completed can be very expensive, especially if the surrounding portion of the pool bottom or pool wall needs to be removed by means of a jackhammer and replaced by new wall material.
[0006] U.S. Pat. No. 4,951,326 (Barnes et al.) discloses several “eyeball” fittings which can be provided in the floor and wall of the swimming pool or spa during construction. The “eyeball” fittings are relatively high-precision, expensive fittings, and their pivoting operation would be impaired by plaster debris introduced into the fittings during plastering of the pool or spa. To avoid this difficulty, the “eyeball” fittings have caps which prevent plaster or other finish from entering the fittings as the finish is applied. In one embodiment, a breakaway cap 30 is integral with a threaded retaining ring that retains a spherical eyeball member in the fitting. After the finishing operation, the retaining ring is threaded further into the fitting, causing pressure of the fitting on the periphery of the cap to break it away from the retaining ring. In another embodiment disclosed in U.S. Pat. No. 4,951,326, a disk-shaped breakaway cap 50 is attached by a frangible web 54 and a pair of dielectrically opposed tabs 61 to an open mouth of the fitting. The tabs 61 act as pivot points when a peripheral point of the breakaway cap is hit with a hammer, causing it to tilt so it can be grasped and removed by breaking the tabs. The device is costly because it requires several separate molded parts. In a third embodiment, a breakaway cap 70 includes hook-like projections that hold the breakaway cap 70 in place during plastering or other finishing by extending into and engaging the socket within which the “eyeball” element is retained. After plastering, a screwdriver is forced through a weak spot 74 in the breakaway cap 70 and tilted so as to disengage the book-like projections and remove the breakaway cap. The devices disclosed in U.S. Pat. No. 4,951,326 are intended to be used as restricted wall return fittings for the purpose of controlling the direction of pool water being returned into the pool.
[0007] U.S. Pat. No. 4,063,759 (Steimle) discloses a water barrier device including the tubular sleeve encircled by flanges having a fluid-tight seal with the exterior of the pipe extending through the wall of the swimming pool. The device must be slipped over the outside portion of pool plumbing in order to be embedded into the gunite or pool finish. Therefore, it is necessary to clean a relatively large surface area of the end of the pipe before the tubular sleeve can be slid over the end of pipe and cemented thereto. However, pool finish contractors usually will not use this type of fitting because the cleaning of the pipes required before installing this type of water barrier is far too time consuming.
[0008] It would be desirable to provide a practical device and technique to prevent leakage of water in a swimming pool around return water pipes and drain pipes extending through the walls of swimming pools and simultaneously provide a convenient, inexpensive way of preventing plaster or other interior surface finishing material from leaking into the open ends of return water pipes and drain pipes while plaster or other interior surface material is being applied onto the gunite layers of partially constructed swimming pools.
SUMMARY OF THE INVENTION
[0009] It is an object of the invention to provide a barrier device and technique for making improved plumbing connections along the interior surface of a swimming pool to avoid leakage of pool water around plumbing connections through the pool wall.
[0010] It is another object of the invention to provide a barrier device and technique to prevent plaster or other interior pool finishing material from entering open ends of plumbing connections such as water return pipes or drain pipes extending through the gunite wall layer of a partially constructed swimming pool during application of plaster or other interior pool surface material to the gunite layer.
[0011] It is another object of the invention to provide a single device that effectively functions as both a barrier device for making improved plumbing connections along the interior surface of a swimming pool to avoid leakage of pool water around plumbing connections through the pool wall and as a barrier device to prevent plaster or other interior pool finishing material from entering open ends of plumbing connections such as water return pipes or drain pipes extending through the gunite wall layer of a partially constructed swimming pool during application of plaster or other interior pool surface material to the gunite layer.
[0012] Briefly described, and in accordance with one embodiment thereof, the invention provides a barrier device and technique for use in the plumbing during construction of a swimming pool. The barrier device ( 1 ) includes a tubular cylindrical section ( 2 ) having an open first end. A pop-out barrier ( 12 ) is integral with the cylindrical section, at a second end portion of the cylindrical section, and is disposed to cover the second end portion of the cylindrical section. In the described embodiment, an annular water barrier flange ( 3 ) is integral with the cylindrical section, and is disposed about a mid portion of the cylindrical section to prevent water leakage around the outer surface of the cylindrical section ( 2 ) when the barrier device is installed on the end of a water return pipe or a drain pipe extending through the wall surface of a swimming pool. The pop-out barrier includes a thin annular section ( 12 A) peripherally connected by a thinned or scored first web ( 15 ) and a thickened hinge portion ( 15 A) of the first web to an edge portion of the second end. The pop-out barrier also includes an inner section ( 12 B) peripherally connected by a end second web ( 17 ) and a thickened hinge portion ( 17 A) of the second web to an inner edge portion of the annular section ( 12 A). In the described embodiment, a barrier device is a debris/water barrier device, wherein an integral annular water barrier flange ( 3 ) is disposed about a mid portion of the cylindrical section to prevent water leakage around an outer surface of the cylindrical section ( 2 ) when the device is installed on an open end of the water return pipe or drain pipe. The annular water barrier flange includes an outer surface ( 3 B) and a peripheral lip ( 3 A) extending outward from the outer surface.
[0013] Construction of the swimming pool includes applying gunite material to form a wall and a floor of the swimming pool so that open end portions of a plurality of water return pipes extend beyond a surface of the gunite material. A debris/water barrier device or the like is attached to each extending open end portion, respectively. A layer of interior finish material is applied to the gunite so that the interior finish material is flush or nearly flush with the pop-out barrier ( 12 ). The inner section ( 12 B) is struck so as to break part of the second web ( 17 ) so that the inner section ( 12 B) hangs inside a volume bounded by the pop-out barrier ( 12 ). A retracting element is inserted into a resulting hole in the annular section, and the annular section ( 12 A) is pulled outward so as to break the first web ( 15 ) in removing the pop-out barrier ( 12 ).
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] [0014]FIG. 1A is a perspective view of a debris/water barrier device for plumbing swimming pools.
[0015] [0015]FIG. 1B is a partial perspective cutaway view of the debris/water barrier device of FIG. 1A.
[0016] [0016]FIG. 2 is a partial perspective view illustrating a water return pipe or drain pipe extending through the gunite wall of a partially constructed swimming pool.
[0017] [0017]FIG. 3 is a partial perspective cutaway section view illustrating installation of the debris/water barrier device of FIGS. 1A and 1B on an open end of the pipe in FIG. 2 extending through the inner surface of a gunite layer of a partially constructed swimming pool.
[0018] [0018]FIG. 4 is a partial perspective cutaway section view illustrating the structure of FIG. 2 after application of a layer of plaster surfacing on the gunite layer.
[0019] [0019]FIG. 5 is a partial perspective cutaway section view illustrating removal of the center popout barrier of the debris/water barrier device of FIGS. 1A and 1B.
[0020] [0020]FIG. 6 is a partial perspective cutaway section view illustrating removal of the outer popout barrier from the debris/water barrier device.
[0021] [0021]FIG. 7 is a partial perspective cutaway section view illustrating an alternative installation of the debris/water barrier device of FIGS. 1A and 1B on an open end of the pipe in FIG. 2 extending through the inner surface of a gunite layer of a partially constructed swimming pool.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] Referring to FIGS. 1A and 1B, debris/water barrier device 1 of the present invention includes a hollow, open-bottom cylindrical section 2 having a 1.5 inch inside diameter into which a standard 1.5 inch PVC schedule 40 pipe can be inserted. Cylindrical section 2 includes a lower section 2 A and an upper section 2 B having the same inside diameter as lower section 2 and a larger outside diameter than lower section 2 A. The lower section 2 A has an outside diameter which is tapered from 2.015 inches at its bottom edge to 2.050 inches at its upper portion. This allows lower section 2 A to be snugly inserted into and cemented within an open end of a standard 2 inch schedule 40 PVC pipe 20 despite variations in the inside diameter thereof, if 2 inch PVC pipe rather than 1.5 inch PVC pipe is used. In a prototype device, the length of cylindrical section 2 (including both sections 2 A and 2 B) is ⅜ inches. This also allows the fitting to be installed precisely perpendicular to the finished interior pool surface.
[0023] The top end 10 of cylindrical section 2 is covered by an integral thin, disk-shaped pop-out barrier 12 which preferably is integral with cylindrical section 2 . Reference numeral 15 indicates a thin cut or thin web around the periphery of pop-out barrier 12 which allows it to be easily popped out from cylindrical section 2 , and reference numeral 15 A designates a thickened “hinge” portion of web 2 to more firmly connect pop-out barrier 12 to the inside of upper section 2 B of cylindrical section 2 when the rest of barrier 12 is popped out. Pop-out barrier 12 includes an annular pop-out section 12 A the periphery of which is connected by thin web 15 directly to upper section 2 B of cylindrical section 2 , and also includes a central circular (or other shape) pop-in barrier 12 B which can be popped inward relative to annular pop-out section 12 A, to allow a hook, finger or the like to be inserted through the resulting hole in order to pull out annular popout section 12 A. Reference numeral 17 indicates a thin cut or thin web around the periphery of central pop-in barrier 12 B which allows pop-in barrier 12 B to be easily popped inward, and reference numeral 17 A designates a thickened “hinge” portion of web 17 to more firmly connect central pop-in barrier 12 B to the inside of upper section 2 B of cylindrical section 2 when the rest of barrier numeral 12 B is popped in. This prevents pop-out section 12 from falling downward into the pipe 20 (FIG. 3) on which debris/water barrier device 1 is installed and therefore avoids the difficulty of retrieving a pop-in barrier 12 B that has fallen into the pipe.
[0024] An annular water barrier flange 3 is attached to and surrounds the mid section of cylindrical section 2 . The diameter of water barrier flange 3 can be 3 inches. Water barrier flange 3 has a raised peripheral lip 3 A which rises ⅛ of an inch above a flat annular upper surface 3 B of water barrier flange 3 as shown in FIG. 1A. The purpose of water barrier flange 3 is to provide a high-integrity seal with the plaster or other interior surface material which is applied to the gunite layer.
[0025] Preferably, debris/water barrier device 2 is a completely integral unit formed of ABS plastic, although other suitable plastic material such as PVC (polyvinyl chloride) or CPVC can be used.
[0026] Referring to FIG. 2, reference numeral 20 designates either the open end section of a drain pipe or the open end of a swimming pool water return pipe coupled to the low pressure side of a pool pump (or the open end of a return pipe extending through the pool wall and coupled to the high pressure side of the pool pump). The open end of pipe 20 extends above or beyond a gunite layer 22 lining the walls and bottom of a hole that has been excavated for construction of the swimming pool. Typically, if pipe section 20 is 1.5 inch PVC pipe, its outer end extends so that it will be flush with the layer of plaster or other finish subsequently applied to gunite layer 22 , and if the pipe section 20 is 2 inch PVC pipe, its outer end extends so that it is approximately ⅝ inches behind the layer of plaster or other finish subsequently applied to the inner surface of gunite layer 22 .
[0027] Normally, the next stage in construction of the pool is to apply a layer of plaster or other pool interior surface material onto the gunite layer surface 22 A. (As previously mentioned, in the past workers sometimes have placed duct tape or sponge over or into the open end of pipe 20 to prevent the plaster or other pool interior surface material from leaking into the pipe 20 .) However, in accordance with the present invention, an end portion of pipe 20 is cleaned to remove gunite debris or other debris there from. For 1.5 inch PVC pipe, the end portion to be cleaned typically is 1 to 3 inches long. Then debris/water barrier device 1 is installed on the open end of pipe 20 , above the gunite surface 22 A as shown in FIG. 3. (If pipe 20 is a water return pipe, then it may extend horizontally beyond, rather than vertically above, the gunite surface.) Depending on whether pipe 20 is 1.5 inch or 2 inch schedule 40 PVC pipe, it can either be slid into the inside passage extending through debris/water barrier device 1 or it can be slid over the slightly tapered outer surface of lower section 2 A as shown in FIG. 7. In either case the joint can be cemented by means of ordinary PVC cement. If pipe 20 is 1.5 inch Schedule 40 PVC pipe, it can be slid entirely through debris/water barrier device 1 if barrier 12 is popped out, so that the outer end of pipe 20 extends beyond the edge 10 . Then a threaded PVC adapter can be cemented to the protruding outer end portion of pipe 20 to facilitate mounting a fixture thereon.
[0028] Referring to FIG. 4, the next step in the pool construction process is to apply a layer 26 of plaster (or other interior pool surface material) on the gunite surface 22 A, so that the outer surface 26 A of the plaster layer is flush with the top of debris/water barrier device 1 . During this process, pop-out barrier 12 prevents any of the plaster (or other interior pool surface material) from entering the open end of pipe 20 . During application of the plaster 26 , the pop-out barrier 12 prevents any plaster (or other interior pool surface material) from entering the open end of pipe 20 , and the annular water barrier flange 3 provides a high-integrity seal with the plaster or other pool interior surface material.
[0029] Removal of pop-out barrier 12 needs to be done in such a manner that it does not fall into pipe 20 . This will not happen if pipe 20 is 1.5 inch schedule 40 PVC pipe as illustrated in FIGS. 2 - 6 , because the diameter of pop-out barrier 12 is greater than the inside diameter of 1.5 inch schedule 40 PVC pipe. However, if pipe 20 is 2 inch schedule 40 PVC pipe and therefore is fit over the outer surface of lower section 2 A of debris/water barrier device 1 , then pop-out barrier 12 may fall into pipe 20 and cause the above mentioned retrieval problem.
[0030] To avoid this problem, pop-out barrier 12 can be removed by a two-step process as shown in FIGS. 5 and 6. First, the small, center pop-in barrier 12 B can be popped inward or downward as shown in FIG. 5. The thickened hinge portion 17 A shown in FIGS. 1A and 1B will cause center pop-in barrier 12 B to hang downward as illustrated.
[0031] Then, as shown in FIG. 6, a screwdriver or the like can be inserted through the center opening left by the removal of center pop-in barrier 12 B and wielded to pop barrier 12 A outward.
[0032] The thickened hinge portion 15 (FIG. 1A) retains pop-out barrier 12 in the configuration shown in FIG. 6. Pop-out barrier 12 then can be easily pulled loose and discarded. Then, if desired, a conventional fitting can be installed on or in the open end of debris/water barrier device 1 .
[0033] The above described debris/water barrier device and method of installation avoids the need to use the above mentioned ineffective duct tape to prevent the leakage of plaster or the like into the open end of return water pipes or drain pipes during the interior pool surface application process. The above described debris/water barrier device and method also prevent undesired leakage of pool water along the outer surfaces of water return pipes and drain pipes, because the annular water barrier flange 3 provides more surface area for the plaster (or other interior pool surface material) to seal with. The provision of the raised lip 3 A allows the plaster 26 to readily fill the recess defined by raised lip 3 A, bottom surface 3 B and the wall of upper section 2 B, and thereby provides increased structural rigidity of the interface between the plaster 26 and the annular flange 3 , which ensures a good seal despite the presence of voids and/or slight distortions of the gunite wall or pipe 20 which weaken the seal, for example, due to thermal gradients and differences in the thermal coefficients, stresses due to the shifting of the earth, etc. The bottom surface of annular flange 3 is flat in order to avoid formation of any void spaces underneath the flange 3 as the plaster 26 flows underneath flange 3 . (Any such voids would reduce the structural integrity of the interface between water barrier flange 3 and the gunite and therefore would reduce the long-tenn reliability of the seal between them.) The increased structural rigidity is desirable to prevent the seal between the plaster and stop leak device 1 from being weakened or disrupted by stress at the interface between plaster layer 26 and gunite layer 22 caused by the different coefficients of expansion of plaster layer 26 and gunite layer 22 . The need to clean a 2 to 3 inch section of pipe 20 as would be necessary for use of the barrier device disclosed in above mentioned U.S. Pat. No. 4,063,759 is avoided. The ability of the described debris/water barrier device 1 to be mounted in either 1.5 inch or 2 inch Schedule 40 PVC pipe avoids the cost of manufacturing and stocking two different sizes thereof.
[0034] While the invention has been described with reference to several particular embodiments thereof, those skilled in the art will be able to make the various modifications to the described embodiments of the invention without departing from the true spirit and scope of the invention. It is intended that all elements or steps which are insubstantially different or perform substantially the same function in substantially the same way to achieve the same result as what is claimed are within the scope of the invention. For example, pop-out barrier 12 could be slightly recessed into the top end 10 of debris/barrier device 1 . | A barrier device ( 1 ) and technique for use in the plumbing during construction of a swimming pool includes a tubular cylindrical section ( 2 ) having an open first end. A pop-out barrier ( 12 ) is integral with the cylindrical section, and is disposed to cover a second end of the cylindrical section. In one embodiment, an annular water barrier flange ( 3 ) is integral with the cylindrical section, and is disposed about a mid portion of the cylindrical section to prevent water leakage around an outer surface of the cylindrical section ( 2 ) when the barrier device is installed on the end of a water return pipe or drain pipe extending through the a wall surface of a swimming pool. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority from U.S. provisional application Ser. No. 61/280,435, filed on Nov. 4, 2009, herein incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to systems and methods for a vehicle exhaust extraction system. More particularly, the invention is directed to systems and methods for a vehicle exhaust extraction system with automatic return.
2. Description of the Related Art
Emergency vehicles, such as fire engines, typically have an exhaust removal/extraction system that is coupled to the exhaust of the vehicle while the vehicle is started in the bay of the station, and travels with the vehicle until the vehicle exits the vehicle bay, at which point the exhaust removal tube detaches from the vehicle. The exhaust removal carriage, which is generally carried along a track above the vehicle, remains at the exit of the bay until it is manually moved back to the bay entrance, where it awaits return of the vehicle.
Accordingly, an object of the present invention is to provide an automated system that automatically returns the exhaust extraction assembly to the rear of the bay upon release of the vehicle. Another object of the present invention is to provide a retrofit system that automatically returns the exhaust extraction assembly to the rear of the bay upon release of the vehicle. At least some of these objectives will be met in the following description.
BRIEF SUMMARY OF THE INVENTION
An aspect of the present invention is an automatic carriage return for an exhaust removal system. In one embodiment, the return is configured to be retrofit to an existing exhaust extraction system having a carriage that is configured to translate along a track tube, the carriage being coupled at a first end to an exhaust extraction hose, the second end of the exhaust extraction hose being coupled to a vehicle exhaust for directing exhaust from the vehicle out the track tube. The automatic carriage return includes a drive cable spanning along a path adjacent to and substantially parallel with the track tube, and an engagement assembly coupled to the carriage. The engagement assembly has an engaged configuration and a non-engaged configuration with respect to the drive cable. A drive motor is coupled to the engagement assembly, the drive motor being configured to drive motion of the carriage along the drive cable when the engagement assembly is in the engaged configuration. In the disengaged configuration, the engagement assembly is configured to be disengaged from the drive cable while the exhaust extraction hose is attached to the exhaust of a vehicle to allow the carriage to freely follow the path of the vehicle. Wherein, upon release of the extraction hose from the vehicle, the engagement assembly is configured to automatically activate to the engaged configuration to engage the drive cable.
In one embodiment, at least one of the engagement assembly and drive motor are pneumatically driven. For example, the drive motor may comprise a pneumatic drive motor, and the engagement assembly comprises a pneumatic drive cylinder that is configured to drive the engagement assembly to and from the disengaged configuration to the engaged configuration.
In another embodiment, the engagement assembly comprises a lever arm housing one or more upper wheels, wherein the lever arm is configured to house the one or more upper wheels at an orientation that does not significantly deflect the drive cable in the disengaged configuration. In the engaged configuration, the lever arm is configured to engage the one or more upper wheels with the drive cable such that the drive cable deflects on to a drive wheel coupled to the drive motor.
In a further embodiment, a first sensor is coupled to the carriage and is configured to sense a first location of the carriage with respect to the track tube and send a signal to operate the pneumatic drive cylinder to engage the engagement assembly and the pneumatic drive motor to drive translation of the carriage along the drive cable.
In another embodiment, the return includes a motor controller valve, wherein the first sensor comprises a first trigger valve, and the motor controller valve is configured to sense a pneumatic signal from the first trigger valve. The motor controller valve is configured to control the delivery of air to the pneumatic drive motor and pneumatic drive cylinder to operate the pneumatic drive motor and pneumatic drive cylinder to operate upon receiving said pneumatic signal.
In one mode of the current embodiment, a second sensor comprising a second trigger valve is included that is configured to sense a second location of the carriage with respect to the track tube. The second trigger valve is configured to send a signal to the motor controller valve to operate the pneumatic drive cylinder to disengage the engagement assembly and the turn off pneumatic drive motor to stop translation of the carriage along the drive cable.
Another aspect is an exhaust removal system with automatic carriage return, comprising a carriage being coupled at a first end to an exhaust extraction hose, wherein the carriage is configured to translate along a track tube. A second end of the exhaust extraction hose is configured to be coupled to a vehicle exhaust for directing exhaust from the vehicle out the track tube; A drive cable spans along a path adjacent to and substantially parallel with the track tube. An engagement assembly is coupled to the carriage, the engagement assembly having an engaged configuration and a non-engaged configuration with respect to the drive cable. A drive motor coupled to the engagement assembly, the drive motor being configured to drive motion of the carriage along the drive cable when the engagement assembly is in the engaged configuration. In the disengaged configuration, the engagement assembly is configured to be disengaged from the drive cable while the exhaust extraction hose is attached to the exhaust of a vehicle to allow the carriage to freely follow the path of the vehicle. Upon release of the extraction hose from the vehicle, the engagement assembly is configured to automatically activate to the engaged configuration to engage the drive cable.
In one embodiment of the current aspect, the drive motor comprises a pneumatic drive motor, and the engagement assembly comprises a pneumatic drive cylinder that is configured to drive the engagement assembly to and from the disengaged configuration to the engaged configuration.
In a further embodiment, a first sensor is coupled to the carriage and is configured to sense a first location of the carriage with respect to the track tube. The first sensor is configured to send a signal to release the second end of the exhaust extraction hose from the vehicle exhaust. The first sensor is further configured to send a second signal to operate the pneumatic drive cylinder to engage the engagement assembly and the pneumatic drive motor to drive translation of the carriage along the drive cable.
Another aspect is a method for automatically returning a carriage for an exhaust removal system. The method includes the steps of coupling a first end of the carriage to an exhaust extraction hose, coupling a second end of the exhaust extraction hose to a vehicle exhaust for allowing the carriage to translate along a track tube as the vehicle moves in a first direction while directing exhaust from the vehicle out the track tube, releasing a second end of the exhaust extraction hose from the vehicle exhaust, engaging a drive cable with an engagement assembly coupled to the carriage, wherein the drive cable spans along a path adjacent to and substantially parallel with the track tube. The engagement assembly has an engaged configuration and a non-engaged configuration with respect to the drive cable. The method further includes driving motion of the carriage in a second direction opposite to the first direction along the drive cable when the engagement assembly is in the engaged configuration. In the disengaged configuration, the engagement assembly is configured to be disengaged from the drive cable while the exhaust extraction hose is attached to the exhaust of a vehicle to allow the carriage to freely follow the path of the vehicle. Upon release of the extraction hose from the vehicle, the engagement assembly is configured to automatically activate to the engaged configuration to engage the drive cable.
In one embodiment of the current aspect, engaging a drive cable and driving motion of the carriage are done pneumatically.
In another embodiment, the method includes sensing a first location of the carriage with respect to the track tube, sending a pneumatic signal to release the second end of the exhaust extraction hose from the a vehicle exhaust, and sending a second signal to operate a pneumatic drive cylinder to engage the engagement assembly and the pneumatic drive motor to drive translation of the carriage along the drive cable.
In another embodiment, the method includes sensing a second location of the carriage with respect to the track tube, and sending a third signal to operate the pneumatic drive cylinder to disengage the engagement assembly and the turn off pneumatic drive motor to stop translation of the carriage along the drive cable.
Further aspects of the invention will be brought out in the following portions of the specification, wherein the detailed description is for the purpose of fully disclosing preferred embodiments of the invention without placing limitations thereon.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of the control side of the automatic carriage return of the present invention.
FIG. 2 is a perspective view of the drive side of the automatic carriage return of FIG. 1 .
FIG. 3 is a rear perspective view of the automatic carriage return of FIG. 1 .
FIG. 4 is a perspective view of the drive side of the automatic carriage return of FIG. 1 with the carriage, track tube and main support bracket removed to show better detail.
FIG. 5A is a side view of the of the automatic carriage return of FIG. 1 with the engagement mechanism disengaged.
FIG. 5B is a side view of the of the automatic carriage return of FIG. 1 with the engagement mechanism engaged.
FIG. 6 illustrates a system air flow chart of the automatic carriage return of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention, detailed in FIGS. 1 to 6 below, is directed to devices and methods for automatic return of the carriage and extraction hose portion of an exhaust removal system to the entrance side of a drive-through vehicle bay after it has been pulled to the exit side by a departing vehicle.
FIGS. 1-4 show various views of an exhaust removal system 10 incorporating the automatic carriage return 20 of the present invention. FIGS. 1 and 2 show perspective views of the control side and drive side, respectively, of the automatic carriage return 20 . FIG. 3 shows a rear view of the automatic carriage return 20 , and FIG. 4 is a perspective view of the drive side of the automatic carriage return with the carriage fairing 22 , track tube 12 , and main support bracket 23 removed to show better detail.
The exhaust removal system 10 comprises an exhaust removal hose 95 that is detachably coupled to the exhaust pipe (not shown) of a service vehicle (not shown). The opposite end of the exhaust hose 95 is coupled to a bottom end 28 of carriage fairing 22 via collar or clamp 53 . The carriage fairing 22 is configured to direct exhaust upward and out slotted upper end 36 toward slot 16 in track tube 12 . The track tube comprises a central channel 14 to receive the exhaust.
Referring to FIG. 3 , the carriage 22 is configured to translate freely in a linear fashion across the bay via two sets of track wheels 26 that are disposed within in the central channel 14 of track tube 12 . The track wheels 26 are rotatably attached to brackets 24 that couple the wheels 26 to the main support bracket 23 . Thus, while the exhaust extraction hose 95 is coupled to the vehicle, it is the vehicles motion that drives motion of the carriage 22 along the track tube 12 .
The return system 20 of the present invention is configured to only engage upon release of the exhaust extraction hose 95 from the exhaust of the vehicle, thus allowing the carriage assembly 30 to move freely within track tube 12 . Furthermore, the return system 20 comprises an engagement assembly 100 and drive means that are powered entirely via a pneumatic air system that used for disengagement/release of the exhaust hose 95 from the truck upon exiting the bay.
As detailed in FIGS. 1 and 6 , the exhaust removal system 10 uses a retention bladder 200 to couple the exhaust hose 95 to the truck exhaust. The system takes high pressure air from the input tube 15 and directs the pressurized air to pressure regulator 40 to send low pressure to the bladder 200 . A portion of the high pressurized air is directed to end trigger valve 50 . Upon the vehicle reaching the exit side of the bay, end trigger valve 50 is activated from pivotable arm 52 rotating after hitting a stop (not shown), indicating the location of the carriage 30 at the end of the bay. Once activated, the trigger valve 50 is then sends a pressure signal via a release signal tube 45 to the bladder valve 29 ( FIG. 6 ). The carriage return system 20 is further configured such that the end trigger valve 50 also sends a signal to activate the automatic return 20 .
Referring now to FIGS. 4 , 5 A and 5 B, the signal from end trigger valve 50 is sent to motor controller valve 70 , which is configured to send high pressure air the pneumatic cylinder 80 and the pneumatic drive motor 170 to operate engagement and return drive means. FIGS. 4 and 5A illustrate the engagement mechanism 100 in a disengaged configuration. In this mode, the carriage assembly 30 is free to translate along the length track tube 12 without any, or substantially any, restriction from the return drive means. The return drive mechanism of the carriage assembly 30 is affected from contact between the drive wheel 130 and drive cable 18 , wherein the position of the bogey 120 dictates whether or not the drive wheel 130 is in contact with the drive cable 18 . As seen in FIGS. 1 , 2 and 3 , drive cable 18 spans across the bay along an axis substantially parallel to the axis of the track tube 12 , at a location below and to one side of the track tube 12 . During the disengaged mode illustrated in FIGS. 4 and 5A , the drive cable has minimal to no contact with the bogey wheels 130 , 140 of bogey 120 .
Referring now to FIG. 5B , the signal from end trigger valve 50 (triggered from the carriage assembly 30 reaching the end trigger valve 50 ) is sent to the motor controller valve 70 , which sends high pressure air the pneumatic cylinder 80 and the pneumatic drive motor 170 to operate engagement and return drive means. The high pressure air drives the pneumatic cylinder 80 extend piston 88 . The pneumatic cylinder 80 has a fixed end 86 that is restrained from translation, thus causing the piston 88 to push rod clevis 82 outward from the cylinder body. Motion of the rod clevis 82 applies a corresponding rotation to the crank arm 90 which is pivotably connected rod clevis pivot 84 . The downward motion of crank arm 90 correspondingly pulls down on the Y Bar 92 , which is coupled to the crank arm 90 at pivot 94 . The Y Bar 92 is pivotably attached to free end of lever or bogey arms 110 at hinge 96 , such that downward motion of the Y Bar 92 pivots the bogey arm 110 lowering the bogey 120 and bogey wheels 122 , 124 until they contact (or push down if already in contact) the drive cable 18 . The opposing end of the bogey 120 is pivotably fixed at hinge 116 such that continued downward motion of the bogey arm 110 causes the drive cable 18 to be pinched between the bogey wheels 122 , 124 and the drive wheel 130 (see FIG. 5B , showing the drive cable 18 being bent around drive wheel 130 . This pinching action creates the friction necessary to drive the carriage assembly 30 forward along the drive cable 18 when the drive wheel 130 is rotated.
It is appreciated that prior to this engagement (which is triggered by release of the extraction hose from the vehicle), the return system 20 of the present invention in no way impedes the natural motion of the carriage assembly 30 as it follows the vehicle out the bay.
Rotation of the drive wheel 130 is accomplished by high pressure air traveling through the pneumatic drive motor 170 , causing the output shaft 162 to rotate. The rotating shaft 162 is connected to the small toothed pulley 160 . The rotation of the small toothed pulley 160 is transmitted via the toothed belt 18 to the large toothed pulley 140 . The large toothed pulley 140 is directly coupled through a cross shaft to the drive wheel 130 . Corresponding rotation of the large toothed pulley 140 directly rotates the drive wheel 130 . Thus, the carriage assembly 30 is powered by the drive wheel 130 and drive cable 18 when in the engaged configuration of FIG. 5B , and travels down the track tube 12 towards the entrance side of the bay.
Upon reaching the entrance side of the bay, the pivoting arm 62 of trigger valve 60 rotates as it engages a stop (not shown) at or near the entrance. The motion of arm 62 activates stop trigger valve 60 , sending a signal to the motor controller valve 70 . The motor controller valve 70 then turns off the pressure supply to the pneumatic cylinder 80 and the pneumatic drive motor 170 . This loss in pressure stops the rotation of the pneumatic drive motor 170 and causes the pneumatic cylinder 80 to retract pivot 88 . The retraction of the cylinder pivot 88 correspondingly drives the engagement assembly linkage back to the disengaged configuration of FIG. 5A , releasing the pinch of bogey 120 on the drive cable 18 . The carriage 30 now remains at the entrance side of the bay until it is pulled by a reconnected vehicle to the exit side of the bay where the return sequence starts again.
FIG. 6 illustrates flow chart of the air control of the carriage return 20 system of the present invention, wherein air from compressor 180 is feed to modulator 40 , trigger valves 50 , 60 , motor controller 70 , bladder valve 29 , retention bladder 200 , cylinder and motor 170 .
It is appreciated that trigger valves 50 , 60 are essentially sensors that detect the position of the carriage assembly 30 , and send a pneumatic signal to valves 29 , and 70 to operate or control various mechanical components of the system. While this configuration is advantageous in that it provides a sensing means that does not require any electrical power (and associated cables and/or batteries), it is understood that other sensors (e.g. pressure, optical, hall-effect sensors, RFID, or the like) available in the art may be used interchangeably with the return system 20 of the present invention.
As detailed in FIG. 6 , high pressure air enters the system through the input tube 15 and travels to T-fitting 41 , which splits the airflow between the pressure regulator 40 and a second T-fitting 42 . Low pressure then travels from the pressure regulator 40 down the bladder valve tube 25 (see also FIG. 1 ) to input 31 of the bladder valve 29 , where it inflates the retention bladder 200 ( FIG. 6 ) to hold the extraction hose 95 to the vehicle's exhaust pipe (not shown).
Second T-fitting 42 splits airflow between line 37 and a third T-fitting 43 that supplies air to the inputs 54 , 64 of respective end trigger valve 50 and return stop trigger valve 60 , and line 51 , which directs airflow to input 74 of motor controller 70 .
Upon the vehicle reaching the exit side of the bay, end trigger valve 50 is activated, sending a pneumatic pressure signal through output 56 and line 39 to fourth T-fitting 45 . Fourth T-fitting 45 splits the airflow between trigger 2 “on” input 72 of motor controller 70 and the release signal line 35 (see FIG. 1 ) coupled to trigger 1 “off” input 32 of the bladder valve 29 . This trigger 1 “off” signal cuts air off of the output 33 and line 34 leading to retention bladder 200 , causing the retention bladder 200 to deflate, thereby releasing the extraction hose 95 from the vehicle's exhaust pipe.
Simultaneous with sending the trigger 1 “off” signal, the air from output 56 of the end trigger valve 50 is also sent via the fourth T-fitting 45 out line 49 to the trigger 2 “on” input 72 of motor controller 70 to activate the automatic return 20 . The signal from the trigger 2 “on” input 72 (indicating that the vehicle has reached the exit side of the bay and pending release of the bladder 200 from the vehicle exhaust) activates the motor controller valve 70 to send high pressure air through output 78 to delay valve 190 . The delay valve 190 suspends the transmission of the air to T-fitting 47 for a specified period of time (e.g. 5 seconds). The delay period may be varied, but only needs to be enough time sufficient to ensure that the bladder 200 has been released from the vehicle exhaust before engagement of the return system 200 . After the specified delay, the air is split at T-fitting 47 between the air cylinder 80 and the pneumatic drive motor 170 to activate engagement assembly 100 and radial motion of drive motor 170 . The engagement assembly 100 then engages cable 18 and drives the carriage assembly 30 along track 12 toward the entrance of the bay.
Upon reaching the entrance side of the bay, the arm 62 of return stop trigger valve 60 is activated, which releases air through output 66 and line 38 to the trigger 3 “off” input 76 of the motor controller valve 70 . The motor controller valve 70 then cuts off the pressure supply from output 78 to the pneumatic cylinder 80 and the pneumatic drive motor 170 . This loss in pressure stops the rotation of the pneumatic drive motor 170 and causes the pneumatic cylinder 80 to retract pivot 88 . The retraction of the cylinder pivot 88 correspondingly drives the engagement assembly linkage back to the disengaged configuration of FIG. 5A , releasing the pinch of bogey 120 on the drive cable 18 . The carriage return assembly 30 is now free to translate along track tube 12 so that it may be free to move once the hose 95 is attached to the vehicle exhaust.
The above illustrated embodiment of automatic carriage return 20 is illustrated in FIGS. 1-6 to be installed as a retro-fit to an existing pneumatically-operated exhaust removal system that may already be in play en the emergency vehicle bay. In such case, the engagement assembly 100 , motor controller 70 delay valve 190 , air cylinder 80 , air motor 170 return stop trigger valve 60 , and accompanying fittings and lines are installed to attach to, or work in concert with, already existing regulator 40 , bladder valve 29 , bladder 200 , end trigger valve 50 , track tube 12 carriage fairing 22 , main bracket, etc. Certain parts may be modified to allow for such retrofit. For example, the main bracket 32 may be modified to provide opening (clearance) 27 for small-toothed pulley 160 .
However, it is appreciated that may comprise an exhaust removal system 10 comprising a carriage return system 20 as an integrated component.
Furthermore, the automatic carriage return 20 illustrated in FIGS. 1-6 is configured to operate pneumatically via pressurized air. However, it is appreciated that the principles of the present invention may be applied to systems using other driving or sensing means, e.g. electronic server motor, electromagnetic actuation, etc., or may include a mixture of components that are pneumatically operated and components using other drive/sensing means. In addition, it is appreciated that certain components may be interchangeably used with other components known in the art. For example, while the bogey/drive cable is a preferred engagement means for affecting return drive of the carriage assembly 30 , it is possible that other possible releasable engagement means (e.g. rack and pinion, worm drive, etc) may be used as well.
Although the description above contains many details, these should not be construed as limiting the scope of the invention but as merely providing illustrations of some of the presently preferred embodiments of this invention. Therefore, it will be appreciated that the scope of the present invention fully encompasses other embodiments which may become obvious to those skilled in the art, and that the scope of the present invention is accordingly to be limited by nothing other than the appended claims, in which reference to an element in the singular is not intended to mean “one and only one” unless explicitly so stated, but rather “one or more.” All structural, chemical, and functional equivalents to the elements of the above-described preferred embodiment that are known to those of ordinary skill in the art are expressly incorporated herein by reference and are intended to be encompassed by the present claims. Moreover, it is not necessary for a device or method to address each and every problem sought to be solved by the present invention, for it to be encompassed by the present claims. Furthermore, no element, component, or method step in the present disclosure is intended to be dedicated to the public regardless of whether the element, component, or method step is explicitly recited in the claims. No claim element herein is to be construed under the provisions of 35 U.S.C. 112, sixth paragraph, unless the element is expressly recited using the phrase “means for.” | An automatic carriage return for an exhaust removal system having a carriage that is configured to translate along a track tube, the carriage being coupled at a first end to an exhaust extraction hose, the second end of the exhaust extraction hose being coupled to a vehicle exhaust for directing exhaust from the vehicle out the track tube. The automatic carriage return includes a drive cable spanning along the track tube, and an engagement assembly coupled to the carriage. The engagement assembly has an engaged configuration and a non-engaged configuration with respect to the drive cable. A drive motor is coupled to the engagement assembly, and drives motion of the carriage along the drive cable when the engagement assembly is in the engaged configuration. In the disengaged configuration, the engagement assembly is configured to be disengaged from the drive cable while the exhaust extraction hose is attached to the exhaust of a vehicle to allow the carriage to freely follow the path of the vehicle. Upon release of the extraction hose from the vehicle, the engagement assembly is configured to automatically activate to the engaged configuration to engage the drive cable. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. Provisional Patent Application No. 61/727,063, filed Nov. 15, 2012 and entitled “SYSTEM AND METHOD FOR CLASSIFYING RELEVANT COMPETITORS,” which is hereby incorporated by reference in its entirety. This application is also related to co-pending, commonly assigned U.S. patent application Ser. No. XX/XXX,XXX [having attorney docket no. HOMR.P0476US], filed Mar. 15, 2013 and entitled “SYSTEM AND METHOD FOR AUTOMATIC WRAPPER INDUCTION BY APPLYING FILTERS,” U.S. patent application Ser. No. XX/XXX,XXX [having attorney docket no. HOMR.P0477US], filed Mar. 15, 2013 and entitled “SYSTEM AND METHOD FOR AUTOMATIC WRAPPER INDUCTION USING TARGET STRINGS,” and U.S. patent application Ser. No. XX/XXX,XXX [having attorney docket no. HOMR.P0478US], filed Mar. 15, 2013 and entitled “SYSTEM AND METHOD FOR AUTOMATIC PRODUCT MATCHING,” the disclosures of which are incorporated by reference in their entirety. Copies of U.S. patent application Ser. Nos. XX/XXX,XXX [having attorney docket no. HOMR.P0476US], XX/XXX,XXX [having attorney docket no. HOMR.P0477US], and XX/XXX,XXX [having attorney docket no. HOMR.P0478US] are attached hereto as Appendices A, B, and C, respectively.
TECHNICAL FIELD
[0002] This disclosure relates generally to the field of competitive intelligence, and specifically to product assortment in the retail industry.
BACKGROUND
[0003] Competitive intelligence, as it relates to pricing, has been an important aspect of the retail business for decades. Today, consumers have tools that allow them to compare prices across thousands of retailers in seconds.
[0004] To be competitive, retailers today must: i) know who their competitors are, ii) know how much their competitors are charging for the goods that they carry, and iii) be able to act on this information.
[0005] Many retailers carry a very large number of products on their catalog, often times in excess of 100,000 different stock keeping units (SKUs) associated with different products. Each SKU is often sold by many different competitors at different prices. Competitors may change their prices for products at any time, which makes it even more difficult to determine the pricing of the products at different retailers.
[0006] Because of the large number of retailers selling goods online, it can be important that retailers know who their relevant competitors are; not only at the store level, but also at the “product group” level. “Product group,” in this case, can be defined as a group of SKUs or other product identifiers. A “product group” can be a product category (e.g., digital cameras), a brand (e.g., Canon® products), or any pre-defined product group (e.g., high-end Canon® digital cameras).
SUMMARY
[0007] An objective of the present disclosure is to provide competitive intelligence related to classifying competitors for a retailer. Another objective of the present disclosure is to help retailers know who their competitors are for any given product-group. These and other objectives can be achieved in embodiments disclosed herein. In particular, embodiments may determine if an online retailer is a potential competitor for a pre-defined product group. Relevancy may be determined, for instance, by looking at product overlap, estimated traffic, average rating of online reviews, and a number of views for a website associated with the potential competitor. A product group may be products in a product category, brand, in a user-defined product group, etc.
[0008] In embodiments, a system may determine web pages for competitors that include relevant products to a customer of the system. One example of such a customer may be a business entity. One example of a business entity can be a retailer. This retailer may be selling a product and is interested in information relating to that product or similar ones from its competitors, including known and unknown competitors. These competitors may have a presence on the Internet. The system may be configured to pull information associated with products or product types from an unbound number of domains on the Internet. Examples of information associated with a product may include name, description, product attributes, SKU, price, image, etc. These competitors as well as their domains and websites may or may not be known by a customer requesting the information.
[0009] In this disclosure, the term “domain” is used in the context of the hierarchical Domain Name System (DNS) of the Internet. Those skilled in the art appreciate that the DNS refers to a hierarchical naming system for computers or any resource connected to the Internet. A network that is registered with the DNS has a domain name under which a collection of network devices are organized. Today, there are hundreds of millions of websites with domain names and content on them. As the number of websites continues to grow, pulling information associated with a product or products from an unbound number of domains on the Internet can be a very complex, tedious, and complicated process.
[0010] Embodiments disclosed herein can leverage wrapper induction and wrapper infection methodologies disclosed in Appendix A and Appendix B attached herewith to automate a data mining process across unbounded domains. Additionally, because each competitor may describe or define a product in different ways, it may be desirable or necessary to determine which products sold by different competitors refer to the same product. Embodiments disclosed herein can also leverage a novel approach disclosed in Appendix C attached herewith to match a product or product type of interest with product information crawled from the Internet. This matching process can help to ensure that any price or feature comparison made between a predefined product/product type and products/product types being sold by different competitors on the Internet are the same and/or relevant. Appendices A, B, and C are hereby incorporated by reference in their entireties.
[0011] In embodiments disclosed herein, a system is operable to obtain or otherwise gain knowledge on the products that competitors are selling and each competitor's pricing of the products. The system includes a user interface through which a customer can identify what products that the customer carries. In one embodiment, a customer can provide the system with a product catalog through the user interface or via other means.
[0012] The system may include a competitor classifier operable to determine what other retailers (potential or actual competitors of the customer of the system) are selling the same products and how much they are selling the products for. The competitor classifier may identify a retailer as a potential competitor of the customer. For each potential competitor, the competitor classifier may determine the following variables: (1) an estimated number of unique visitors to the potential competitor's website; (2) a number of user-reviews that the potential competitor has; (3) a review-rating associated with the potential competitor; (4) a percentage of product that overlap between a product group of the customer and the potential competitor (e.g., the potential competitor carries 80% of the same digital cameras products carried by the customer); and (5) a number of products that the potential competitor's product group overlaps with the customer's product group (e.g., the potential competitor carries 500 of the same digital cameras products carried by the customer).
[0013] Those skilled in the art will appreciate that the above list of variables is meant to be illustrative and that other variables may also be determined. In some embodiments, each variable may be associated with a weight. In some embodiments, the variables may be computed, weighted, added, and normalized to generate a value. In some embodiments, the generated value may be a number between 0 and 100. In some embodiments, if the generated value is above a configurable threshold (e.g., 60%), then the potential competitor may be considered a relevant competitor for the product group of interest.
[0014] Embodiments can provide many advantages. For example, although retailers often know who their top competitors are, it is difficult to determine who their relevant competitors are for each one of their product groups. This method allows a retailer to know who their top competitors are for each one of their product groups. With this information in hand, retailers can create pricing rules for a certain product group against the competitors that are relevant for that product group. For example, while a company may have many competitors for their store in general, in a particular product group such as digital cameras, they may be competing with many niche stores that specialize in digital cameras. Knowing who their competitors are allows the company to create effective, targeted pricing rules.
[0015] These, and other aspects will be better appreciated and understood when considered in conjunction with the following description and the accompanying drawings. The following description, while indicating various embodiments and numerous specific details thereof, is given by way of illustration and not of limitation. Many substitutions, modifications, additions or rearrangements may be made within the scope of this disclosure, which includes all such substitutions, modifications, additions or rearrangements.
DESCRIPTION OF THE FIGURES
[0016] The drawings accompanying and forming part of this specification are included to depict certain aspects of various embodiments. A clearer impression of these embodiments, and of the components and operation of systems provided with them, will become more readily apparent by referring to the exemplary, and therefore nonlimiting, embodiments illustrated in the drawings, wherein identical reference numerals designate the same components. Note that the features illustrated in the drawings are not necessarily drawn to scale.
[0017] FIG. 1 depicts a block diagram of one embodiment of an architecture in which a competitor classifier system may be implemented.
[0018] FIG. 2 depicts an example user interface of an embodiment of a competitor classifier system.
[0019] FIGS. 3-5 depict an example user interface of an embodiment of a competitor classifier system through which competitor reports may be generated and presented to an authorized user of a customer of the system in various ways.
[0020] FIG. 6 depicts a flow chart illustrating operation of an example system for classifying relevant competitors.
DETAILED DESCRIPTION
[0021] Various features and advantageous the present disclosure are explained more fully with reference to the nonlimiting embodiments that are illustrated in the accompanying drawings and detailed in the following description. Descriptions of well-known starting materials, processing techniques, components and equipment are omitted so as not to unnecessarily obscure the present disclosure. It should be understood, however, that the detailed description and the specific examples, while indicating preferred embodiments, are given by way of illustration only and not by way of limitation. Various substitutions, modifications, additions and/or rearrangements within the spirit and/or scope of the underlying inventive concept will become apparent to those skilled in the art from this disclosure. Embodiments discussed herein can be implemented in suitable computer-executable instructions that may reside on a computer readable medium (e.g., a hard disk (HD)), hardware circuitry or the like, or any combination.
[0022] Before discussing specific embodiments, a brief overview of the context of the disclosure may be helpful. Embodiments of systems and methods described herein may determine if an online retailer is a potential competitor for a customer in a particular product group (e.g., a product group defined by the customer using, for instance, SKUs or other product identifiers). A product group may include products in a product category, brand, in a user-defined product group, etc. Relevancy of potential competitors may be determined, for instance, by looking at product overlap, estimated traffic, average rating of online reviews, and a number of views for a website associated with a potential competitor. By knowing who their competitors are for a product group of interest, a retailer may create targeted pricing rules for the product group.
[0023] Turning now to FIG. 1 , a block diagram illustrating an exemplary system 100 is shown. System 100 couples to a network such as the Internet 101 and has access to domains 110 a . . . 110 n. Each domain may have a common network name (domain name) under which a collection of network devices are organized (e.g., domain.com). Each domain may have one or more sub-domains (e.g., abc.domain.com, xyz.domain.com, etc.) according to the hierarchical Domain Name System (DNA) of the Internet. The collection of network devices in a domain may include one or more server machines hosting a website representing the domain (e.g., www.domain.com).
[0024] A website (also referred to as Web site, web site, or site) refers to a set of related web pages (also referred to as pages) containing content such as text, images, video, audio, etc. A website can be accessible via a network such as the Internet or a private local area network through an Internet address known as a Uniform Resource Locator (URL). All publicly accessible websites collectively constitute the World Wide Web.
[0025] Crawler 130 of system 100 may crawl the Internet 101 across domains 110 a - 110 n for data and store them in raw data database 140 . The data obtained by crawler 130 may be associated with retail products. Wrappers 160 may be generated using techniques disclosed in Appendix A and/or Appendix B to extract desired information, such as domain product and price information, from the raw data obtained by crawler 130 . Other suitable wrapper generation techniques may also be used. The domain product and price information thus obtained may be stored at database 170 .
[0026] System 100 may include competitor classifier system or module 150 . Functionality of this feature will now be described in detail. Competitor classifier module 150 may be configured to receive a user defined product group and determine who are the relevant competitors associated with the product group. The relevant competitors for the product group may be determined based on weighted variables associated with a number of unique visitors that the competitor's website has over a time period, a number of reviews and review ratings of the competitor's website, a number of overlapping products that the retailer and a competitor carry, a percentage of overlapping products that the retailer and a competitor carry etc.
[0027] The number of unique visitors that a competitor's website has may be obtained from a data source or website communicatively connected to system 100 . An example data source or website that provides this type of information may be www.compete.com. Likewise, the number of reviews and the review ratings associated with a potential competitor's website may be obtained from a data source or website. An example data source or website that provides this type of information may be www.google.com. In some embodiments, the number and percentage of overlapping products that a retailer and their competitor(s) carry may be determined utilizing embodiments described in the attached Appendices A, B, and C, which form part of this disclosure.
[0028] In one embodiment, each of the variables may have a relative weight. In one embodiment, the variables may be weighted, added together, and normalized to produce a value indicating relevancy. If the relevancy value is above a certain threshold, then the potential competitor may be considered a relevant competitor for the product group of interest. An example threshold may be 60.
[0029] FIG. 2 depicts one embodiment of a table 200 associated with a product group of interest for a potential competitor. Table 200 may include variables such as the product percentage overlap 210 , the number of visitors 215 the potential competitor's website had over a period of time, the number of reviews 220 the competitor's website had, the average of the reviews 225 , and the product overlap count 230 .
[0030] Each of the variables may have different threshold ranges 235 with respective weights 240 . In one embodiment, product percentage overlap variable 210 may have thresholds ranges 235 associated therewith if a potential competitor has a product overlap of 0-10%, 10-20%, 60-100%, etc. Based on which threshold range 235 a competitor should be classified for a particular variable and the weight 240 , a total number of points 237 may be determined for a potential competitor for that variable. For example, as shown in FIG. 2 , a potential competitor may have a product percentage overlap 210 in the range of 60-100% and the weight 240 for that threshold range 235 may be four. Therefore, the potential competitor may be assigned a total number 237 of four points for the percentage overlap variable 210 .
[0031] This calculation is performed for each of the variables 210 , 215 , 220 , 225 , and 230 to generate a total number 237 for each variable. The total numbers 237 are then added to produce a total score points 250 . The total score 250 is computed relative to the maximum possible score points 255 to generate a relevancy score 260 . If the relevancy score 260 is higher than a relevancy threshold 265 , then the potential competitor is considered a relevant competitor and displayed accordingly in box 270 .
[0032] Accordingly, total point score 250 may represent a summation of points score 237 for each weighted variable. Max score 255 may represent a summation of the highest possible point score of the weighted variables for a potential competitor. Relevancy score 260 may represent how relevant a potential competitor is, and may be based on max score 255 and point score 250 . In one embodiment, relevancy score may be determined by dividing point score 250 by max score 255 .
[0033] Relevancy threshold 265 may be a threshold associated with the relevancy of a potential competitor. If a potential competitor has a relevancy score 260 above relevancy threshold 265 , then relevancy indicator 270 may indicate that the potential competitor is a relevant competitor for the product group. If the potential competitor has a relevancy score 260 below relevancy threshold 265 , then the relevancy indicator 270 may indicate that the potential competitor is not a relevant competitor for the product group.
[0034] One skilled in the art will appreciate that threshold ranges 235 , weights 240 for threshold ranges 235 , relevancy score 260 , and/or relevancy threshold 265 may be determined based on a desired configuration for a product group and may vary from implementation to implementation.
[0035] In one embodiment, each variable may include a disqualifier 245 , where if the potential competitor has a variable in a certain disqualified range or value, then the potential competitor is automatically disqualified from being a relevant competitor, even if the potential competitor's relevancy score 260 is above the relevancy threshold 265 . For example, in one embodiment, if the product overlap variable is between 0-10% (i.e., there is no or little overlap of products in the product group), then the potential competitor may be automatically disqualified from being a relevant competitor.
[0036] Now that relevant competitors are determined, FIG. 3 depicts an example user interface 300 through which relevant competitors can be compared according to one embodiment. User interface 300 may include a table 310 with entries associated with a product group 320 for a retailer (e.g., customer 102 of system 100 ). In one embodiment, the product group 320 may be monitors. For each entry 320 in table 310 , user interface 300 may include data associated with how many products the retailer carries for the product group, a number of relevant competitors the retailer has in the product group, etc. An authorized user of the customer may be able to select, via user interface 300 , the relevant competitors in product group 320 to view further information associated with the relevant competitors. This is further illustrated in FIG. 4 .
[0037] As shown in FIG. 4 , a user interface 400 implementing an embodiment of competitor classifier module 150 may provide data associated with a product group 410 for a retailer. In one embodiment, product group 410 may be monitors, and user interface 400 may provide data associated with product group 410 , including, but are not limited to, a number of products (e.g., identified by SKUs) a customer carries for product group 410 , a number of relevant competitors the customer has in product group 410 , relative price index in product group 410 , profit margin for product group 410 , etc. An authorized user of the customer may be able to select, via user interface 400 , the relevant competitors that the customer has in product group 410 to view further information associated with the relevant competitors. In the example of FIG. 4 , the customer has 35 relevant competitors, as determined by an embodiment of competitor classifier module 150 . FIG. 5 depicts a user interface 500 providing further information associated with such relevant competitors.
[0038] As illustrated in FIG. 5 , a customer may have a set of relevant competitors (e.g., 35 ) in a product set (e.g., product category 510 ). A list of top relevant competitors in product category 510 may be generated and displayed via user interface 500 to authorized user of the customer. User interface 500 may include various information such as the relevancy scores of the relevant competitors, names of the relevant competitors, a relevancy index associated with how relevant a competitor is, etc.
[0039] User interface 500 may also include additional information such as a product overlap associated with products that the relevant competitors carries and the products in the product group, a number of unique visitors that the relevant competitor's website has over a time period, a number of reviews associated with the competitor's website, and the average rating of the reviews associated with the competitor's website that are used to determine the competitor's relevancy score.
[0040] By determining what competitors are relevant competitors for a product set, a retailer may determine the products for a product group of interest, determine products that relevant competitors carry that the retailer does not, determine what products the retailer carries that the relevant competitors do not, etc. This can help the retailer to refine their product offerings and further improve their bottom line, thereby becoming more competitive in each product group of interest.
[0041] FIG. 6 depicts an example flow chart 600 illustrating an embodiment of a method for determining relevant competitors for a product group of interest to a retailer.
[0042] At step 610 , a weighted variable associated with a number of unique visitors that a potential competitor's website had over a time period may be determined.
[0043] At step 620 , a weighted variable associated with the number of user-reviews that the potential customer's website has may be determined.
[0044] At step 630 , a weighted variable associated with the average rating of the user-reviews that the potential customer's website has may be determined.
[0045] At step 640 , a weighted variable associated with the percentage overlap between the products within the product group and the products the potential competitor carries.
[0046] At step 650 , a weighted variable associated with the number of the products within the product group that the products the potential competitor carries.
[0047] At step 660 , the weighted variables may added together to determine a relevancy score.
[0048] At step 670 , the relevancy score may be compared to a relevancy threshold to determine if the potential competitor is a relevant competitor.
[0049] Although the present disclosure has been described in terms of specific embodiments, these embodiments are merely illustrative, and not restrictive. The description herein of illustrated embodiments, including the description in the Abstract and Summary, is not intended to be exhaustive or to limit the disclosure to the precise forms disclosed herein (and in particular, the inclusion of any particular embodiment, feature or function within the Abstract or Summary is not intended to limit the scope of the disclosure to such embodiments, features or functions). Rather, the description is intended to describe illustrative embodiments, features and functions in order to provide a person of ordinary skill in the art context to understand the present disclosure without limiting same to any particularly described embodiment, feature or function, including any such embodiment feature or function described in the Abstract or Summary. While specific embodiments are described herein for illustrative purposes only, various equivalent modifications are possible, as those skilled in the relevant art will recognize and appreciate. As indicated, these modifications may be made in light of the foregoing description of illustrated embodiments and are to be included within the spirit and scope of the disclosure. Thus, various changes and substitutions are intended in the foregoing disclosures, and it will be appreciated that in some instances some features of embodiments will be employed without a corresponding use of other features without departing from the scope and spirit as set forth. Therefore, many modifications may be made to adapt a particular situation or material.
[0050] Reference throughout this specification to “one embodiment,” “an embodiment,” or “a specific embodiment” or similar terminology means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one embodiment and may not necessarily be present in all embodiments. Thus, respective appearances of the phrases “in one embodiment,” “in an embodiment,” or “in a specific embodiment” or similar terminology in various places throughout this specification are not necessarily referring to the same embodiment. Furthermore, the particular features, structures, or characteristics of any particular embodiment may be combined in any suitable manner with one or more other embodiments. It is to be understood that other variations and modifications of the embodiments described and illustrated herein are possible in light of the teachings herein.
[0051] In the description herein, numerous specific details are provided, such as examples of components and/or methods, to provide a thorough understanding of described embodiments. One skilled in the relevant art will recognize, however, that an embodiment may be able to be practiced without one or more of the specific details, or with other apparatus, systems, assemblies, methods, components, materials, parts, and/or the like. In other instances, well-known structures, components, systems, materials, or operations are not specifically shown or described in detail to avoid obscuring aspects of embodiments. A person of ordinary skill in the art will recognize that additional embodiments are readily understandable from the disclosure.
[0052] Embodiments discussed herein can be implemented in a computer communicatively coupled to a network (for example, the Internet), another computer, or in a standalone computer. As is known to those skilled in the art, a suitable computer can include a central processing unit (“CPU”), at least one read-only memory (“ROM”), at least one random access memory (“RAM”), at least one hard drive (“HD”), and one or more input/output (“I/O”) device(s). The I/O devices can include a keyboard, monitor, printer, electronic pointing device (for example, mouse, trackball, stylist, touch pad, etc.), or the like.
[0053] ROM, RAM, and HD are computer memories for storing computer-executable instructions executable by the CPU or capable of being complied or interpreted to be executable by the CPU. Suitable computer-executable instructions may reside on a computer readable medium (e.g., ROM, RAM, and/or HD), hardware circuitry or the like, or any combination thereof. Within this disclosure, the term “computer readable medium” or is not limited to ROM, RAM, and HD and can include any type of data storage medium that can be read by a processor. For example, a computer-readable medium may refer to a data cartridge, a data backup magnetic tape, a floppy diskette, a flash memory drive, an optical data storage drive, a CD-ROM, ROM, RAM, HD, or the like. The processes described herein may be implemented in suitable computer-executable instructions that may reside on a computer readable medium (for example, a disk, CD-ROM, a memory, etc.). Alternatively, the computer-executable instructions may be stored as software code components on a direct access storage device array, magnetic tape, floppy diskette, optical storage device, or other appropriate computer-readable medium or storage device.
[0054] Any suitable programming language can be used, individually or in conjunction with another programming language, to implement the routines, methods or programs of embodiments described herein, including C, C++, Java, JavaScript, HTML, or any other programming or scripting language, etc. Other software/hardware/network architectures may be used. For example, the functions of the disclosed embodiments may be implemented on one computer or shared/distributed among two or more computers in or across a network. Communications between computers implementing embodiments can be accomplished using any electronic, optical, radio frequency signals, or other suitable methods and tools of communication in compliance with known network protocols.
[0055] Different programming techniques can be employed such as procedural or object oriented. Any particular routine can execute on a single computer processing device or multiple computer processing devices, a single computer processor or multiple computer processors. Data may be stored in a single storage medium or distributed through multiple storage mediums, and may reside in a single database or multiple databases (or other data storage techniques). Although the steps, operations, or computations may be presented in a specific order, this order may be changed in different embodiments. In some embodiments, to the extent multiple steps are shown as sequential in this specification, some combination of such steps in alternative embodiments may be performed at the same time. The sequence of operations described herein can be interrupted, suspended, or otherwise controlled by another process, such as an operating system, kernel, etc. The routines can operate in an operating system environment or as stand-alone routines. Functions, routines, methods, steps and operations described herein can be performed in hardware, software, firmware or any combination thereof.
[0056] Embodiments described herein can be implemented in the form of control logic in software or hardware or a combination of both. The control logic may be stored in an information storage medium, such as a computer-readable medium, as a plurality of instructions adapted to direct an information processing device to perform a set of steps disclosed in the various embodiments. Based on the disclosure and teachings provided herein, a person of ordinary skill in the art will appreciate other ways and/or methods to implement the described embodiments.
[0057] It is also within the spirit and scope of the disclosure to implement in software programming or code an of the steps, operations, methods, routines or portions thereof described herein, where such software programming or code can be stored in a computer-readable medium and can be operated on by a processor to permit a computer to perform any of the steps, operations, methods, routines or portions thereof described herein. Various embodiments may be implemented by using software programming or code in one or more general purpose digital computers, by using application specific integrated circuits, programmable logic devices, field programmable gate arrays, optical, chemical, biological, quantum or nanoengineered systems, or components and mechanisms may be used. In general, the functions of various embodiments can be achieved by any means as is known in the art. For example, distributed, or networked systems, components and circuits can be used. In another example, communication or transfer (or otherwise moving from one place to another) of data may be wired, wireless, or by any other means.
[0058] A “computer-readable medium” may be any medium that can contain, store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, apparatus, system or device. The computer readable medium can be, by way of example only but not by limitation, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, system, device, propagation medium, or computer memory. Such computer-readable medium shall generally be machine readable and include software programming or code that can be human readable (e.g., source code) or machine readable (e.g., object code). Examples of non-transitory computer-readable media can include random access memories, read-only memories, hard drives, data cartridges, magnetic tapes, floppy diskettes, flash memory drives, optical data storage devices, compact-disc read-only memories, and other appropriate computer memories and data storage devices. In an illustrative embodiment, some or all of the software components may reside on a single server computer or on any combination of separate server computers. As one skilled in the art can appreciate, a computer program product implementing an embodiment disclosed herein may comprise one or more non-transitory computer readable media storing computer instructions translatable by one or more processors in a computing environment.
[0059] A “processor” includes any, hardware system, mechanism or component that processes data, signals or other information. A processor can include a system with a general-purpose central processing unit, multiple processing units, dedicated circuitry for achieving functionality, or other systems. Processing need not be limited to a geographic location, or have temporal limitations. For example, a processor can perform its functions in “real-time,” “offline,” in a “batch mode,” etc. Portions of processing can be performed at different times and at different locations, by different (or the same) processing systems.
[0060] It will also be appreciated that one or more of the elements depicted in the drawings/figures can also be implemented in a more separated or integrated manner, or even removed or rendered as inoperable in certain cases, as is useful in accordance with a particular application. Additionally, any signal arrows in the drawings/figures should be considered only as exemplary, and not limiting, unless otherwise specifically noted.
[0061] As used herein, the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, product, article, or apparatus that comprises a list of elements is not necessarily limited only those elements but may include other elements not expressly listed or inherent to such process, process, article, or apparatus.
[0062] Furthermore, the term “or” as used herein is generally intended to mean “and/or” unless otherwise indicated. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present). As used herein, including the claims that follow, a term preceded by “a” or “an” (and “the” when antecedent basis is “a” or “an”) includes both singular and plural of such term, unless clearly indicated within the claim otherwise (i.e., that the reference “a” or “an” clearly indicates only the singular or only the plural). Also, as used in the description herein and throughout the claims that follow, the meaning of “in” includes “in” and “on” unless the context clearly dictates otherwise. | Competitors are classified in terms of products the competitors offer. A product set is generated from product information received from a user. Also, a competitor set is generated, where the competitor set comprises at least one competitor determined to be relevant to one or more products in the product set. A target price rule is generated that is operative to change a price offered by the user for the at least one product. A competitors relevancy can be determined by considering factors such as: (1) unique visitors to the competitor's website, (2) reviews on the competitor's website (3), ratings on the competitor's website, (4) absolute number of products common to the user's website and the competitor's website, (5) percentage number of products common to the user's website and the competitor's website, and (6) number of products offered by the competitor that comprise the product set. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention provides a toy air pistol for launching a missile bullet; particularly, it relates to an air pistol comprising an air-compression mechanism and a triggering mechanism inside the pistol body portion. When pulling the trigger, the piston will compress the air swiftly to push the missile bullet out of the barrel to let the player imagine a real missile being launched.
2. Description of the Prior Art
The children toys in the current are varied; for instance, there are many different kinds only for the toy gun. Most of them can only provide a sound, or sound and light. Some of them may be able to launch light weight bullets by means of explosive or spring force; the toy gun using explosive can only launch its bullet at very short range, while the gun using spring as a launching power would soon fail to launch bullet as a result of metal fatigue.
SUMMARY OF THE INVENTION
In view of the drawbacks of the aforesaid prior art, the inventor has developed a toy air pistol that can launch a missile-shaped bullet by means of an air pressure. The feature of the present invention is that an air-compression mechanism is installed inside the pistol body portion, and it can compress the air into a given powerful pressure. The pistol of the present invention comprises also a triggering mechanism for launching the bullet upon the trigger being pulled. It is deemed that the present invention has a highly amusement result and a high safety to the player.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a disassembled view of the embodiment according to the present invention.
FIG. 2 is a sectional view of the present invention.
FIG. 3 is a perspective view of the air-compression mechanism in the present invention.
FIGS. 4 and 5 illustrate the operation of the air-compression mechanism of the present invention.
FIG. 6 is a perspective view of the missile bullet being used in the present invention.
FIG. 7 is a sectional view of FIG. 6.
FIG. 8 is a perspective view of FIG. 7.
FIGS. 9 and 10 illustrate another embodiment of the structure shown in FIG. 8.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, there is shown the body comprising two body parts 1, which are assembled together with a plurality of screws. The space behind the barrel is a hollow space for mounting therein an air-compression mechanism and a triggering mechanism. The middle portion of the body portion of the air pistol has a space 11 for mounting a revolving cylinder 2. A barrel 3 is mounted in the front of the body portion, through which a missile bullet is to be shot out. One of the two body parts 1 has a lateral channel portion 12. Under the space 11, there is mounted with a supporting axle 13 for positioning a trigger 14. The handle 15 has an inner hollow space to be used as a battery chamber 16 for receiving battery 161 and mounting a leaf-spring switch 162. The switch 162 is connected with the bulb 17 on the outside of the barrel by means of wire. When . the trigger 14 is pulled, the leaf-spring switch 162 will turn on the circuit as shown in FIG. 2 to light up the bulb.
The major features designed in the present invention are the air-compression mechanism, the positioning and stop mechanism, and the structure of the missile bullet, which are described respectively as follows:
Referring to FIG. 1, there shows the air-compression mechanism, which comprises a cylinder 4, a piston 41, a compression spring 42, and a rear cap 43. The front end of the cylinder 4 has an air hole 401, and two sets of lugs 402 on the outer surface thereof so as to fix the cylinders 4 with screws in the hollow space of the body portion. Under the mid-portion of the cylinder 4, there is an elongated hole 403; also, there is a slot 404 under the cylinder 4 extended from the middle portion to the rear end of the cylinder 4. A piston 41 is mounted inside the cylinder 4; the front end of the piston 41 is in a closed condition, being mounted with a flexible collar seal 411. Under the front end of the piston, there is a stop hole 412, and the rear end of the piston is furnished with a pulling handle 413 extending out of the cylinder 4 beside the slot 404 so as to prevent the piston 41 from rotating radially. The inner part of the piston 41 is a hollow space, in which a rod 414 and a compression spring 42 are mounted. The compression spring 42 is mounted in the piston, and extending out of the piston until the rear end of the cylinder 4, and it is limited within the cylinder 4 by means of a rear cap 43 attached on the rear end of the cylinder 4; the compression spring 42 can only be compressed and can extend axially within and between the piston 41 and the cylinder 4. By means of a rod 414, the spring 42 would not be bent upon being compressed. The rear cap 43 is used for closing the rear end of the cylinder 4 as a stop member of the compression spring 42.
FIG. 3 illustrates a perspective view of the air-compression mechanism, and the operation condition of the piston 41 being pulled with a pulling handle 413. FIG. 2 shows a sectional view of the position and assembled state of the air-compression mechanism. After the air-compression mechanism being mounted in place, the air hole 401 of the cylinder 4 will be in alignment with any one of cartridge chambers 21 of the revolving cylinder 2.
The triggering mechanism of the present invention comprises a trigger 14, a rocking lever 6 and a stop lever 5. The stop lever 5 is mounted on the body part 1 by means of a screw 51, which is also used as a fulcrum to make the lever 5 rock. The rear end of the stop lever 5 is also used as a stop member 52 upon moving upwards at an angle because of the stop member 52 extending into the elongated hole 403 of the aforesaid cylinder 4. The front end of the stop lever 5 is used as a pushing member 53. Between the pushing member 53 and the screw 51, there is a screw 54 to fix one end of a pulling spring 55, while the other end of the spring 55 is fixed with a screw (not shown) to the body part. The stop lever 5 would have its stop member 52 moved upwards upon being pulled by the pulling spring 55. The rocking lever 6 is mounted on the body part 1 with a screw 61 as a fulcrum so as to have the lever 6 rock. The mid-part of the rocking lever 6 has a screw 62 to fix one end of a pulling spring 63, while the other end of the spring 63 is fixed to the body part 1 with a screw; the rocking level 6 would swing downward upon being pulled by the spring 63. The free end of the rocking lever 6 has a round and smooth portion being engaged in a curved recess 141 on the upper rear portion of the trigger 14; when the trigger 14 being pulled, the rocking lever 6 will be pushed upwards at a given distance. The upper end of the rocking lever 6 is mounted with a driving lever 7, of which the lever end is in contact with the free end of the rocking lever 6, while the upper end of the lever 7 is furnished with a right-angle portion extending toward the barrel direction through the body part 1, being engaged with one of the driven teeth 22, of which the function is to be described herein after.
According to the aforesaid pistol structure, the revolving cylinder 2 has a plurality of cartridge chambers 21, i.e., through holes for guiding the missile bullets. Each of the driven teeth 22 at the rear end of the revolving cylinder 2 is corresponding, in position, to each of the cartridge chamber 21. After the revolving cylinder 2 being mounted in the space 11 by means of the supporting pivot 23 pivotally engaged with the body part 1, the revolving cylinder 2 can be driven to revolve; in that case, one of the cartridge chambers 21 will be in alignment with the air hole 401 of the air-compression mechanism and the barrel 3. With the pulling handle 413 being pulled backwards as shown in FIGS. 4 and 5, the piston 41 will be moved backwards to such an extent that the stop hole 412 on the front portion of the piston 41 is aligned with the elongated hole 403 of the cylinder 4; then, the stop member 52 of the stop lever 5 will enter the stop hole 412 to prevent the piston 41 from moving axially. The compression spring 42 between the piston 41 and the rear cap 43 is under a compressed state; the cylinder 4 would take in a lot of air from the air hole 401 to be compressed later for generating a powerful pushing force.
Referring to FIG. 5, it shows that, when the trigger 14 is pulled, the rear edge of the trigger 14 will push the pushing member 53 of the stop lever 5 to cause the lever 5 to turn at an angle around the screw 51 as a fulcrum; as a result, the stop member 52 of the lever 5 moves downwards and out of the stop hole 412 of the piston 41 to release the piston 41, and then the compression spring 42 is released immediately to push the piston 41 forwards rapidly for compressing the air inside the cylinder 4. The air under high pressure will be jetted out of the air hole 401 to drive the missile bullet in the cartridge chamber 21 to shoot out. Simultaneously, when the trigger 14 being pulled, the free end of the rocking lever 6 would move upwards at a given angle to push the upper end of the driving lever 7 upwards to bias at an angle so as to drive the revolving cylinder 2 to rotate one step (because of that upper end being engaged with the driven tooth 22); then, one of the cartridge chambers 21 will be in alignment with the air hole 401. In other words, with the trigger 14 being pulled once, the driving lever 7 will be actuated to drive the revolving cylinder 2 to rotate one step so as to have one cartridge chamber 21 aligned with the air hole 401 (because of the rocking lever 6 being engaged with the trigger 14, and the driving lever 7 being actuated first); then, the stop lever 5 is to be actuated to cause the piston 41 to compress the air. After the trigger 14 is released, the rocking lever 6 and the stop lever 5 will return to their former positions respectively as a result of the pulling springs 63 and 55, and the next operation will be ready. The driving lever 7 is mounted with a return spring (not shown) for pulling the lever back to its former and standby position. When the trigger 14 is pulled, the rear edge of the trigger will push a leaf-spring switch 162 to turn on a bulb circuit, and the bulb will be lighted up upon the pistol firing the bullets. So as to increase the fun when playing with the toy.
The missile bullet 8 according to the present invention is shown in FIG. 6; the bullet 8 includes a conic portion 81, a trumpet-shaped tail 82, and several stabilizing fins 83 being furnished symmetrically around the outer surface thereof. Inside the missile bullet, there is an air chamber 84, of which the front end is closed, while the rear end is opened, being in communication with the trumpet-shaped tail 82. After the missile bullet 8 has been loaded in the cartridge chamber 21 of the revolving cylinder 2, the trumpet-shaped tail 82 is the only portion in contact with the inner surface of the cartridge chamber 21 for holding the bullet 8 in position; the other surface portions of the bullet 8 are not in contact with the inner surface of the cartridge chamber 21 as shown in FIG. 2 so as to minimize the frictional resistance during the bullet being shot. The trumpet-shaped tail portion of missile bullet 8 can completely cover the air hole 401, and therefore the powerful air pressure generated by the piston 41 would enter into the air chamber 84 completely to drive the missile bullet 8 out of the barrel. FIG. 7 illustrates a sectional view of the missile bullet 8. In order to let the missile bullet 8 resemble a missile, the front conic portion 81 of the bullet is mounted with a explosive charge 85 as shown in FIG. 8. When the missile bullet 8 struck a hard object such as the ground surface or a wall, the impact force would cause the explosive charge 85 to generate an exploding sound, being similar to a real firearm. In order to protect children from being harmed when playing the toy, the conic portion 81 of the missile bullet 8 is furnished with a protective cap 86 made of soft rubber as shown in FIGS. 9 and 10. The rear end of the protective cap 86 has a fitting hole 861 to facilitate the cap 86 to be mounted on the conic portion 81. Since the protective cap 86 is made of soft rubber, it would not cause any injury upon shooting to some part of a person's body; in other words, the present invention is a safety toy.
Briefly, the air pistol toy according to the present invention is considered novel in terms of structure. By means of a logical assembly between the air-compression structure and the triggering mechanism, the pistol can have the missile bullets loaded in the revolving cylinder shoot out one after another to fulfill the requirements of a toy, i.e., the amusement and funny result. The front end of the missile bullet is mounted with an explosive charge or a soft protective cap so as to let the missile bullet generate an exploding sound, or shoot a person's body without causing any harm, but with more fun; therefore, the present invention is deemed a perfect toy air pistol. | A toy air pistol for launching missile bullets includes chiefly an air-compression mechanism and a triggering mechanism, a revolving cylinder, and a barrel. The revolving cylinder has several cartridge chambers for loading missile bullets. The air hole of the air-compression mechanism can be aligned with any one of the cartridge chambers. The triggering mechanism releases the compression spring and piston to generate a powerful air pressure out of the air hole to launch the missile bullet out of the barrel. The missile bullet has a trumpet-shaped tail and an air chamber extending almost the whole length of the body thereof for receiving the air pressure as a propelling force for the missile bullet. The front end of the missile bullet may be mounted with an explosive charge or a protective cap so as to have the bullet look and act like a real one, or to increase its safety during play. | 0 |
CROSS-REFERENCE AND PRIORITY CLAIM TO RELATED APPLICATIONS
[0001] This application claims priority to European Patent Application No. EP09176850.7, filed Nov. 24, 2009, entitled “System for and method of installing foundation elements in a subsea ground formation,” which application is incorporated herein by reference and made a part hereof in its entirety.
BACKGROUND
[0002] Systems (denoted by numeral 1 in FIGS. 1 and 2 ) of this type are generally known and usually comprise an impact weight ( 2 ), a hydraulic cylinder ( 3 ), a piston ( 4 ) reciprocatingly accommodated in the hydraulic cylinder ( 3 ) and connected to the impact weight ( 2 ), high and low pressure accumulators ( 5 , 6 ), often also referred to as feed and return accumulators ( 5 , 6 ), a valve system ( 7 ) for alternately connecting the hydraulic cylinder ( 3 ) to the high and low pressure accumulators ( 5 , 6 ), a tank ( 8 ) for a hydraulic medium, such as hydraulic oil, and a pump ( 9 ) for pressurizing the hydraulic medium, i.e. for providing the hydraulic energy required to operate the system.
[0003] If the impact weight is accelerated by means of a gas ( FIG. 1 ), a gas spring also known as “cap” ( 10 ) is positioned above the piston ( 4 ). If the impact weight is accelerated by means of the hydraulic medium ( FIG. 2 ), the valve system ( 7 ) comprises a reversing valve for alternately supplying the hydraulic medium to the cylinder spaces above and below the piston ( 4 ).
[0004] The pressure in and hence the ‘stiffness’ of the system, in particular the pressure in the accumulators and, if present, the gas spring, increases with increasing depth. At extreme depths, such as 1500 meters and deeper, the pressure in the system causes several problems. E.g., it is no longer possible to fill the accumulators from pre-filled gas cylinders. High pressure compressors are required instead.
[0005] Further, during acceleration of the impact weight, the pressure in the return accumulator increases to a much greater extent, in turn requiring a higher pressure in the gas spring, if present, and in the feed accumulator. In hydraulically driven systems ( FIG. 2 ), as disclosed in for instance U.S. Pat. No. 4,367,800, to ensure sufficient acceleration at the end of the stroke a very high initial pressure in the feed accumulator is required.
[0006] In general, at higher pressures, variations in the operating pressure are amplified, which complicates setting and maintaining the striking energy at a preselected level.
[0007] It is an object of the present invention to improve the system according to the opening paragraph.
SUMMARY
[0008] The invention relates to a system for and a method of installing or removing (decommissioning) foundation elements, such as piles, anchors, and conductors, in a subsea ground formation.
[0009] To this end, the system according to the present invention comprises a pump for generating an underpressure in the hydraulic cylinder such as to lift and/or accelerate the impact weight by means of this underpressure. Examples of suitable pumps include electrically or hydraulically driven piston pumps.
[0010] By generating an underpressure in e.g. the low-pressure (return) accumulator or return conduit, the pressure required for accelerating the impact weight is also reduced, thus reducing the problems discussed above.
[0011] The (relative) underpressure that can be generated by means of the pump increases with increasing depth. Current systems work with pressure differences of at least 50 bar. Accordingly, it is preferred that, during operation, the pump for generating an underpressure is positioned or positionable at a depth of at least 500 meters, preferably at least 1000 meters below sea level. The pump is preferably integrated in a so-called underwater power pack which receives electrical or hydraulic power from a surface vessel or facility via e.g. an umbilical or drill string.
[0012] To further facilitate relatively low operating pressures, it is preferred that the pump for generating an underpressure is positioned or positionable at a depth of less than 1000 meters, preferably less than 500 meters above the hydraulic cylinder and more preferably at substantially the same depth as the hydraulic cylinder.
[0013] In a preferred embodiment, the hydraulic cylinder is connected, e.g. via or in conjunction with a high pressure accumulator and a valve, also to the pressure line of the pump for generating an underpressure, i.e. a single pump is employed to generate both an underpressure on one side of the piston in the hydraulic cylinder and a relatively high pressure on the other side of the piston, obtaining a ‘closed loop’.
[0014] To prevent the free piston typically present in the accumulator(s) from hitting the bottom of the accumulator, it is preferred that the system comprises a regulator for maintaining the amount of hydraulic fluid in the hydraulic circuit at a substantially constant level. Usually, systems for subsea installation and removal of foundation elements comprise a unit, known as scavenger, for withdrawing hydraulic fluid from the circuit and subsequently treating, e.g. cooling, filtering, dewatering, degassing, and/or returning the fluid. It is preferred that the regulator is integrated in this unit.
[0015] The invention further relates to a method of installing or removing foundation elements, such as piles, anchors, and conductors, in a subsea ground formation, by means of a hydraulic driver comprising an impact weight, a hydraulic cylinder, and a piston accommodated in the hydraulic cylinder and connected to the impact weight, which method comprises the steps of mounting the impact driver on a foundation element, driving the foundation element into respectively out of the ground formation by alternately lifting and accelerating the impact weight respectively away from and towards the element, wherein the impact weight is lifted and/or accelerated by means of an underpressure above respectively beneath the piston.
[0016] GB 2 078 148 relates to a drop hammer apparatus, wherein a hammer (E) is interconnected with a piston (B) by means of a piston rod. An upright cylinder (A) is open at its upper end, the piston is slidable within the cylinder and the piston rod is slidable through the lower end of the cylinder. The space within the cylinder below the piston is selectively connected to a source (C) of pressurized liquid e.g. water and exhausted by means of a valve (D).
[0017] GB 1 397 137 discloses an apparatus for the driving of piles underwater and comprising a hollow tube connected to the pile, the tube being sequentially evacuated by pump and filled with ambient water by opening a valve at the end of the tube, the incoming water, when it strikes the lower end of the tube or any residual water therein producing a driving pulse. The embodiment shown in FIG. 13 involves repetitively and alternately raising a piston ( 160 ) with a winch ( 125 ) and dropping the piston. Raising of the piston evacuates an enclosure defined by the pile tip and side walls. Quick release of the piston and rapid descent thereof through the pile accelerate a mass of water above the piston. As similar system is shown in U.S. Pat. No. 3,820,346.
[0018] GB 2 069 902 relates to a submersible hammer ( 21 ) for driving piles comprising a piston ( 36 ) and cylinder ( 35 ) assembly provided in conjunction with a ram ( 30 ) to move the same upwardly when the piston is lifted. Sea water is supplied as power medium at a pressure in excess of the ambient pressure and an inlet valve ( 50 ) effects fluid communication between the pressurized sea water and the piston to lift the piston, and thus the ram, and to terminate such communication when the piston reaches a predetermined level. An exhaust valve ( 51 ) vents the sea water allowing the piston and ram to fall until the ram impacts the upper end of a pile to drive the same into the sea bed.
[0019] GB 1 452 777 relates to a gas discharge powered pile driver comprising an “airgun”. WO 2004/051004 discloses a “pile-driving apparatus comprising a pile, a shoe tip coupled to a toe of the pile, and a drill string disposed within the pile.” U.S. Pat. No. 4,964,473 relates to a method for driving a hydraulic submerged tool, wherein the hydraulic pressure energy is generated in a submerged power converter. U.S. Pat. No. 4,089,165 relates to a water pressure-powered pile driving hammer. The piston of the pile driving hammer is raised by hydraulic (water) pressure. In the underwater pile driving apparatus according to U.S. Pat. No. 4,367,800 the hammer is movable upwards and downwards in a housing which, in operation, is filled with a liquid which is present both above and below the hammer, the hammer being driven at least on the upwards direction by a driving liquid which is pressurized by a motor driven pump located on or adjacent the housing and which is the same as the liquid in which the hammer moves. Other prior art relating to underwater pile driving includes EP 301 114, EP 301 116 and U.S. Pat. No. 4,043,405.
[0020] Within the framework of the present invention “underpressure” is defined as a pressure lower than the pressure that prevails in the surroundings of the system. It is noted that in prior art systems underpressure can arise e.g. from inertia of moving components, in particular from the ram at the end of lifting or directly after impact when bouncing upwards. However, these effects are small compared to the underpressure generated by a pump in accordance with the present invention and insufficient to drive the impact weight autonomously.
[0021] The invention will now be explained in more detail with reference to the figures, which show a preferred embodiment of the present system.
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] FIGS. 1 and 2 show prior art systems comprising, respectively, a gas spring and a reversing valve for hydraulically operating the system.
[0023] FIGS. 3 and 4 show systems similar to those in
[0024] FIGS. 1 and 2 comprising a pump for generating an underpressure in accordance with the present invention.
[0025] FIGS. 5 and 6 show closed loop systems.
[0026] FIGS. 7 and 8 show systems without a high pressure accumulator.
[0027] FIGS. 9 and 10 show systems wherein the impact weight reciprocates in water and is driven by water as the hydraulic medium.
[0028] It is noted that the figures are schematic in nature and that details, which are not necessary for understanding the present invention, may have been omitted. Elements that are identical or perform the same or substantially the same function are denoted by the same numeral.
DETAILED DESCRIPTION
[0029] FIG. 3 shows a first embodiment of the system 1 according to the present invention, which comprises an impact weight 2 , a hydraulic cylinder 3 , a piston 4 reciprocatingly accommodated in the hydraulic cylinder 3 and connected to the impact weight 2 by means of a rod 4 A, high and low pressure accumulators 5 , 6 , and first and second valves 7 A, 7 B for alternately connecting the cylinder space beneath the piston 4 in the hydraulic cylinder 3 to the high and low pressure accumulators 5 , 6 . The system further comprises a tank 8 for a hydraulic medium, such as hydraulic oil, a first or feed pump 9 for pressurizing the hydraulic medium and connected, via the high pressure accumulator 5 and the first valve 7 A, to the hydraulic cylinder 3 , a gas spring or “cap” 10 above the piston 4 , and a second pump 11 for generating an underpressure in the hydraulic cylinder 3 .
[0030] When the first valve 7 A is open and the second valve 7 B is closed, the high pressure accumulator 5 communicates with the cylinder space beneath the piston 4 and the piston 4 and impact weight 2 are lifted by the hydraulic medium and the medium, typically air or water, surrounding (the tip of) the impact weight against the action of the gas spring 10 . When the first valve 7 A is closed and the second valve 7 B is open, the hydraulic medium is withdrawn from beneath the piston 4 by the underpressure in the return accumulator 6 and the suction line of the second pump 11 and the impact weight 2 is accelerated by the gas spring 10 in opposite direction, i.e. typically towards a foundation element.
[0031] More specifically, with the system including e.g. an IHC Hydrohammer S-90 and an underwater power pack accommodating the pump for generating underpressure both at a depth of e.g. 2000 meters, the pump can generate an underpressure of up to approximately 200 bar, enabling operating pressures in the high and low pressure accumulators and the cap of approximately 180 bar, 2 bar, and 185 bar, respectively. I.e., during lifting the sum of the pressure of the gas surrounding the impact weight and the pressure of the hydraulic medium beneath the piston results in a force greater than the force resulting from the gas pressure in the cap. During acceleration in the opposite direction, the pressure of the hydraulic medium beneath the piston is reduced almost to zero and said sum of pressures results in a force smaller than the force resulting from the gas pressure in the cap.
[0032] If the underwater power pack is positioned at a different depth than the hammer, e.g. at 1000 meters, the pump can generate an underpressure of up to approximately 100 bar, still enabling operating pressures as low as approximately 280 bar, 200 bar, and 100 bar, respectively.
[0033] In comparison, if the pump is located at sea level, e.g. on deck of a ship, the operating pressures are approximately 380 bar, 215 bar, and 200 bar, see also the Table below. This effect becomes more pronounced with increasing depth.
[0000]
Table for
S-90
Pump on deck
at 1000 m
at 2000
HP accu (bar)
380
280
180
LP accu (bar)
200
100
2
Cap (bar)
215
200
185
[0034] FIG. 4 shows a hydraulically driven system 1 comprising a second pump 11 for generating an underpressure in the low pressure accumulator 6 and a 4/2 valve 7 for alternately connecting the cylinder spaces beneath and above the piston 4 in the hydraulic cylinder 3 to the high and low pressure accumulators 5 , 6 , thus lifting the impact weight and reversing the connections to accelerate it in opposite direction. In this system, pressures are obtainable similar to those in the Table above, e.g. with the hammer and the pump at a depth of 2000 meters and the pump operating at maximum capacity the pressures in the high and low pressure accumulators amount to approximately 180 bar and 2 bar, respectively.
[0035] As shown in FIGS. 5 and 6 , the systems according to the present invention can be simplified by connecting the hydraulic cylinder 3 not just to the suction line of the pump 11 for generating an underpressure but also to its pressure line. I.e., a single pump fulfils the tasks of generating an underpressure on the low pressure (hydraulic fluid outlet) side of the hydraulic cylinder and a relatively high pressure on the high pressure (hydraulic fluid inlet) side of the hydraulic cylinder thus obtaining a ‘closed loop’.
[0036] In such embodiments, a scavenger is preferably added to the system for withdrawing hydraulic fluid from the circuit and subsequently treating, e.g. cooling, filtering, dewatering and/or degassing, the fluid. Further, it is preferred that the scavenger is arranged to maintain the amount of hydraulic fluid in the hydraulic circuit at a substantially constant level, inter alia to prevent the free pistons in the accumulators from hitting the bottoms of the accumulators.
[0037] Also, as shown in FIGS. 7 and 8 , the system can be simplified even further by omitting the high pressure accumulator and the corresponding valve. In systems comprising a gas spring 10 , the system can be operated merely by means of the valve 7 B between the hydraulic cylinder 3 and the low pressure accumulator 6 . When this valve 7 B is closed, the pressure line of the pump 11 communicates with the cylinder space beneath the piston 4 and the piston 4 and impact weight 2 are lifted by the hydraulic medium against the action of the gas spring 10 . When the valve 7 B is open, the hydraulic medium is withdrawn from beneath the piston 4 by the underpressure in the return accumulator and the suction line of the pump 11 , i.e. the hydraulic medium is circulated through the system by the pump, and the impact weight is accelerated by the gas spring.
[0038] If the system is at a sufficient depth, e.g. at depths greater than 500 meters, preferably greater than 1000 meters, the gas spring can also be omitted by establishing fluid communication between the cylinder space above the piston and the surroundings, e.g. by a hydraulic cylinder that is open at one end.
[0039] In hydraulically operated systems, shown in FIG. 8 , in a first position of the valve, in this example a 3/2 valve 7 , the low pressure accumulator 6 and the suction line of the pump 11 communicate with the cylinder space beneath the piston 4 but the cylinder space above the piston 4 communicates with the pressure line of the pump 11 and the impact weight 2 is accelerated by the pressure difference. A compensator 12 can be included to guarantee a sufficient supply of hydraulic medium to the cylinder space above the piston 4 . In the other position of the valve 7 , the low pressure accumulator 6 and the suction line of the pump 11 communicate with both the cylinder space beneath and the cylinder space above the piston 4 and the impact weight 2 is lifted by the medium, typically air or water, surrounding the impact weight 2 .
[0040] In further embodiments, the impact weight is accessible for water from the surroundings such that, during operation, the weight reciprocates in water. Although dissipation is thus increased, the system no longer requires the feeding of gas to the hammer.
[0041] In the embodiments shown in FIGS. 9 and 10 , the hydraulic circuit is arranged to withdraw water from and exhaust water to the surroundings, i.e. seawater is employed as the hydraulic medium for driving the impact weight. In such embodiments, it is preferably that water withdrawn from the surroundings passes through a filter 13 first.
[0042] It is understood that any feature described in relation to any one embodiment may be used alone, or in combination with other features described, and may also be used in combination with one or more features of any other of the embodiments, or any combination of any other of the embodiments. | The invention relates to a system for installing or removing foundation elements, such as piles, anchors, and conductors, in a subsea ground formation, comprising an impact weight, an hydraulic circuit in turn comprising an hydraulic cylinder for lifting and/or accelerating the impact weight respectively away from and towards the element, the cylinder comprising a piston connected to the impact weight, and wherein a pump for generating an underpressure in the hydraulic cylinder such as to lift and/or accelerate the impact weight by means of this underpressure. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 335,171 filed Dec. 28, 1981 now abandoned by Manfred A. A. Lupke and Gerd P. H. Lupke.
FIELD OF THE INVENTION
The present invention relates to the perforating of pipes and particularly to perforating corrugated thermoplastic pipes at spaced points. The perforated pipes are commonly used in underground drainage applications.
BACKGROUND OF THE INVENTION
It is known that the size and configuration of the holes in an underground soil drainage pipe can effect the performance of the pipe. For example, pipes with large holes are readily silted up if used in fine silt or sandy soils. Thus, a demand has arisen for different types of drainage pipes to be used under differing conditions. This has lead to a parallel demand for machinery capable of producing the various pipe hole configurations at high production speeds.
One known prior apparatus is described in U.S. Pat. No. 3,824,886 issued July 23, 1974 to Wilhelm Hegler. The apparatus disclosed in that patent includes a knife with a piercing point leading a concave cutting edge. In perforating a pipe, the piercing point moves into and through the pipe wall, the knife turns and the concave cutting edge moves tangentially through the pipe wall to cut a slot in it. The knife again turns to bring the piercing point through the pipe wall from the inside to the outside at the end of the slot. This piercing, slotting and severing action serves to chip a slot out of the pipe wall. To achieve the desired motion of the knife, it is mounted on a carrier that rotates about its own axis and revolves about the pipe. The rotation and revolution are so related that the leading end of the knife follows a path in the shape of an epitrochoid and chips slots from the pipe as it travels through nodes of the epitrochoid.
In another slot cutter described in the applicants'U.S. Pat. No. 4,180,357 issued Dec. 25, 1979, the knives are mounted on rotary but otherwise fixed spindles.
In all such slotters, the slot size is difficult to control as it varies widely with relatively small changes in other parameters such as the pipe wall thickness, knife adjustment and knife sharpness. This variance results primarily from the tapering of the ends of the slot as described, for example, in the Hegler Patent referred to above. Consequently, to provide for a more uniform opening size and a smaller opening size than is possible with a slot cutter, other types of machine have been developed which use a punching action in which a tool with a cutting end is driven radially through the pipe wall to form a perforation that is of substantially the same size and shape as the punching tool. Typical machines are described in Zieg et al U.S. Pat. No. 3,620,115 issued Nov. 16, 1971 and in Leloux German Pat. No. 2,652,169 of Oct. 2, 1980. While these punching type of perforators can produce holes of controlled size and shape, they require either an intermittent stopping of the pipe advance during the punching action or a complex mechanism to move the punching tool axially with the pipe as it is driven radially through the pipe wall.
SUMMARY OF THE INVENTION
The object of the present invention is to provide a relatively simple punching apparatus that can produce substantially uniform perforations of controlled size and configuration at high speed and with continuous pipe feed.
According to the invention, this is accomplished by mounting a punch with a piercing end on a spindle that, like the knife carrier in the Hegler slotter, rotates about its own axis and revolves about the pipe, but wherein the relative speeds of the rotation and revolution are controlled to drive the punch around the pipe in what is substantially an epicycloid rather than the epitrochoid required for the slotting type cutter of Hegler. With this arrangement, the punch perforates the pipe substantially radially even though the action of the apparatus is purely rotary.
To ensure proper registration of the punch with corrugations in the pipe wall, and to drive the pipe through the apparatus, the spindle may be equipped with a helical rib matching the pipe corrugations in pitch. Where the punch is to act at the roots of the corrugations, the punch will project from a base surface of the spindle at the crown of the rib. To perforate the crests of the corrugations in the pipe, the comparable base surface is at the root of the rib. To provide for the desired path, a drive means is provided for rotating the spindle about its axis and revolving the spindle about the pipe while maintaining the ratio W/W2=A/B. W1 is the angular speed of rotation of the spindle about its axis, while W2 is the angular speed of revolution of the sindle about the pipe. A is the outside radius of the pipe where it contacts the base surface of the spindle and B is the radius of the base surface of the spindle.
BRIEF DESCRIPTION OF THE DRAWINGS
In the accompanying drawings, which illustrate exemplary embodiments of the present invention;
FIG. 1 is a schematic illustration showing the position of a punch on a carrier and a portion of the path of the punch with respect to a pipe to be perforated;
FIG. 2 is a sectional side elevation, taken on line 2--2 in FIG. 3 of an apparatus for perforating corrugated pipe;
FIG. 3 is a section on line 3--3 in FIG. 2;
FIGS. 4 and 5, located on the same sheet as FIG. 1, are front and side views, partly in section, of a punch mounted on a carrier.
FIG. 6, located on the same sheet as FIG. 3, is a partly sectional schematic showing the punch of FIGS. 4 and 5 as it perforates the wall of a pipe;
FIG. 7, located on the same sheet as FIG. 2, illustrates a length of corrugated pipe after being perforated by punches like those shown in FIGS. 4 and 5;
FIG. 8 is a schematic illustration of another embodiment of the apparatus for producing a filter pipe; and
FIG. 9 is an elevation of a filter pipe produced by the apparatus of FIG. 8.
DETAILED DESCRIPTION
Referring to the drawings, FIG. 1 illustrates a cross section of a pipe 10 with a central axis O. The pipe 10 is corrugated, having a wall thickness T in the troughs between the crests 11. The external radius of the pipe at the troughs is A.
A cutter for perforating the tube includes a tool carrier in the form of a cylindrical spindle 12 with a portion of radius B tangential to the pipe 10 at the base of the illustrated trough. A punch 14 is mounted on the spindle and projects radially from the portion of radius B by a distance slightly greater than the pipe wall thickness T. The spindle 12 rotates about its axis X causing the punch 14 to rotate about the axis X. The spindle is in turn caused to revolve in a circular path about the central axis O of the tube. The ratio of the angular velocity of the spindle about axis X to the angular velocity of axis X about axis O is A:B. This means that the portion of the spindle 12 of Radius B rolls about the pipe 10 without slip and a point Q where the punch meets the surface of the spindle is caused to follow an epicycloidal path E having a cusp which touches the surface of the pipe at point P. At the point P, the punch 14 penetrates the wall of the pipe 10 to form an aperture. The penetration is substantially radial so that there is no tangential force exerted on the pipe.
In the embodiment schematically illustrated in FIG. 1, the radii A and B are equal so that the angular velocities of the punch 14 about axis X and of axis X about axis O are equal. The epicycloidal path E is a cardoid with a single cusp. In other embodiments, the radii A and B may not be equal. They are preferably in a simple whole number ratio e.g. 1:2, 2:1 or 3:1. In any event, even if thr radii A and B are not in a simple whole number ratio, the angular velocities are in the ratio A:B to produce the desired epicycloidal path.
In FIG. 1, a single spindle with a single punch is shown for simplicity of illustration. In the apparatus illustrated in FIGS. 2 and 3, three spindles, each with a single punch, are disposed symetrically about the tube. In other embodiments, other numbers of spindles or punches may be employed.
Referring more specifically to FIGS. 2 and 3, the apparatus illustrated includes a housing 15 with end walls 16 and 17. End wall 17 has a central circular opening 19 for receiving a pipe to be perforated. The end wall 16 has a larger circular opening that is aligned with the opening 19 and has a counterbore on the outside. A ball bearing 22 is fitted into the counterbore and is retained in position by an end cover 22a. The bearing 22 carries the cylindrical sleeve of an adaptor 20. The adaptor 20 also has a circular flange fastened to the side face of a sheave 29 by cap screws 29a. The adaptor 20 and sheave 29 have a through bore 18 that is the same size as the opening 19 in end wall 17 and aligns with that opening so that a pipe 10 may pass into and out of the apparatus through the openings 18 and 19.
A stationary ring gear 21 is secured to the inside face of wall 17 by bolts 21a. The gear is aligned with the opening 19 so that the pipe 10 can pass through the gear. The hub of the gear 21 carries a ball bearing 23, which in turn supports a gear housing 25. The housing is sealed to the gear 21 by seals 25a and 25b.
The gear housing 25 carries three shafts 26a parallel to the gear 21. A pinion 26 is keyed to each of the shafts 26a and meshes with the teeth 24 of the ring gear 21. Each shaft 26a also carries a gear 26b. Three idler gears 28 carried by the housing 25 mesh with the gears 26b.
Three drive bars 30 (one shown) extend between the gear housing 25 and the sheave 29. The bars are secured to both the housing and the sheave so that these parts rotate as a unit.
Also extending between the gear housing 25 and the sheave 29 are three spindles 33. At one end each spindle shaft extends into the gear housing 25 and is keyed to a gear 27 meshing with a respective one of the idlers at 28. The other end of the spindle shaft is mounted on the sheave 29 by ball bearing 33A.
Between the gear housing 25 and sheave 29 each of the spindles 33 has an enlarged cylindrical section 34. This section 34 carries a helical rib 35 on its outer surface and a punch at the location indicated by the circle Y. The punch will be described in more detail in connection with FIGS. 4 and 5.
A drive shaft 32 extends through the housing 15, parallel to the pipe 10. It is mounted in bearings 32a and 32b in the end walls 16 and 17 respectively. The shaft 32 carries sheave 42 aligned with sheave 29. Sheave 42 drives sheave 29 through a series of V belts 31.
As mentioned above, the punch is more clearly illustrated in FIGS. 4 and 5. As illustrated in those figures, the body 34 of the spindle 33 has a stepped bore 37a aligned with the rib 35. A cylindrical body 37 of the punch fits into the bore 37a and is held in place by a cap screw 38 extending into the bore 37a from the opposite side and threaded into a bore in the inner end of body 37. The punch has a cutting head 36 with a V-shaped cutting edge along the end facing radially away from the axis of the spindle. The cutting edge serves for punching short rectangular slots in the pipe. The punch is shown in FIG. 6 engaged with the wall of the pipe 10 and piercing the pipe in the desired manner. FIG. 7 illustrates a helically corrugated pipe 10 with slots 40 produced by the punch.
In operation of the apparatus, the drive shaft 32 is driven from an external power source of any appropriate sort. This drives the sheave 40, the belts 31 and sheave 29. Rotation of sheave 29 acts through drive bars 30 to rotate the gear housing 25. As the sheave 29 and gear housing 25 rotate, the spindles 33 are revolved about the pipe 10 extending through the housing. The gear train consisting of stationary gear 21, pinions 26 and 26b, idlers 28 and gears 27 rotate the spindles 33 about their respective axes. Appropriate selection of the gear ratios insures that the ribs 35 of the spindles 33 will roll on the surface of the pipe 10 without slipping, so that the punches will progress around the pipe in epicycloidal paths.
The helical ribs 35 on the spindles 33 engage the corrugations of the corrugated pipe to advance the tube through the cutter. With a pipe having helical corrugations such as that shown in FIG. 7, the ribs 35 may be annular rather than helical. Helical ribs are required for a pipe with annular corrugations.
FIG. 8 illustrates an embodiment of the apparatus for punching a large number of very small holes in the wall of a thermoplastic pipe with a double corrugation as illustrated in FIG. 9. The pipe 43 shown in FIG. 9 has primary troughs 44 separated by annular crowns 46. Each crown 46 is in turn formed with a small annular secondary trough 48. A row of small drain holes is formed along the root of each primary and secondary trough to form a "filter pipe" that is useful for drainage purposes in fine or sandy soils.
Referring to FIG. 8, the illustrated pipe is shown as having an outside radius A at the base of the primary trough and an outside radius C at the base of the secondary trough. The secondary trough is quite shallow and for the sake of clarity, has been shown as though it was flat rather than concave.
A spindle 50 has a helical rib 52 meshing with the primary trough 44 of the pipe 43. The spindle has an axis Y parallel to the axis O of the pipe 43. The spindle has a base surface of radius D at the root of the rib 52. The radius D is equal to the pipe radius C. Small pin-like punches 54 are uniformly spaced around the spindle 50.
The punches project radially from the base surface of the spindle between adjacent turns of the rib 52. In FIG. 8, one row of punches is illustrated. Other rows, with the punches offset angularly from those illustrated, may be included in preceding or following sections of the spindle. This use of plural staggered rows of punches provides for a large number of very closely spaced holes in the pipe while maintaining sufficient space between adjacent punches on the spindle to allow for installation and service.
Two smaller diameter spindles 60 have axes Z that are parallel to the pipe 43. Each spindle 60 has a helical rib 62 that extends into the primary trough 44 of the pipe 43 and engages the base of the trough. The base surface of each spindle 60 is at the crown of the rib and has a radius E equal to the outside radius A of the pipe 43 at the base of the primary trough. Pin-like punches 64 project radially from the rib 62 and are spaced along one or more turns of the rib. Where more than one turn is equipped with punches, the punches in adjacent turns are offset angularly from one another to provide a uniform distribution of punches around the spindle. The two spindles 60 are so oriented angularly about the axis Z that the punches of one will perforate the pipe between the perforations produced by the punches of the other. This adjustment is readily made through adjustment of the engagement between the idler 28 and the pinion 27 (FIG. 2).
In operation, the three spindles revolve about the pipe 43, rotating about their individual axes at the same angular speed. Because the radius D of the base surface of the spindle 50 equals the pipe radius C, the spindle rolls on the crowns 46 of the corrugations without tangential slip. The punches 54 roll into and out of the base of each secondary trough to produce a series of small drain holes as illustrated in FIG. 9. Similarly, the ribs 62 of spindles 60 roll on the bases of pipe primary troughs 44 without slip. The punches 64 roll into the pipe to produce a series of small diameter holes spaced along the base of the trough.
While particular embodiments of the invention have been described in the foregoing, it is to be understood that other embodiments are possible within the scope of the present invention. The invention is to be construed as limited only by the apended claims. | A pipe perforating apparatus has a spindle carrying a cutting tool and a drive for rotating the spindle about its own axis while revolving the spindle about the pipe. The cutter periodically engages and perforates the pipe. To provide for small, uniform sized holes in the pipe, the cutting tool is an end cutting punch and the spindle is rotated and revolved around the pipe to roll the punch into and out of the pipe without exerting a tangential force on the pipe. | 8 |
BACKGROUND OF THE INVENTION
For several decades, the use of the Eschweiler-Clarke ("E-C" for brevity) reaction has been used in laboratory procedures for the methylation of simple acyclic and cyclic amines, with excellent results, the reaction proceeding essentially quantitatively with only a relatively small excess of formaldehyde (HCHO) and enough formic acid (HCOOH) to solvate the amine reactant, typically from a 2-fold to 4-fold molar excess of HCOOH. If a much larger excess of HCHO and HCOOH is necessary, the E-C reaction is not used, as far as we know, commercially. The reason is that it is impractical to recover the unused excess reactants.
Because of the convenient and economical way in which the E-C reaction can introduce a methyl substituent on an amine N atom, the reaction has attracted particular attention for the methylation of the hindered N atom of hindered piperidyl, piperazinyl, piperazin-2-one, diazepine and diazepin-2-one groups, in stabilizer compounds commonly referred to as "hindered amines". Except that, because of the highly hindered N atom to be methylated, the reaction is usually carried out in the laboratory with at least a 2-fold molar excess of HCHO and a much larger excess of HCOOH. Most of the excess HCOOH is recoverable for reuse by an economical distillation but excess of HCHO is wasted. Thus, with a 2-fold molar excess of HCHO, one mole is wasted for each mole used. This is too large an excess of HCHO to be economical. I decided to investigate solutions to this problem, namely the methylation of the hindered N atom in hindered amine light and heat stabilizers for organic compounds.
In UK Pat. appl. GB 2,194,237 (Mar. 2, '88) piperidyl-containing compounds were methylated using the E-C procedure. Example 1 discloses preparation of a tetramine containing plural triazine rings, each substituted with two pentamethylated piperidyl substituents. The amine to be methylated is N 1 ,N 2 ,N 3 , N 4 -tetrakis-[2,4-bis[N-(2,2,6,6-tetramethyl-4-piperidyl)-n-butylamino]-l,1,3,5-triazin-6-yl]-4,7-diazadecane-1,10-diamine; it has 2 terminal -NH groups and 8 tetramethyl-4-piperidyl substituents, each with a >NH group. To a solution of 0.02 moles of this amine in 100 ml of water is added 0.4 moles of formic acid (two-fold molar excess) and 0.4 moles of a 40% aqueous formaldehyde solution (two-fold molar excess). The solution is heated under reflux for 8 hr; after cooling to room temperature, an additional amount of 0.2 moles (stoichiometric for all NH groups to be methylated) of 40% formaldehyde is added and the solution refluxed for an additional 5 hr. Repeating this reaction with a simpler piperidyl-substituted compound and a two-fold excess of HCHO and HCOOH, I found that methylation proceeded with excellent conversion, albeit relatively slowly. However, when the reaction was starved of HCHO by decreasing the molar excess of HCHO to 50% (in steps, from 200%) the reaction mass was so difficult to work up, that a NMR (nuclear magnetic resonance) mass spectrographic analysis of the concentrated reaction mass had to done, and this indicated less than 50% methylation of the >NH group irrespective of how much HCOOH was used.
Several methylated piperazine- and piperazin-2-one-containing stabilizers have been disclosed in Japanese Pat. application No. 63-86711 published Apr. 18 1988. In such PSP-containing compounds, the hindered N 4 atom in the diazacycloalkan-2-one ring is substituted at both the 3-and 5- positions. The N 4 atom is hindered in all such PSPs. This N 4 atom is termed "the hindered N atom" because it is flanked by disubstituted 3- and 5-carbon atoms, either or both of which may have a spiro substituent. Homologous (with the piperazin-2-ones) are diazepin-2-one compounds containing a seven-membered diaza ring. The polysubstituted piperazin-2-one ("PSP") and diazepin-2-one substituents are each diazacycloalkan-2-one substituents which are together referred to herein by the acronym "DCA", for convenience.
A polysubstituted diazacycloalkan-2-one and compounds containing one or more DCA substituents are "DCA-containing" compounds referred to herein as "complex amines". In the Japanese reference, methylated PSP stabilizers are said to improve the color of polyacetals. There is no teaching of how such methylated compounds were prepared, but because such methylated stabilizers are not commercially available, it is expected they were synthesized in the laboratory. Since I was particularly interested in methylating DCA-containing compounds, and more particularly, PSP-containing compounds, my efforts were directed to converting an uneconomical laboratory process for methylating such compounds to an economical one.
The process of this invention exploits the peculiar and unique susceptibility of a DCA group to a starved E-C procedure. The unique configuration of a DCA group imbues it with characteristics which permit easy methylation of only the NH groups in the DCA, while failing to methylate other -NH groups which may be present in complex amines.
Examples of DCAs are those referred to in U.S. Pat. No. 4,190,571 the disclosure of which is incorporated by reference thereto as if fully set forth herein, and the aforementioned Japanese 63-86711. Illustrative of DCA-containing compounds are (a) triazine compounds having PSP substituents such as those disclosed in U.S. Pat. Nos. 4,480,092; 4,629,752; and, 4,639,479 (referred to as "PIP-T" compounds); and (b) N-(substituted)-α-(3,5-dialky-4-hydroxyphenyl)-α,α-disubstituted acetamides disclosed in U.S. Pat. No. 4,780,495 (referred to as "3,5-DHPZNA" compounds); the disclosure of each of which foregoing references is incorporated by reference thereto as if fully set forth herein. Methylated PSPs, 3,5-DHPZNAs and PIP-Ts, in each of which the NH groups are methylated, are excellent stabilizers for polyoxymethylene resins, particularly polyacetals.
A typical E-C process is described under the heading "Methylation of Amines with Formaldehyde" in Organic Reactions, Vol V by M. L. Moore, pg 307 et seq., as follows: "One molecular proportion (or slight excess) of formaldehyde and two to four molecular proportions of formic acid are used for each methyl group introduced, indicating that it is mainly the formic acid that supplies the hydrogen involved in the reduction. The reaction is carried out on a steam bath." The HCHO contributes the carbon atom of the methyl group, the HCOOH solvates the amine reactant and provides the hydrogen (proton) for reduction.
This typical E-C reaction, carried out with a primary or secondary amine, results in the methylated amine when the reactants are heated for several hours after the evolution of gas has ceased. The formic acid functions as both a co-reactant and a solvent. The function of formic acid as a solvent is particularly important when the amine to be methylated is poorly soluble in water.
Unhindered amines such as benzylamine and secondary amines such as piperidine and piperazine are expected to be methylated with a slight excess of HCHO to give almost theoretical conversion to the corresponding methylated amines, and in practice, provides a highly acceptable conversion, even if not quantitative. But because hindered amines are so highly hindered, they are not expected to provide essentially complete conversion, are expected to require a large excess of HCHO. The overall yield of the reaction is further reduced by the difficulty of recovering the desired product from the reaction mass ("work-up"). The result is an unacceptably low yield from a high-priced complex amine starting material, and the low yield makes the E-C process uneconomical.
In a text-book procedure for a typical E-C reaction (see Moore, supra pg 323), benzylamine (1 mole) is added with cooling, to 5 moles of 90% formic acid. Then 2.2 moles of 35% formaldehyde solution is added, and the mixture is heated on a steam bath under reflux for 2 to 4 hours after evolution of gas has ceased (8 to 12 hr in all). Slightly more than 1 mole of concentrated hydrochloric acid is then added and the formic acid and any excess formaldehyde are evaporated on a steam bath. The colorless residue is dissolved in water and made alkaline by the addition of 25% aqueous sodium hydroxide, and distilled over sodium. The product, N,N-dimethylbenzylamine is recovered in excellent yield.
Carrying out this reaction commercially is burdened with the costs of recovering the large excess of formaldehyde or formic acid, or both. For example, Czech appln. No. 82/5562 filed July 21, 1982 discloses treating the methylated product with HCl, then distilling under vacuum to remove volatiles. The yield was 66-70% which is commercially unacceptable because of the high cost of a DCA-containing amine to be methylated. Such a distillation process still leaves the problem of separating the large excess of formic acid from the formaldehye.
Separating formaldehyde and formic acid as aqueous solutions of chosen concentration (which may later be diluted) by distillation, is not practical because of the too-close boiling points. For example, USSR appln No. 80/22299, filed Oct 10, 1980 discloses distillation in a column the pressure at the top and bottom of which was 20 mm and 2 atm respectively.
My process is applicable only to the methylation of DCA-containing compounds and not to piperidines or diazacycloalkanes because the latter two are not susceptible to methylation when starved of HCHO. It was surprising that only a DCA group can be methylated with only a bare excess of formaldehyde, much less than the amount one would typically expect to use in a conventional E-C reaction (hence my process is referred to as the "starved E-C process"). The amount of water present during the starved E-C reaction is not critical except for the effect on the time required to complete the reaction. In general, the more dilute the reaction mass, the longer the time for the reaction, and in a commercial process, it is generally desired to run under conditions which provide maximum reactor productivity.
Neither could it have been foreseen that, after the reaction is completed and the formic acid neutralized with sufficient aqueous alkali to make the reaction mass basic ("basified"), the methylated product would separate from solution, and would be so insoluble in water that it could be washed with water without sacrificing any more than 1% of its weight. This ability to wash out essentially all impurities from the solvent phase, including unreacted formaldehyde, formic acid and salt formed upon neutralization, enhances the efficiency of, and vastly simplifies the recovery procedure for the methylated product. It will be recognized that not all methylated complex amines will be so insoluble as to lose less than 5% upon repeated washing with water, so that my process is specifically directed to those which do.
Irrespective of the dilution of the reaction mass with water, the starved E-C reaction is carried out at above about 60° C., and CO 2 formed during the reaction is driven off. A higher temperature shortens the time for the reaction, producing the methylated DCA substantially quantitatively, typically in less than 8 hr.
It will be evident from the foregoing, that the steps under which adequate conversion is obtained in a reasonable amount of time, and the steps of a "work-up", taking advantage of the substantial insolubility of the methylated complex amine in water (under process conditions provided in the recovery system), must together provide a high enough yield of essentially pure product to make the process commercially successful.
The difficulty of methylating the hindered N atom of a piperidyl group, Piccinelli et al (Eur. Pat. appln. 0319480 published June 7, 1989) used an alkylbenzene solvent in a modification of the usual E-C procedure. They methylated triazine compounds containing 2,2,6,6-tetramethylpiperidyl groups. But there is no indication of either what percentage of the piperidyl groups were methylated, or what the yields might have been.
My process relates specifically to methylating the hindered N atom of a DCA group by starving the well-known E-C reaction of HCHO, yet achieving essentially stoichiometrically complete conversion of the >NH group(s) in any DCA-containing compound. This process takes advantage of the discovery that the NH group in a DCA is uniquely susceptible to methylation without a large excess of HCHO. This discovery provides the basis for a commercial process.
SUMMARY OF THE INVENTION
It has been discovered that the hindered N atom of a polysubstituted diazacycloalkan-2-one ("DCA"), whether a diazepin-2-one or a piperazin-2-one ("PSP"), may be methylated with substantially stoichiometrically complete conversion by using a "starved" Eschweiler-Clarke ("E-C") procedure. This procedure starves the reaction of HCHO. In some instances only a molar amount of HCHO results in complete conversion of the starting amine to methylated product. The starved E-C process comprises adding enough formic acid as will form a solution with the DCA under reaction conditions, and no more than a bare molar excess of formaldehyde, so as to produce a N 4 - or N 5 -methylated amine without using any solvent. The formic acid reactant serves as solvent. The amount of water present is not critical and the methylation of the hindered N 4 - or N 5 -atom will be substantially stoichiometric under either "dilute" (more than 30% by weight of the reaction mass is water) or "concentrated" (from about 1% to 30% by weight is water) conditions. After neutralization of the reaction mass, the product separates spontaneously, generally as a water-insoluble solid which can be washed with water without significant loss, typically providing an yield in excess of 90%.
It is therefore a general object of this invention to provide a starved E-C process for methylating a DCA or DCA-containing complex amine ("starting amine") using less than 2 mols HCHO per >NH group, preferably no more than 50% over stoichiometric of HCHO, which excess fails to methylate the >NH group of a polysubstituted piperidine, piperazine or diazepine (hindered amine), so as to produce more than 50% conversion (molar) of the starting amine.
It is also a general object of this invention to provide a starved E-C process which results in substantially stoichiometric methylation of the hindered N 4 or N 5 - atom of the starting amine without using more than a 50% molar excess of HCHO, present either as aqueous formaldehyde or substantially anhydrous paraformaldehyde; and, sufficient formic acid to form a solution of the starting amine under the conditions at which it is methylated. Whether under "dilute" or "concentrated" conditions, all the water, including the water formed during the reaction, may remain in the reaction mass; or, some or most of the water may be separated during the reaction if the reaction mass is to be concentrated while the reaction proceeds. In either case, there is a single liquid phase present before the excess formic acid is neutralized and the reaction mass basified.
It has also been discovered that the foregoing starved E-C process produces a methylated DCA or DCA-containing complex amine which typically has so low a solubility in water under the alkaline conditions prevailing upon basifying the reaction mass, that methylated amine which separates may be washed with water with the loss of less than 5%, and preferably less than 1% of the methylated product.
It is therefore another object of this invention to provide a starved E-C process in which, under concentrated conditions, (a) solid paraformaldehyde is substituted for aqueous formaldehyde; (b) the amount of concentrated aqueous formic acid (at least 88% by weight HCOOH) is only sufficient to form a saturated solution of the starting amine under the temperature and pressure conditions of the reaction; (c) the methylation is carried out at or below reflux temperature so that the starting amine is substantially stoichiometrically converted; (d) after neutralization with excess aqueous alkali, the methylated amine separates from the reaction mass; (e) separated methylated amine is then washed with water without transferring more than 5% by wt, preferably less than 1% by wt, of the methylated product to the aqueous phase; and, (e) the yield of the methylated amine is at least 90%, and preferably 95% or more.
It is a specific object of this invention to provide the foregoing starved E-C process wherein the molar ratio of the >NH group(s) in the DCA or DCA-substituted compound and HCHO is in the range from about 1:1 to about 1:1.5, preferably in the range from 1:1.02 to 1:1.5, and most preferably from 1:1.05 to 1:1.2.
It is yet another specific object of this invention to provide the foregoing starved E-C process for the methylation of each hindered N 4 or N 5 -atom in the diaza ring of a DCA or DCA-substituted compound, the process being carried out in an oxygen-free reaction zone operating at relatively low, preferably autogenously developed pressure at the temperature of reaction.
It is a further specific object of this invention to provide the foregoing starved E-C process comprising (a) operating a reaction zone at or below the boiling point of the reactants in solution and at autogeneous pressure, said zone containing only as much HCOOH as is required to dissolve the starting amine under reaction conditions, and less than a 50% molar excess of HCHO theoretically required to methylate only the amine >NH groups (the amide NH group in the DCA cannot be methylated) in the starting amine; (b) maintaining the conditions of reaction until essentially stoichiometrically complete methylation is obtained; (c) thereafter neutralizing the reaction mass so as to precipitate methylated amine product; and, (d) separating and washing the product with water, yet removing in the water) less than 1% by weight of the product.
BRIEF DESCRIPTION OF THE DRAWING
The foregoing and other objects and advantages of our invention will appear more fully from the following description, made in connection with the accompanying flowsheet of a preferred embodiment of the invention, illustrating a single multi-purpose reactor and associated equipment, in which reactor a DCA or DCA-substituted compound is methylated.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
It will now be evident that use of only a bare excess of HCHO, and sometimes only an equimolar amount, equal to the number of NH groups in the starting amine, permits the essentially complete conversion of the DCA or DCA-substituted compound to be methylated. This is attributable to the unique characteristics of the 2-keto group in the DCA. Also evident is that, because the reaction mass must be water-washed to remove the unreacted HCHO, HCOOH, and unwanted byproducts, it is fortuitous that, not only does the desired methylated amine product separate spontaneously upon neutralization of the reaction mass, but that the product is essentially insoluble in water.
By "essentially complete conversion" I refer to methylation of at least 95%, and preferably 99% of the NH groups in the starting amine. By "essentially insoluble" I mean that the solubility is less than 1 part of product per 100 parts of water, so that upon washing, less than 1% by weight of the product recovered after neutralization of the reaction mass, is lost in the water wash.
It is most preferred, to save on the cost of recovering unreacted excess HCOOH, to use only as much as is necessary to solvate the complex (starting) amine at the temperature at which the reaction is to be carried out, provided that at least 1 mol of HCOOH is used for each NH group to be methylated. With many complex amines, from 1 to 2 mols of HCOOH will suffice for each >NH group to be methylated. Thus, the starved E-C reaction is starved not only of HCHO but also of HCOOH relative to the amounts used in a conventional E-C reaction.
To minimize the amount of water in the reaction, it is preferred to use paraformaldehyde and conc HCOOH which is at least 88% HCOOH, and preferably 95-97% HCOOH.
The general structure of a polysubstituted diazacycloalkan-2-one ("DCA")which is so effectively methylated in my process is represented by ##STR1## wherein, m represents an integer in the range from 1 to 6, being the number of methylene groups some of which, (a) together with the carbons to which they are bound, may form a cyclopentyl, cyclohexyl or cycloheptyl endo ring, or (b) be substituted; when m is 1 then (I) represents a polysubstituted piperazin-2-one moiety, and when m is 5, and two of the methylene groups of the diaza ring are cyclized with four methylene groups to form a fused six-membered ring, then (I) typically represents a polysubstituted 2-keto-decahydroquinoxaline;
R 1 independently represents hydrogen, C 1 -C 24 alkyl, C 1 -C 12 aminoalkyl or iminoalkyl, and C 1 -C 12 hydroxyalkyl; and when (I) is a substituent, R 1 represents a bond to an amine;
R 2 , R 3 , R 4 and R 5 independently represent C 1 -C 24 alkyl; and,
R 2 with R 3 , or R 4 with R 5 , together cyclized, form C 5 -C 7 cycloalkyl.
The best mode of our process relates to methylation of PSPs such as those disclosed in aforementioned Japanese No. 63-86711 and U.S. Pat. Nos. 4,167,512; 4,190,751; 4,304,712; 4,309,336; 4,415,684; 4,480,092; 4,629,752; 4,639,479 and 4,780,495, the disclosures of which are incorporated by reference thereto as if fully set forth herein. Only the hindered N 4 - or N 5 -atom of each NH group, is methylated.
Illustrative PSPs in which the N 4 -atom is methylated are represented by the structures: ##STR2## wherein, R 2 , R 3 , R 4 and R 5 independently represent --CH 3 or --C 2 H 5 ; and when R 2 and R 3 , or R 4 and R 5 are cyclized, each represents a pentamethylene spiro substituent; and,
R 1 is selected from --CH 3 ; --C 2 H 5 ; --CO--CH 3 and --CO--C 6 H 5 ; Particular PSPs are illustrated by the following:
1-[3-(isopropylamino)propyl]-3,3,5,5-tetramethylpiperazin-2-one;
1-[2-(isopropylamino)ethyl]-3,3,5,5-tetramethylpiperazin2-one;
1-[2-(butylamino)ethyl]-3,3,5,5-tetramethylpiperazin-2one; and,
1-[2-(cyclohexylamino)ethyl]-3,3,5,5-tetramethylpiperazin2-one; inter alia.
Examples of particular PSPs (III) are: trans-3,3-pentamethylene-decahydro-2-quinoxalinone; and, 3-hexyl-3-methyl-cis-decahydroquinoxalin-2-one.
Other PSP-containing compounds have the structure: ##STR3## wherein, R 2 , R 3 , R 4 and R 5 independently represent --CH 3 or --C 2 H 5 ; and when R 2 and R 3 , or R 4 and R 5 are cyclized, each represents a pentamethylene spiro substituent; and,
R is selected from --(CH 2 )n wherein n is an integer from 1 to 6; --CO--(CH 2 ) 4 --CO-- and --CH 2 --C 6 H 4 --CH 2 --.
Particular PSPs are 1,2-ethane-bis-(Nl-3,3,5,5-tetramethyl -piperazin-2-one) and 1,1'-(1,4-p-xylene)-bis(3,3,5,5-tetramethyl-piperazin-2-one). Similarly bis compounds of decahydroquinoxalin-2-one may be methylated. A particular such compound is 1,1'-(1,4-p-xylene)-bis-(3,3-pentamethylene-decahydroquinoxalin-2-one).
Illustrative 1,4- and 1,5-diazepin-2-ones in which the N 4 - and N 5 -atoms respectively, are methylated are represented by the structures: ##STR4## wherein, R 6 has the same connotation as R 2 , R 3 , R 4 and R 5 hereinabove, and R 1 is the same as before.
Particular compounds (V) and (VI) are as follows: N 1 -(butyl)-3,3,5,5,7-pentamethyl-l,4-diazepin-2-one; N 1 -(butyl)-3,3-pentamethylene-5,5,7-trimethyl-1,4-diazepin-2-one;
4,4-dimethyl-decahydrobenzo-l,5-diazepin-2-one; and,
4,4-pentamethylene-decahydrobenzo-l,5-diazepin-2-one.
Bis-(1,4- and 1,5-diazepin-2-ones), similar to structure (IV) for PSPs, may also be methylated. Particular bis-1,4-diazepin-2-one compounds are: 1,2-ethane-bis-(N 1 -3,3,5,5,7-pentamethyl-1,4-diazepin-2-one); 1,2-ethane-bis-(N 1 -(butyl)-3,3-pentamethylene-5,5,7-trimethyl-1,4-diazepin-2-one; and, 1,4-p-xylene-bis-(3,3-pentamethylenedecahydroquinoxalin-2-one). Particular bis-(1,5-diazepin-2-ones) are 1,2-ethane-bis-(N 1 -4,4,6,6-tetramethyl-1,5-diazepin-2-one) and 1,1'-(1,4-p-xylene)-bis-(4,4,6,6-tetramethyl-1,5-diazepin-2-one). Similarly bis compounds of decahydrobenzo-1,5-diazepin-2-one may be methylated.
PIP-Ts are typically prepared by substituting at least one, and most preferably, each of two or three chlorine (or other halogen) atoms on a di- or trihalo-s-triazine, specifically cyanuric chloride, with a PSP, so as to form a substituted triazine. Such PIP-T compounds in which the diazacycloalkane ring is connected to the triazine ring through an alkyleneimine linkage (hence termed "distally connected"), are identified more fully herebelow for illustrative purposes, and in the foregoing '092, '752 and '479 patents.
A preferred substituted triazine is represented by the structure ##STR5## wherein PSP represents a substituent selected from the group consisting of structures ##STR6## wherein, R 1 is C 1 -C 24 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 20 aralkyl, C 1 -C 24 azaalkyl, and C 6 -C 20 azacycloalkyl;
R 2 , R 3 , R 4 , and R 5 independently represent C 1 -C 24 alkyl; R 6 , and R 7 independently represent C 1 -C 24 alkyl and polymethylene having from 4 to 7 C atoms which are cyclizable; and, p represents an integer in the range from 2 to about 10;
R 8 represents H, C 1 -C 6 alkyl and phenyl; and M may be the same as PSP or a bond to the N atom of any amine.
Other preferred PIP-Ts are represented by structures: ##STR7## wherein n' represents an integer from 0 to 6; n" is 0 or 1;
p' and p" independently represent an integer in the range from 2 to about 20; ##STR8## Z' represents ##STR9## or --HN--(CH 2 ) p --NH-- M represents --(Bu) 2 where Bu=butyl, ##STR10## and, M may be the same PSP.
The terminal --NH groups in the foregoing PIP-Ts are generally not methylated under the conditions of the starved E-C process.
A particular PIP-T is formed by the reaction of cyanuric chloride with a particular PSP amine reactant, 1-[3-(cyclohexylamino)propyl]-3,3,5,5-tetramethylpiperazin-2-one, familiarly referred to as cyclohexylpiperazinone, ("CHP" for brevity), represented by the structure: ##STR11##
The structure of the PIP-T which is to be methylated is represented as follows: ##STR12## wherein PSP" represents the same structure written for the other substitutent.
The structure of the desired methylated PIP-T product is represented as follows: ##STR13## wherein PSP'" represents the same structure written for the other substituent.
Crystallizable triazines with other PSP moieties as substituents, whether di- or tri-substituted, may also be methylated as described. The PIP-Ts are formed by reaction of cyanuric chloride with the following polysubstituted piperazin-2-ones:
1-[3-(isopropylamino)propyl]-3,3,5,5-tetramethylpiperazin-2-one;
1-[2-(isopropylamino)ethyl]-3,3,5,5-tetramethylpiperazin-2-one;
1-[2-(butylamino)ethyl]3,3,5,5-tetramethylpiperazin-2-one; and,
1-[2-(cyclohexylamino)ethyl]-3,3,5,5-tetramethylpiperazin-2one; inter alia.
3,5-DHPZNA compounds which may be methylated are N-(substituted)-1-(piperazin-2-onealkyl)-α-(3,5-dialkyl-4-hydroxyphenyl)-α,α-substituted acetamides, represented by the structure ##STR14## wherein, R 1 , R 2 and R 5 each represent hydrogen, C 1 -C 12 alkyl, phenyl, naphthyl, C 4 -C 12 cycloalkyl, and, alkylsubstituted cycloalkyl, phenyl and naphthyl, each alkyl substituent being C 1 -C 8 , and at least one of R 1 and R 2 is t-C 4 -C 12 alkyl;
R 3 and R 4 independently represent C 1 -C 18 alkyl, and C 5 .C 12 cycloalkyl, phenyl and naphthyl, and, alkyl-substitute cycloalkyl, phenyl and naphthyl, each alkyl substituent being C 1 -C 8 , and, when together cyclized, R 3 with R 4 may represent C 4 -C 12 cycloalkyl, and C 1 -C 8 alkyl-substituted cycloalkyl;
R 6 , R 7 , R 8 and R 9 each represent C 1 -C 12 alkyl, or, when together cyclized, R 6 with R 7 , and R 8 with R 9 , may represent C 4 -C 12 cycloalkyl, and C 1 -C 8 alkyl-substituted cycloalkyl;
R 11 and R 12 independently represent hydrogen and C 1 -C 18 alkyl; and,
n is an integer in the range from 1 to about 8. The foregoing compounds are made as taught in the aforementioned '479 U.S. patent. Illustrative of such compounds are the following:
N-isopropyl-N-[2-(2-keto-3,3,5,5-tetramethyl-1-piperazinyl)ethyl]-2-(3,5-di-t-butyl-4-hydroxyphenyl)-2-methylpropanamide represented by the structure ##STR15## N-[1-(2-keto-3,3,5,5-tetremethyl-1-piperazinyl-2-methyl-2-propyl]-2-(3,5-di-to-butyl-4-hydroxyphenyl)-2-methyl-propanamide represented by the structure ##STR16## N-[1-(2-keto-3,3-pentamethylene-5,5-dimethyl-1-piperazinyl) -2-methyl-2-propyl]-2-(3,5-di-t-butyl-4-hydroxyphenyl) -2,2-pentamethylene acetamide represented by the structure ##STR17## N-[1-(2-keto-3,3,5,5-tetramethyl-1-piperazinyl-2-methyl 2-propyl]-2-(3,5-di-t-butyl-4-hydroxyphenyl)-2,2-pentamethylene acetamide represented by the structure ##STR18## N-cyclohexyl-N-[2-(2-keto-3,3,5,5-tetramethyl-1-piperazinyl ethyl]-2-(3,5-di-t-butyl-4-hydroxyphenyl)-2,2-pentamethylene acetamide represented by the structure ##STR19##
The processing aspects of the starved E-C reaction compared to those of a conventional E-C reaction will be more fully recognized in the following illustrative examples in which complex amines with the following structures: ##STR20##
In the following illustrative examples, the methylated PSP-containing product was produced essentially stoichiometrically within about 8 hr. It was thereafter washed repeatedly, the slurry centrifuged and the waterwet cake dried in an oven. Because of the difficulty of removing small quantities of moisture, and to produce product with less than 100 ppm moisture, it is sometimes desirable to dry the recovered product in an oven, then dissolve the dried product in a good solvent such as methylene chloride or other halohydrocarbon. Bone-dry product (less than 100 ppm. and preferably less than 10 ppm water) is then percipitated from the solution, for example, by adding a precipitation agent such as heptane/toluene mixture.
As an alternative, the methylene chloride solvent may be added before the methylated product is dried, and the organic phase separated from the aqueous phase. The product is then precipitated from the organic phase, as before.
EXAMPLE 1
Conventional E-C reaction of 2,2,6,6-tetramethyl-4-piperidine (RX-1) using a 2-fold molar excess of HCHO and 4-fold molar excess of HCOOH: ##STR21##
Into a three-neck, 3-liter round-bottomed flask fitted with a condenser, thermometer and mechanical stirrer, was placed about 130 ml 96% HCOOH and 141.2 g of the starting amine to be methylated. An additional 27 ml of starting amine to be methylated. An additional 27 ml of the 96% HCOOH was used to rinse starting amine remaining on the funnel into the flask which is heated to about 80° C., at which temperature all the starting amine was dissolved. Then 162.1 g of 37% formaldehyde is gradually added to the flask and the contents heated to 95° C. After about 3 hr, the reaction was continued under reflux conditions at atmospheric pressure. After refluxing for about 12 hr the reaction mass is worked up by removing water distilled over thus concentrating the reaction mass. The mixture is then basified with 50% aqueous NaOH, further concentrated and precipitated by the addition of methylene chloride.
Conversion to the pentamethyl-piperidine was essentially complete (about 99%) and the yield after recrystallization from a heptane/toluene mixture is about 90%.
EXAMPLE 2
Starved E-C reaction of 2,2,6,6-tetramethyl-4-piperidine (RX-1) using a 1.5-fold (50%) molar excess of 37% HCHO and 4-fold molar excess of 96% HCOOH:
In a manner analogous to that described immediately hereinabove, the reaction is carried out with only a 50% molar excess of HCHO. The reaction mass was difficult to work up. Upon NMR analysis of the reaction mass it is found that less than 50 mol% of the starting amine was converted to pentamethyl-piperidine.
EXAMPLE 3
Conventional E-C reaction of N 1 -propyl-3,3,5,5-tetramethyl-piperazin-2-one (RX-2) using a 2.4-fold molar excess of 37% HCHO and 25.4-fold molar excess of 96% HCOOH: ##STR22##
In a manner analogous to that described hereinabove 900 ml 96% HCOOH and 421.2 g of the starting amine RX-2 was added to the flask through a funnel. An additional 100 ml HCOOH was used to rinse a little RX-1 remaining on the funnel all being dissolved in the HCOOH as the flask is heated to about 80° C. Then the 37% HCHO is gradually added to the flask and the contents heated to 95° C. After about 3 hr, the reaction was continued under reflux conditions. After refluxing for 0.5 hr the heating mantle was dropped to allow the flask to cool and an additonal 24 g (0.8 mol) of paraformaldehyde added. The reaction was continued under reflux for an additional 12 hr, and the reaction mass worked up by concentrating it to remove most of the HCOOH. The mixture is then basified with 50% aqueous NaOH. Because of difficulty separating the methylated product, methylene chloride is added to dissolve the methylated RX-2 and form an organic layer which is separated, washed with saturated NaCl solution and dried overnight.
Conversion of the RX-2 to 3,3,4,5,5-pentamethylpiperazin-2-one was essentially complete (about 99 mol%) and the yield is about 90%.
EXAMPLE 4
Starved E-C reaction of N1-propyl-2,2,6,6-tetramethylpiperazin -2-one (RX-2) using a 1.4-fold (40%) molar excess of 37% HCHO and 4-fold molar excess of 96% HCOOH:
In a manner analogous to that described immediately hereinabove, the reaction is carried out with only a 40% molar excess of HCHO. Upon basifying the reaction mass pentamethyl-piperazinone separates as a solid. Upon filtration, less than 1 mol% is found in the filtrate. Upon recrystallization of the solid from heptane it is found that the yield is about 99 mol%. Comparable results are obtained when only 1.9 mols (90% excess) of HCOOH are used.
EXAMPLE 5
Starved E-C reaction of RX-3 using a 50% excess of 37% HCHO and 5-fold excess of 96% HCOOH:
The compound RX-3 was methylated in a manner analogous to that described hereinabove, except that only a 50% molar excess of HCHO was used. Upon concentration of the reaction mass, after the reaction was run for the same time as that in example 4 above, a thick oil was formed. Upon basifying with aqueous NaOH no product separates from the reaction mass. Efforts to separate methylated product from the oily mass were unsuccessful, so the thick oil was analyzed. The NMR mass spectra showed the presence of methylated >NH groups in the product, but less than 50% of the RX-3 was converted to methylated product.
EXAMPLE 6
Starved E-C reaction of RX-4 using a 50% excess of 37% HCHO and 5-fold excess of 96% HCOOH:
A comparison is made with RX-3 because there is no practical way to make a PSP-substituted compound corresponding to RX-3. The PSP-substituted complex amine RX-4 represented by the structure hereinabove is a closely analogous (to RX-3) structure for the purpose of this comparison.
The compound RX-4 was methylated in a manner analogous to that described in example 5 hereinabove. Upon concentration of the reaction mass, after the reaction was run for the same time as that in example 5 above, a clear syrup is obtained. Upon basifying with aqueous NaOH a white product separates from the reaction mass. Upon washing repeatedly with water and drying, methylated RX-4 is recovered with an yield of about 95 mol%. Analysis of the filtrate indicates that less than 1 mol% of the RX-4 rremains unconverted, indicating essentially complete (99 mol%) conversion.
EXAMPLE 7
In a manner analogous to that described hereinabove, the PIP-T (XII) was methylated under starved E-C conditions, as follows: ##STR23##
To a 5 liter reactor is charged 289 g (0.3 mole) PIP-T XII, 64.9 g of HCHO (in 37% solution) and 313.9 g of formic acid (in 90%). The mixture is heated to 65° C. with stirring and when the temperature reaches about 80° C., the remaining PIP-T is added. The temperature of the reaction mass is raised to about 102° C. and the reaction monitored by liquid chromatographic (LC) analysis, to monitor the disappearance of the PIP-T. Since there is a substantial amount of XII remaining after 8 hr, the reaction is continued until essentially all the XII has disappeared, which takes about 12 hr.
The reaction mass obtained is a colored oil which, when cooled to room temperature, is highly viscous. To precipitate the methylated product from this oil, it is heated to about 80° C. and 1 liter of water added to obtain a slurry having a pH of about 3. When this slurry is neutralized with a large excess of 25% NaOH solution, a foamy solid is precipitated.
To work up this solid, the neutralized solution is filtered. The aqueous filtrate contains a substantial amount of XIII which does not precipitate. The white filter cake (965 g) is washed with about 2 liter of demineralized (DM) water in a 5 liter flask, and filtered.
After washing repeatedly to remove HCHO and formate, the washed cake is dried to yield 478 g of essentially pure methylated product. Since theoretical yield is 604.2 g it is evident that the solubility of the methylated PIP-T is substantial enough to necessitate the recovery of product remaining in both the aqueous alkaline filtrate as well as the first water wash.
The filtrate and water wash are heated with an additional amount of 25% NaOH to precipitate more solid which is washed and dried as before, to yield 102 g of product. Recovery of a total of 580 g of product represents a yield of 96%.
The process is schematically illustrated in the Figure in which a reaction vessel 10 provides a reaction zone for obtaining essentially complete conversion of a DCA-containing compound with a starved E-C procedure. In the first step, the HCOOH is charged as a 96% HCOOH aqueous solution. The DCA is added to the reactor and the contents are heated to reaction temperature while stirring so that the DCA dissolves. The first step is identified by reference numeral 1, written in a circle to distinguish the symbol from numerals used to identify equipment.
In the second step (identified as step 2), the HCHO, preferably as paraformaldehyde, is gradually added and the reaction conditions maintained until the reaction is complete. To concentrate the solution and to speed up the reaction, it is completed under reflux (step 3), water being withdrawn from the reflux condenser 11. A surge tank 12 is provided for safety reasons. The reaction is tracked by periodic analysis of the reactor's contents.
After the reaction is complete, neutralization of the contents of the reactor either with a solution of an alkali metal hydroxide or ammonium hydroxide (step 4), results in separation of a water-insoluble (in non-alkaline water) methylated amine in an aqueous alkaline slurry, if the solution has been sufficiently concentrated. Typically, methylated DCA is precipitated as solid by cooling hot super-saturated alkaline solution. The supernatant solution of HCHO and formate, along with impurities and unwanted byproducts is conveniently drained (step 5) from the reactor. The separated solid is washed with distilled water (step 6), several times if necessary, to remove the formate and unreacted paraformaldehyde, and any water-soluble byproducts which may be formed. The wash water is drained from the reactor in step 7.
As shown in the Figure, concentration of the solution is done prior to neutralization but may also be done after neutralization, if desired. Further, the methylation reaction, precipitation of the methylated DCA, and washing out the unreacted formaldehyde, the formate formed after neutralization, and other impurities, are shown as being done in the reactor to avoid transferring the contents of the reactor (after the reaction is completed), to another vessel(s) for "work-up" and recovery of the essentially pure methylated DCA.
It is preferred to use the reactor solely for carrying out the methylation reaction, and to work-up the formate solution in which the methylated DCA is dispersed, in separate unit operations.
The slurry from the reactor is flowed to a centrifuge 13, in which the centrifuged solids may be further washed with successive water washes to free the cake from impurities. The wet cake from the centrifuge is then dried in a vacuum oven 14. The dried product, essentially free of contaminants, is then transferred to suitable containers.
Since the main use of the methylated DCAs is in polyacetals and polyamides to stabilize them against degradation due to heat and particularly to light, it is generally required that the product be bone-dry not only with respect to water, but also with respect to solvent. The latter being more easily removed than the former, a purification step, as described hereinabove, precipitating the product from a solvent, is generally desirable.
Further, for economic reasons, as little excess of HCHO and HCOOH are used as will yield essentially complete conversion to the methylated product. As might be expected, some DCAs might provide better reactor productivity (pounds product/unit volume of reactor) with more than 1.5 mol HCHO per >NH group, but the ratio will always be less than 2. Similarly, though less than 2 mols of HCOOH will preferably be used per >NH group, more than 2 may improve productivity. The higher the temperature of reaction the better, as long as the temperature is below that at which at least 90% by weight of the complex amine is converted to methylated product, and the generation of impurities is mept to a minimum. The operating pressure is generally about atmospheric but may be as high as 5 atm if such high pressure is economically justified. | The difficulty of methylating a hindered piperidinyl, piperazinyl, or diazepinyl group with an Eschweiler-Clarke ("E-C") procedure without using a large molar excess (more than double) of formaldehyde is surprisingly found to be non-existent in the case of a diazacycloalkan-2-one group with a hindered N 4 - or N 5 -atom of its NH group which is to be methylated. The N 4 - or N 5 -atom of a polysubstituted diazacycloalkan-2-one group ("DCA") is substantially stoichiometrically converted even when a conventional E-C procedure is starved of HCHO, that is, with a much smaller molar excess of formaldehyde than deemed necessary. The effective molar ratio of NH groups: HCHO in the starved E-C process is in the range from 1:1 to 1:1.5, in the presence of enough formic acid to function both as reactant and solvent not only for a DCA-containing complex amine ("starting amine") to be methylated, but also for the methylated amine (product). Such a starting amine may have one or more DCA substituents which, in turn, may be connected to any other structure. Because this process is starved of at least HCHO, and usually both HCHO and HCOOH, it is referred to herein as the "starved E-C process". Upon completion of the reaction any excess HCOOH is neutralized with aqueous alkali, and the product separates from the reaction mass. Though the starting amine is often substantially soluble in water, it usually becomes substantially insoluble after it is methylated. Less than 5% of product is lost in the aqueous wash. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates generally to agents for improving the quality of citrus fruits and to a method of improving the quality of citrus fruits by application of such agents.
Chemicals capable of adjusting the metabolism of sugars and/or organic acids of citrus fruits are very useful, because they can improve the quality of citrus fruits and adjust the shipping time of the fruit. Chemicals capable of performing this function such as lead arsenate and naphthylacetic acids, are known. Lead arsenate has a pronounced effect of decreasing acidity of citrus fruits. However, lead arsenate is harmful to fruit trees and is residual in the fruit. Therefore, this agent is not preferable in view of the safety factor. Naphthylacetic acids also decrease the acidity in citrus fruit; but delay maturity of the fruit. This creates a problem in scheduled shipping time of the fruit, thus proving to be of little practical use.
As a result of various studies, it has been found that certain compounds as set forth below can increase or decrease the amount of organic acids in citrus fruits, when applied to the fruit trees without doing any harm to the fruit trees or having any adverse effect upon the maturity of the fruit.
SUMMARY OF THE INVENTION
In accordance with the present invention, the metabolism of citric fruit is modified by application of a modifying agent containing, as an active ingredient, at least one compound represented by the general formula (I): R-X-Y, wherein R represents a lower alkyl group, an alicyclic alkyl group or ##STR1## (wherein X 1 represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogen atom, or a nitro group, n is an integer of 1-5, m is 0 or 1, and when n is 2 or more, X 1 may be the same or different); X represents ##STR2## and Y represents ##STR3## [wherein R 1 represents a hydroxyl group, a lower alkoxy group, or ##STR4## (wherein R 2 and R 3 may be the same or different and are hydrogen atoms, lower alkyl groups, alicyclic alkyl groups, or aryl groups, or R 2 and R 3 form an oxa-hetero cycle with a nitrogen atom)].
The present invention also pertains to novel compounds included within the above general formula (I), with the exception of: ##STR5## and the compounds wherein ##STR6## which are known.
The present invention is advantageous in that with an increase in the amount of organic acids in fruit, the preservability of the fruit after harvesting is improved; and with a decrease in the amount of organic acids, the ratio of sugar content to organic acid is raised and, therefore, the fruit can be harvested at an earlier time.
DESCRIPTION OF THE INVENTION
The compounds contemplated by the present invention, represented by the foregoing general formula (I), are set forth below in Table 1 by their structural formulae and melting points.
Table 1__________________________________________________________________________Compound Meltingnumber Structural formula point (°C.) Process*__________________________________________________________________________ ##STR7## 140 C2 ##STR8## 144-145 C3 ##STR9## 103-104 B4 ##STR10## 91-92 B5 ##STR11## 210-211 B6 ##STR12## 121.5-123 B7 ##STR13## 97-100 B8 ##STR14## 76-77 A9 ##STR15## 73-74 A10 ##STR16## 168-169 B11 ##STR17## 46 B12 ##STR18## 171 B13 ##STR19## 163 B14 ##STR20## 90 B15 ##STR21## 57-59 A16 ##STR22## 97 A17 ##STR23## 113-114 A18 ##STR24## 140 A19 ##STR25## 139 A20 ##STR26## 138 B21 ##STR27## 203 B22 ##STR28## 90-91 A23 ##STR29## 116-116.5 A24 ##STR30## 170.5-172 A25 ##STR31## 122-125 A26 ##STR32## 94-95 A27 ##STR33## 81-83 A28 ##STR34## 92-95 A29 ##STR35## 90.2 A30 ##STR36## 68-69.5 A31 ##STR37## 86-87 A32 ##STR38## 63-64 A33 ##STR39## 135-136 B34 ##STR40## 131-133 B35 ##STR41## 76 B36 ##STR42## 105-106.5 A37 ##STR43## 111-112 B38 ##STR44## 126-127 C__________________________________________________________________________ *In the foregoing Table 1, A, B nd C indicate the general methods [A], [B], and [C] described hereinafter by which the compound may be prepared.
Among the above-mentioned compounds, compound numbers 1, 15 and 18 are known and are disclosed in Chemical Abstracts 51 11251e, Chemical Abstracts 49 14641c, and Chemical Abstracts 49 14640e, respectively. The remaining are believed to be novel compounds. Among the compounds represented by the general formula (I), those compounds wherein ##STR45## are disclosed in the specification of Japanese Patent Application No. 61061/77.
The compounds used in the present invention may be prepared by the following general methods:
Process [A]
A compound represented by the general formula (I): R-X-Y [wherein R, X and Y have the same meanings as defined above] can be obtained by reaction of a halide represented by the general formula (II): R-X-Z (wherein R and X have the same meanings as defined above, and Z is a halogen atom) with a compound represented by the formula (III): H-Y (wherein Y has the same meaning as defined above). The process is indicated by the following reaction formula: ##STR46##
(a) As an example, when the compound represented by the general formula (II) has ##STR47## that is, in the case of a proline derivative, the procedure is as follows:
A compound represented by the general formula (III) is dissolved or suspended in water, an organic solvent, or a mixture thereof, and reacted with a halide represented by the general formula (II) with or without addition of a base, to obtain a compound represented by the general formula (I).
The proline derivatives represented by the general formula (II) are generally well-known compounds, or can be produced according to well-known methods. That is, when R 1 in ##STR48## is a hydroxyl group, the compound represented by the general formula (III) is proline; when R 1 is a lower alkoxy group, the compound represented by the general formula (III) can be obtained by esterifying proline according to well-known esterification methods; when R 1 is ##STR49## (wherein R 2 and R 3 have the same meanings as defined above), the compound represented by the general formula (II) can be obtained by condensing a proline, masked by a masking group such as a t-butyloxycarbonyl group, a benzyloxycarbonyl group, or the like according to the known methods employed in amino acids and peptide synthetic chemistry, with the corresponding amine, and then eliminating the masking group.
The proline used may be any of the optically active or optically inactive compounds.
Examples of a base used to promote the reaction [A] include organic bases such as triethylamine, dimethylaniline, N-methylmorpholine, pyridine, etc,; and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc.
Organic solvents used in the reaction can be any of the organic solvents which do not take part in the reaction and inert organic solvents. Preferably, aromatic hydrocarbons, such as benzene, toluene, xylene, etc.; halogenated hydrocarbons, such as methylene chloride, chloroform, ethane dichloride, carbon tetrachloride, etc; esters, such as methyl acetate, ethyl acetate, etc,; ethers such as diethyl ether, dioxane, tetrahydrofuran, etc.; ketones such as acetone, methylethylketone, etc.; acetonitrile, dimethylformamide, etc. are used either alone or in mixture. The amount of the solvent used depends upon the reaction conditions, but usually 1 to 20 parts by weight of the solvent is used per part of starting material.
The reaction is carried out of a temperature range of -50° C. to 100° C., preferably -5° C. to 50° C., and is usually completed within 30 minutes to 24 hours.
The desired product can be isolated from the reaction mixture according to the ordinary isolation and purification procedures employed in the art of organic synthetic chemistry.
(b) When compounds represented by the general formula (III) wherein Y is ##STR50## are used as the starting material, compounds represented by the general formula (I) can be obtained by conducting the reaction in the same manner as in the case of the proline derivative ##STR51## but these starting materials have less reactivity as compared with the proline derivatives, and thus are preferably treated with sodium hydride, sodium alkoxide, or the like in advance according to well-known procedures to undergo the reaction in the form of an alkali metal salt. In such case, the starting materials can be prepared according to ordinary well-known synthetic methods. As a solvent for the reaction, aromatic hydrocarbons such as benzene, toluene, xylene, etc.; esters such as methyl acetate, ethyl acetate, etc.; ethers such as diethyl ether, dioxane, tetrahydrofuran, etc.; dimethyl formamide, etc. can be used either alone or in mixture.
Process [B]
When X in the general formula (I) is ##STR52## the compounds represented by the general formula (V) can be obtained by conducting the reaction in the same manner as in the case (a) or (b) of Process [A], except that an isocyanate derivative represented by the general formula (IV): R-NCO (wherein R has the same meaning as above) is used in Process [A] in place of the compound of the general formula (II). The process is indicated by the following reaction formula: ##STR53##
Process [C]
When X=--SO 2 --and ##STR54## in the general formula (I), that is, when the compounds are ##STR55## R-SO 2 NH(CH 2 ) 3 COOH synthesized according to ordinary procedures in the art of peptide synthesis is subjected to cyclocondensation in the presence of an appropriate condensing agent to obtain a compound represented by ##STR56## Dicyclohexyl carbodimide (DCC), ClCOOR 4 (wherein R 4 represents methyl, ethyl, sec-butyl, etc.), and the like are suitable condensing agents.
To promote the reaction, a base such as triethylamine, dimethylaniline, N-methylmorpholine, pyridine, N-methylpiperidine, etc. can be used. As the organic solvent used in the reaction, aromatic hydrocarbons such as benzene, toluene, xylene, etc.; halogenated hydrocarbons such as methylene chloride, chloroform, ethane dichloride, carbon tetrachloride, etc.; esters such as ethyl acetate, etc.; and the like can be used either alone or in mixture. The amount of the solvent used is usually 1 to 20 parts by weight per part of the starting material.
The reaction rapidly proceeds at a temperature range of -10° to 50° C., and is usually completed within 30 minutes to 24 hours.
The desired product can be isolated from the reaction mixture according to ordinary isolation and purification procedures employed in the art of organic synthetic chemistry.
Examples of the synthesis of certain specific compounds of the present invention are set forth below.
EXAMPLE A
In this example, 118 g of N-p-chlorophenylsulfonyl-γ-aminobutyric acid is suspended in 300 ml chloroform, and then 51 g of triethylamine is added in drops thereto in a water bath (about 20° C). A solution of ethyl chlorocarbonate (61.0 g) in chloroform (50 ml) is then added in drops to the reaction mixture for about 60 minutes with stirring while cooling the reaction mixture in an ice-salt bath (0°-5° C). After the addition, stirring is continued for two hours, and then the reaction mixture is admixed with 200 ml of ethyl acetate, and then washed twice with 100 ml of water. Then the reaction mixture is washed with 200 ml 1N hydrochloric acid, followed by two additional washings with 100 ml water, and finally dried over anhydrous sodium sulfate. The reaction mixture is filtered, and the filtrate is concentrated under reduced pressure. The resulting precipitate is recrystallized from ethanol, whereby 1p-chlorophenylsulfonylpyrolidone-2 (compound number 2; 105.7 g; mp 150°-151° C.) is obtained. Yield: 98.78%.
Elemental analysis Calculated: C:46.25, H:3.88, N:5.39%. Found: C:46.30, H:3.97, N:5.48%.
Compound numbers 1 and 38 are prepared in the same manner as described above.
EXAMPLE B
In this example, 14.3 g of methyl 2-pyrolidone-5-carboxylate and 10.1 g triethylamine are dissolved in 100 ml of ethyl acetate. Phenyl isocyanate (11.9 g) is added thereto, and the resulting solution is left standing at room temperature overnight. The reaction mixture is then filtered, and the filtrate is washed twice with 100 ml of 1N hydrochloric acid, and then three times with 100 ml water. Then, the filtrate is dried over anhydrous sodium sulfate, and then filtered. The filtrate is concentrated under reduced pressure, and the resulting viscous material is dissolved in 100 ml ether, admixed with 100 ml n-hexane, and recrystallized, whereby methyl 1-phenylcarbamoyl-2-pyrolidone-5-carboxylate (compound number 4; 17.5 g; mp 91°-92° C.) is obtained. Yield: 66.8%.
Elemental analysis Calculated: C: 59.53, H: 5.38, N: 10.68%. Found: C: 59.56, H: 5.40, N: 10.80%.
Compound numbers 3 and 5 are prepared in the same manner as described above.
EXAMPLE C In this example, 117.0 g of L-proline and 0.7 g of sodium hydroxide are dissolved in 250 ml water, and then admixed with 250 ml acetonitrile. After cooling in an ice bath (5°-10° C.), a solution of 100 g isopropyl isocyanate dissolved in 100 ml acetonitrile is added in drops thereto for about 30 minutes with vigorous stirring. The solution is left standing at room temperature overnight, and then the reaction mixture is washed twice with 100 ml ethyl acetate. The aqueous layer is adjusted to pH 3-4 with 2N hydrochloric acid, and then evaporated to dryness under reduced pressure. The residue is admixed with 500 ml ethyl acetate, and heated to 70°-75° C. Insoluble materials are filtered off, and the filtrate is concentrated under reduced pressure. The resulting viscous material is admixed with 100 ml n-hexane, and crystallized, whereby n-isopropyl-carbamoyl-L-proline (compound number 6; 169.6 g; melting point 121.5°-123° C.) is obtained. Yield: 84.0%.
Elemental analysis Calculated (as C 9 H 16 N 2 O 3 ): C: 53.98, H: 8.06, N: 13.99%. Found: C: 53.99, H: 8.16, N: 13.78%.
Compound numbers 7, 10, 12, 13, 20, 21, 33, 34 and 37 are prepared in the same manner as described above.
EXAMPLE D
In this example, 11.5 g L-proline and 8.0 g magnesium oxide are dissolved in 100 ml water, and then admixed with 60 ml ether. A solution of p-methylphenyl chloroformate [8.5 g; boiling point: 109°-110° C. (28-30 mmHg)] dissolved in 50 ml ether is added thereto, while cooling the mixture in an ice bath (5°-10° C.). After stirring for 30 minutes, the reaction solution is acidified by adding 60 ml concentrated sulfuric acid, and extracted three times with 60 ml ethyl acetate. The extract is washed three times with 40 ml 2N HCl and four times with 50 ml water, and then dried overnight over anhydrous sodium sulfate (30 g). After drying, the extract is filtered, and the filtrate is concentrated under reduced pressure. The resulting oily materials are admixed with 100 ml n-hexane, and left standing in a refrigerator (about -15° C.). The deposited crystals are filtered, and recrystallized from ethyl acetate-n-hexane (1:1 by volume), whereby p-methylphenyloxycarbonyl-L-proline (compound number 8; 9.25 g; mp: 76°-77° C.) is obtained. Yield: 74.3%.
Elemental analysis Calculated (as C 12 H 15 NO 4 ); C: 60.75, H: 6.37, N: 5.90%. Found: C: 60.67, H: 6.43, N: 5.83%.
Compound number 9 is prepared in the same manner as described above.
EXAMPLE E
In this example, 11.1 g of L-proline methyl ester hydrochloride and 6.7 g triethylamine are added to 100 ml chloroform, and 12.5 g of 3,4-dichlorophenyl isocyanate is added thereto with stirring. The resulting mixture is subjected to reaction overnight with stirring, and the reaction solution is then filtered. The filtrate is washed twice with 100 ml of 2N hydrochloric acid, and then four times with 100 ml water, dried over anhydrous sodium sulfate (30 g), and then filtered. The filtrate is concentrated under reduced pressure, and the resulting oily materials are recrystallized from about 200 ml ethanol, whereby N-3,4-dichlorophenylcarbamoyl-L-proline methyl ester (compound number 14; 18.8 g; m.p. 171° C.) is obtained. Yield: 79.5%.
Elemental analysis Calculated (as C 13 H 14 N 2 O 3 Cl 2 ): C: 49.23, H: 4.45, N: 8.83%. Found: C: 49.33, H: 4.47, N: 8.74%.
Compound numbers 11 and 35 are prepared in the same manner as described above.
EXAMPLE F
In this example, L-proline (11.5 g; 0.10 mole) and caustic soda (8.0 g; 0.2 moles) are dissolved in 100 ml water, and a solution of p-methylphenylsulfonyl chloride (20.9 g) dissolved in ether (80 ml) is added thereto with vigorous stirring under cooling in an ice bath (5°-10° C.). After reaction for about 5 hours, the reaction mixture is left standing, and the upper ether layer is removed. The remaining aqueous layer is admixed with 2N hydrochloric acid to adjust the pH to 3-4. After being left standing in a cool place (0°-5° C.), the deposited crystals are filtered off. The crystals are recrystallized from an aqueous 60% ethanol solution (about 200 ml), whereby p-methylphenylsulfonyl-L-proline (compound number 15; 20.1 g; m.p. 57°-59° C.) was obtained. Yield: 70%.
Compound number 16 is prepared in the same manner as described above.
EXAMPLE G
In this example, 8.07 g of N-p-methylphenylsulfonyl-L-proline and 3.03 g of triethylamine are dissolved in 100 ml ethyl acetate, and then dicyclohexyl carbodiimide (DCC; 6.18 g) is added thereto under ice cooling (5°-10° C.). The mixture is stirred for 20 minutes. After addition of 2.79 g aniline, the mixture is subjected to reaction at room temperature overnight with stirring. The deposited precipitate is filtered off, and the filtrate is washed three times with 100 ml water, twice with 100 ml 1N HCl, and then three times with 100 ml water. After drying over anhydrous sodium sulfate (about 30 g), the filtrate is concentrated under reduced pressure, and recrystallized from ethyl acetate-n-hexane (2:1 by volume), whereby N-p-methylphenylsulfonyl-L-proline anilide (compound number 18; 4.9 g; m.p. 140° C.) is obtained. Yield: 47.5%.
Elemental analysis Calculated: C: 59.99, H: 5.59, N: 7.77%. Found: C: 60.20, H: 5.68, N: 7.83%.
Compound numbers 17 and 19 are prepared in the same manner as described above.
EXAMPLE H
In this example, L-proline (3.5 g; 0.03 mole) and sodium carbonate (6.3 g; 0.075 mole) are dissolved in 90 ml water, and a solution of p-chlorophenylthiocarbonyl chloride (5.7 g; 0.033 mole) dissolved in 60 ml dioxane is added in drops thereto at 2°-10° C. under ice cooling for 15 minutes. After the addition, stirring is continued for five hours at 2°-5° C. After the completion of the reaction, the reaction solution is washed twice with 50 ml ether, and then the aqueous layer is acidified to pH 3-4 with concentrated hydrochloric acid, and separated oily substances are twice extracted with 50 ml ethyl acetate. The ethyl acetate layer is washed twice with 100 ml water, and then dried over sulfuric anhydride (about 10 g). The solvent is distilled off under reduced pressure, and the resulting syrupy material is admixed with 30 ml ether and 100 ml n-hexane, and left standing in a cool place (about - 15° C.). The deposited crystals are filtered by suction, whereby white crystals of N-p-chlorophenylthiocarbonyl-L-proline (compound number 23; 5.0 g; m.p.: 116°-116.5° C.) is obtained. Yield: 65.9%.
Elemental analysis Calculated: C: 50.50, H: 4.20, N: 4.91%. Found: C: 50.63, H: 4.38, N: 4.94%.
EXAMPLE I
In this example, L-proline methyl ester hydrochloride (16.6 g; 0.1 mole) is dissolved in 100 ml chloroform, and the resulting solution is admixed with triethylamine (13.9 ml; 0.1 mole) under ice cooling (5°-10° C.) for 5 minutes. Then, 4-chlorophenylthiocarbonyl chloride (10.4 g; 0.05 moles) is added in drops at 2°-5° C. for 30 minutes. After stirring for three hours, the reaction solution is washed respectively with about 100 ml water, about 100 ml 2N hydrochloric acid and about 100 ml water, and then dried over anhydrous sodium sulfate (30 g). The solvent is distilled off under reduced pressure, and the resulting crystals are recrystallized from ethyl acetate (about 50 ml) and n-hexane (150 ml), whereby 4-chlorophenylthiocarbonyl-L-proline methyl ester (compound number 22; 18.0 g; m.p.: 90°-91° C.) is obtained. Yield: 60%.
Elemental analysis Calculated: C: 52.09, H: 4.70, N: 4.67%. Found: C: 52.21, H: 4.73, N: 4.76%.
Compound numbers 24-32 and 36 are prepared in the same manner as described above.
To modify the quality of citrus fruit according to the present invention, at least one of the compounds represented by the general formula (I) is sprayed upon citrus trees after appropriate dilution in a carrier. The compound can be applied as a solution, emulsion, suspension or dust produced according to ordinary methods for preparing plant growth regulators. Appropriate solid carriers include mineral powders such as clay, talc, kaolin, bentonite, diatomaceous earth, white carbon, and the like; and vegetable powders of soybean powder, wood dust, wheat flour, starch, fructose, etc. Appropriate liquid carriers include water; alcohols such as methanol, ethanol, ethyleneglycol, etc,; ketones such as acetone, methylisobutylketone, acetophenone, isophorone, etc.; ethers such as dioxane, tetrahydrofuran, ethyleneglycol, monobutyl ether, etc.; aromatic hydrocarbons such as benzene, toluene, xylene, methylnaphthalene, tetraline, etc.; kerosene, low or high boiling point petroleum fractions; polar solvents such as dimethyl formamide, dimethyl sulfoxide, acetonitrile, etc.
To improve the properties of preparations according to the invention and to increase the effect, various ionic and nonionic surfactants such as sodium laurylsulfate, sodium salts of higher alcohol sulfate esters, polyoxyethylene oleylether, or polymeric materials such as sodium alginate, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, casein, etc. may be employed in combination with the carrier.
The preparation of the present invention can be used in mixture with other plant growth regulators as well as fungicides, miticides, insecticides, and the like.
The concentration of the active ingredients in the preparation is not especially critical, but in any formulation, the concentration is usually 100-2,000 ppm; and, upon application, it is preferably to spray the compound at a ratio of 300-600 L (active ingredient) per 10 acres of orchard having 60-80 fruit trees. The compound is sprayed once or twice in one season at any time during the fruiting period.
The carrier and other additives in a preparation can be used in such concentration ranges as used in ordinary plant growth regulators.
The effect of the agents of the present invention is illustrated by the following representative examples.
EXAMPLE 1
In this example, each of the compounds identified in Table 2 is dissolved in a small amount of methanol (20 mg/0.5 ml), and diluted with a 0.05% (w/v) aqueous solution of Gramine (trademark of a wetting agent made by Sankyo Seiyaku K.K.) to make up a concentration of 1000 ppm, in an aqueous solution.
The solution is sprayed on one-year old seedlings of Japanese summer orange at the fruiting period of the sprouts in early summer, so that the aqueous solution is thoroughly applied to the leaves. After one month, the treated leaves are collected, and the content of organic acid in the leaves is determined.
After extraction of the organic acids from the leaves by hot water, the organic acids are purified by ion exchange resin treatment using Amberlite CG-120 (made by Rohm & Haas), converted to a butyl ester, and then quantitatively determined by gas chromatography. The amount of organic acids in the fruit is proportionate to the amount of organic acids in the leaves (see "Shokucho" 10, No. 4, pages 14-19 (1976), or "Horticultural Utilization of Plant Growth Regulators", published by Seibundo-Shinko-sha Publishing Company, 1973), and thus the amount of organic acids in the leaves can serve as an index for indicating the amount of organic acids in the fruit.
As controls, lead arsenate and naphthylacetic acid (NAA) are used in place of the test compounds, and the amount of organic acids in the leaves is determined in the same manner as above. The results are set forth in Table 2 below.
Table 2______________________________________Compound *A/B x Compound A/B x Compound A/B xnumber 100(%) number 100(%) number 100(%)______________________________________Leadarsenate 56 10 53 22 80NAA 74 11 55 23 82 12 53 24 1351 84 13 48 25 862 48 14 35 26 1293 124 15 78 27 1184 76 16 62 28 1205 140 17 85 29 1146 43 18 89 30 1057 342 19 92 31 1068 76 20 60 32 1089 74 21 57______________________________________ *A is the amount of organic acids in the treated leaves in terms of citri acid, and B the amount of organic acids in nontreated leaves in terms of citric acid.
EXAMPLE 2
In this example, ten parts by weight of the test compounds identified in Table 3, 5 parts by weight of sodium alkylbenzenesulfonate, 40 parts by weight of talc, and 45 parts by weight of bentonite are thoroughly pulverized and uniformly mixed in a mill to obtain a water dispersible powder. The water dispersible powder is diluted with a 0.05% aqueous solution of Gramine to make up an active ingredient concentration of 1,000 ppm, and sprayed on selected branches of 15 year-old, early ripening tangerine trees, at a rate of about 10 L per fruit tree to the same degree as in Example 1 (spraying date: July 17, 1976).
The fruit was harvested from the treated branches, and non-treated branches as control on Oct. 19, 1976, and the degree of coloring of the fruit, acidity of the fruit juice, and sugar content were measured. The amount of organic acids was determined by titration and calculated in terms of citric acid. The sugar content is measured by a refractometer and calculated in terms of glucose. The coloring is determined according to a ten-mark evaluation method. The results are given in Table 3.
Table 3______________________________________ Sugar Acidity Degree ofCompound content (g/100 ml) sweetnessnumber Coloring (P) (Q) (P/Q)______________________________________Control(non-treaed) 5.5 9.4 1.22 7.74Lead arsenate 6.0 9.7 1.09 8.92 6.0 9.6 1.05 9.144 6.0 9.8 1.15 8.526 5.5 9.6 0.96 10.010 5.0 9.7 1.09 8.914 5.0 9.5 0.90 10.5623 6.0 9.9 1.18 8.39______________________________________
EXAMPLE 3
In this example, the water dispersible mixture of Example 2 is diluted with a 0.5% aqueous solution of Gramine to make an active ingredient concentration of 2,000 ppm. The resulting solution is sprayed on 10-year old Japanese summer orange trees "Kawano" to the same degree as in Example 1 (spraying date: July 23, 1976). The fruit was harvested from the treated trees and non-treated trees as controls on Dec. 28, and the sugar content and acidity of the fruit juice was measured in the same manner as in Example 2. The results are given in Table 4.
Table 4______________________________________ Sugar Acidity Degree ofCompound content (g/100 ml) sweetnessnumber (P) (Q) (P/Q)______________________________________Control(non-treated) 9.8 2.55 3.84Lead arsenate 9.1 1.76 5.172 9.7 2.02 4.804 9.8 2.25 4.366 9.8 1.63 6.0110 9.7 2.07 4.6914 9.6 1.80 5.3323 9.8 2.29 4.28______________________________________
EXAMPLE 4
In this example, forty parts by weight of the compounds identified in Table 5, 10 parts by weight of Sorbol 8067 (trademark of an anionic surfactant, made by Toho Kagaku Co., Ltd.), and 50 parts by weight of xylene were uniformly mixed and dissolved to obtain an emulsion. The emulsion is diluted with a 0.05% aqueous solution of Gramine to make up an active ingredient concentration of 500 ppm. The solution is sprayed on 15-year old, ordinary tangerine trees to the same degree as in Example 1 (spraying date: July 17, 1976). The fruit was harvested from the treated trees and non-treated trees on August 6, and the sugar content and acidity of fruit juice measured in the same manner as in Example 2. The results are given in Table 5.
Table 5______________________________________ Sugar Acidity Degree ofCompound content (g/100 ml) sweetnessnumber (P) (Q) (P/Q)______________________________________Control(non-treated) 7.1 4.11 1.73Lead arsenate 7.2 3.36 2.142 7.3 3.63 2.014 7.3 3.85 1.905 7.0 4.87 1.446 7.1 2.99 2.3710 7.0 3.66 1.9114 7.2 3.31 2.1816 7.2 3.72 1.9423 7.3 3.88 1.88______________________________________ | Novel compounds are disclosed which are useful as agents capable, when applied to citrus tree, of modifying the metabolism and organic acid content of the citrus fruit. | 2 |
This is a division, of application Ser. No. 517,736 filed Oct. 24, 1974, now U.S. Pat. No. 3,957,907.
BACKGROUND OF THE INVENTION
This invention provides new fast-curing liquid adhesives for laminating and sealant purposes.
Known adhesive compositions which cure in the presence of free-radical catalysts, often called vinyl-polymerizable sealants, are generally based on syrupy solutions containing various olefinically unsaturated monomers and various compatible polymers. Thus, for example, U.S. Pat. No. 3,333,025 discloses compositions comprising monomeric styrene and methyl methacrylate and their partially polymerized copolymers in the presence of polychloroprene and optionally up to 5% acrylic acid. U.S. Pat. No. 3,725,504 discloses similar compositions containing also acrylate polymers such as interpolymers of methyl methacrylate and ethyl acrylate, and containing about 8 to 12% of monomeric methacrylic acid. Compositions such as these are cured through the catalytic agency of a free-radical donor such a benzoyl peroxide or azobisisobutyronitrile.
In commercial application of such adhesive systems, there is an ever-increasing demand for rapid cure, i.e. there is a requirement for short "cure time", defined as the duration of time between the time of contacting the composition with catalyst and the time when the assembly bearing the adhesive can be easily handled without causing relative movement of the joined parts.
Formulations of the prior art commonly provide "cure times" of around a half-hour. More quickly curing variations can be made which become set in about ten minutes or in some cases even as quickly as about five minutes, but this is often at the expense of other desirable properties such as flexibility, toughness, adhesive bonding strength or storage stability of the uncatalyzed composition. Furthermore, in the design of many commercial operations, there is now a trend toward even shorter cure-times, of the order of one minute.
The new adhesives of this present invention contain substantial amounts of tris(dimethylaminomethyl)phenol. To the best knowledge of the inventor, there has been no prior disclosure of any composition containing acrylate or related ethylenically unsaturated monomers together with tris(dimethylaminomethyl)phenol. Perhaps one of the reasons for this is that other phenolic derivatives such as, for example, hydroquinone and catechol are known to be inhibitors of free-radical polymerization of olefinically unsaturated monomers even when present in relatively small amounts.
SUMMARY OF THE INVENTION
A means has now been found whereby storage-stable vinyl-polymerizable liquid sealants can be made which provide both accelerated curing rates and superior adhesion.
Briefly stated, the present invention provides a composition comprising from about 5% to 90% by weight of the salt formed by reacting three mols of methacrylic acid with one mol of tris(dimethylaminomethyl)phenol in admixture with conventional olefinically unsaturated monomers and optionally with conventional compatible polymers.
Exemplarily, it has been surprisingly found that a conventional vinyl-polymerizable sealant capable of curing in the presence of benzoyl peroxide within about 5-10 minutes is made to cure within about one minute by the admixture of as little as 5% or less, by weight, of the tri(hydrometharylate) of tris(dimethylaminomethyl)phenol. Likewise, when a conventional sealant already contains methacrylic acid, its curing is accelerated by the addition of up to one mol of tris(dimethylaminomethyl)phenol for every 3 mols of methacrylic acid. Changing the composition thus to include the tri(hydromethacrylate) of tris(dimethylaminomethyl)phenol also has the effect of substantially increasing shear strength.
DETAILED DESCRIPTION
The base, tris(dimethylaminomethyl)phenol whose methacrylic acid salt is used in this invention is obtainable by Mannich condensation of phenol, formaldehyde and dimethylamine, as disclosed in U.S. Pat. Nos. 2,033,092 and 2,220,834. This base is available as a commercial product under the proprietary name "DMP-30" comprising substantially the 2,4,6-isomer, containing about 0.7% water, and boiling at 143-149° C at 3 mm Hg. This product has been recommended as an intermediate in synthesis of wetting agents and emulsifiers and as a polymerization inhibitor. It has found extensive use as a catalyst in the manufacture of epoxy and polyurethane resins.
The salt used in the compositions of this invention is formed by reacting three mols of methacrylic acid with one mol of the base, tris(dimethylaminomethyl)phenol, corresponding to the use of 258 grams of pure methacrylic acid per 265 grams of pure base. While it is preferred to use pure materials, when commercial grades are used, the relative amounts to form the salt are calculated on the basis of their pure content.
The salt, hereinafter sometimes designated as the "tris" salt, can be prepared as a first step before admixing with the remaining constituents of the composition of this invention. Alternatively, the methacrylic acid and base can each be added individually to the composition whereby the salt is formed in situ on mixing.
It is generally desirable to use at least the stoichiometric amount of methacrylic acid, namely 258/265 or 0.97 parts by weight of the acid per one part of the base. It is preferred to use the methacrylic acid in excess of the stoichiometric amount, for example in at least one percent excess over the stoichiometric amount. While excess methacrylic acid in amount up to 20% of the total composition can give benefits of this invention, it is preferred to use the methacrylic acid in amount corresponding to from about 0.1% to 5% of the total composition weight. Thus when the amount of "tris" salt used is to be around 25% of the total composition, it is convenient to admix in overall about equal weights of methacrylic acid and tris(dimethylaminomethyl)phenol.
Monomers which can be used in admixture with the "tris" salt in the composition of this invention include any liquid or soluble olefinically unsaturated compounds capable of polymerizing by free-radical catalysis, i.e. capable of vinyl polymerization. The lower alkyl acrylates and methacrylates are particularly suitable, including methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, secondary butyl acrylate, tertiary butyl acrylate, tertiary butyl methacrylate, the amyl(meth)acrylates and the hexyl(meth)acrylates. Small amounts of higher acrylates or methacrylates may also be included as for the purpose of increasing the composition viscosity small amounts of 2-ethyl hexyl acrylate can be added. Monomers such as methacrylamide or acrylamide which are solid at ambient temperatures can be included in amounts sufficiently low to maintain their solubility in the liquid composition, as will be understood by those skilled in the art. There can also be used styrene, acrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride, chloroprene, acrylic acid, methacrylic acid or itaconic acid and the like. The preferred liquid monomer is methyl methacrylate.
Optionally, the composition can also include a polymer such as conventionally used in vinyl-polymerizable adhesive compositions for purposes of thickening or making more syrupy. Such a polymer can be a polyester or it can be an acrylic or vinyl-acrylic polymer or "pre-polymer".
Polyesters which are particularly suitable for use in compositions if this invention are those derived by reaction of at least one dihydric alcohol with at least one difunctional organic acid. Suitable dihydric alcohols include ethylene glycol, propylene glycol, neopentyl glycol and the like. Difunctional acids can be saturated or unsaturated, straight-chained branched or benzenoic and include malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, malic, maleic, fumaric, phthalic and isophthalic acids. Particularly suitable polyesters include polyesters of 4 mols ethylene or propylene glycol with 1 to 3 mols of isophthalic or phthalic acid and correspondingly 3 to 1 mols of maleic or fumaric acids.
When the polymer used is an acrylic or vinyl-acrylic polymer or "pre-polymer", the monomers polymerized or co-polymerized therein can be, singly or in combination, a lower alkyl acrylate or methacrylate such as those above enumerated, or styrene, acrylonitrile, vinyl acetate, vinyl propionate, vinyl chloride, acrylamide, methacrylamide, chloroprene, acrylic acid, methacrylic acid, itaconic acid, or the like. Exemplarily, the polymer can be polychloroprene or a copolymer of methyl methacrylate and ethyl acrylate or a copolymer of methyl acrylate and vinyl acetate.
The composition of this invention can include also small amounts of various adjuvant substances conventionally used in the making of adhesives of this sort, such as crosslinking agents, redox agents and the like. Thus there can be added up to 10% by weight, preferably up to about 5%, of triallyl cyanurate, allyl methacrylate, allyl sorbate, diethylene glycol diacrylate, vinyl crotonate or the like, as well as small amounts of various tertiary amines such as trimethylamine, diethylpropylamine, tripropylamine, tri-isopropylamine, tri-n-butylamine, tri-isobutylamine, tri-tertiary-butylamine, benzyl dimethylamine, triethanolamine, ethyl dimethylamine, 2-diethylaminoethanol, piperidine, dimethyl aniline, diethylaniline, dimethyl-p-toluidine, dimethyl-o-toluidine, diethyl-p-toluidine and the like. When a tertiary amine is used, amines with low degree of volatility are most suitable, dimethyl-p-toluidine being preferred.
In summary, the three main components of the compositions of this invention can be used in the following effective ranges of parts by weight per 100 parts
______________________________________ Permissible Preferred Most preferred______________________________________"Tris-salt" 5-90 15-50 20-30Monomer (s) 10-90 30-60 40-50Polymer (s) 0-60 10-40 20-30______________________________________
Compositions of this invention have been kept in storage for as long as one year or longer without significant change in properties. In order to become polymerized or cured they are placed into contact with a sufficient amount of conventional free-radical catalyst for vinyl polymerization, i.e. any substance capable of yielding by scission or under influence of a reducing agent a moiety having an unshared electron. Such free-radical donors are exemplarily benzoyl peroxide, lauroyl peroxide, cumene peroxide or hydroperoxide, tertiary butyl peroxide or hydroperoxide, azobisisobutyronitrile or the like. The free-radical catalyst can be added to the composition of this invention either by itself or in a suitable solvent, just prior to application of the resulting adhesive to the surface or surfaces to be bonded. Characteristically such addition can be made in an amount corresponding to between about one and five percent by weight of catalyst, based on weight of composition used. Exemplarily a paste can be prepared from equal parts by weight of benzoyl peroxide and dibutyl phthalate, and 3% of this paste is used, based on the weight of the sealant.
Alternatively, one or both of the surfaces to be bonded is first primed with a solution or lacquer containing the catalyst in amount so as to effect the desired ratio of catalyst to sealant at the locus of adhesion. According to a wellknown procedure in the prior art, benzoyl peroxide, for example, is dissolved in an appropriate solvent together with a compatible polymer in sufficient amount to thicken the solution into a lacquer which will stay in place on the primed surface while the solvent evaporates. Such a lacquer can be prepared, for example from 10 parts benzoyl peroxide, 5 parts of polymethyl methacrylate, and 85 parts trichloroethylene or a 50/50 mixture of trichloroethylene and methyl isobutyl ketone. Alternate polymers can be selected from the acrylic or vinyl-acrylic polymers described on page 6 above.
The sealants of the present invention can be used to bond a wide variety of substrates including metals, synthetic plastics and other polymers, glass, ceramics, wood and the like. After treatment and assembly of the surfaces to be bonded as above described, the assembly is permitted to stand. As stated, one of the principal features of the present adhesives is that within a relatively brief period after application of the adhesive and joining of the parts to be bonded, the bonded assembly can be handled.
It is obvious that traces of grease, lacquers and the like as well as certain electro-plated coatings in the case of some metal substrates, may retard polymerization or decrease the attainable bond strength. For this reason, it is desirable to remove such traces of grease or lacquer, conveniently by solvent treatment, before applying the adhesive and catalyst system of this invention.
This invention will be further illustrated by description in connection with the following specific examples of the practice of it wherein as also elsewhere herein proportions are in parts by weight unless stated otherwise.
EXAMPLE I
A solution was prepared of 45 parts by weight methyl methacrylate monomer, 12.8 parts methacrylic acid, 12.8 parts tris(dimethylaminomethyl)phenol, 4.6 parts triallyl cyanurate, 0.8 parts dimethyl-p-toluidine and 24.0 parts of a commercial glycol isophthalic polyester resin powder, Aropol 7200MC. (This commercial polyester had specific gravity 1.20, acid number 10 and an SPI gel time of 7.5 minutes at 180° F in the presence of 1% benzoyl peroxide.)
This solution was stable indefinitely at room temperature.
A drop of this solution was placed between solvent-wiped clean steel coupons primed with a polyacrylic lacquer containing about 5% benzoyl peroxide (Hughson Chemical Corp. Accelerator No. 4.) The coupons were bonded together in 45 seconds and had a shear strength of 3500 psi after 2 hours at room temperature.
EXAMPLE II
A solution of 18.2 grams tris(dimethylaminomethyl)phenol, 18.2 grams of methacrylic acid, 70.0 grams methyl methacrylate and 1.1 grams diethyl-p-toluidine was prepared. A drop of this solution was placed between solvent wiped steel coupons primed with a benzoyl-peroxide-acrylic polymer lacquer. The coupons were bonded together in 1 minute 15 seconds and had a shear strength of 1080 psi after 2 hours at room temperature.
EXAMPLE III
To a master solution of 13 parts tris(dimethylaminomethyl)phenol, 26 parts methacrylic acid, 59 parts methyl methacrylate and 1 part N,N-diethyl-p-toluidine, there was added 30 parts of a commercial polyester (ICI, Atlac 387). When this solution was used to bond solvent wiped steel coupons primed with a benzoyl peroxide-acrylic polymer lacquer, curing was obtained in 2 minutes and the shear strength was 2180 psi after 2 hours at room temperature.
EXAMPLE IV
To 100 parts of a proprietary adhesive formulation shown by infra-red analysis to contain at least 10% methacrylic acid (RD 2316-55 manufactured by Hughson Chemical Co.) there was added 10 parts tris(dimethylaminomethyl)phenol. In applying the respective adhesives to clean steel coupons as in the preceding examples, it was found that the addition of the tris(dimethylaminomethyl)phenol reduced the cure time from six minutes and 15 seconds to one minute, and increased the shear strength from 920 psi to 1014 psi after 2 hours at room temperature. | The admixture of the tri(hydromethacrylate) of tris(dimethylaminomethyl)phenol with conventional monomer and polymer components of vinylpolymerizable liquid sealants yields compositions which have accelerated cure times and superior adhesion. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 61/312,285, filed Mar. 10, 2010 and herein incorporated by reference.
TECHNICAL FIELD
The present invention relates to optical modulators and, more particularly, to semiconductor-based optical modulators including a separate phase control segment to adjust the amount of chirp present in the modulated output signal.
BACKGROUND OF THE INVENTION
For many years, optical modulators have been made out of electro-optic material, such as lithium niobate. Optical waveguides are formed within the electro-optic material, with metal contact regions disposed on the surface of each waveguide arm. A continuous wave (CW) optical signal is launched into the waveguide, and an electrical data signal input is applied as an input to the metal contact regions. The applied electrical signal modifies the refractive index of the waveguide region underneath the contact, thus changing the speed of propagation along the waveguide. By applying the voltage(s) that produce a 7 C phase shift between the two arms, a nonlinear (digital) Mach-Zehnder modulator is formed.
Although this type of external modulator has proven extremely useful, there is an increasing desire to form various optical components, subsystems and systems out of semiconductor material systems (e.g., InP, GaAs, silicon, or the like), with silicon-based platforms being generally preferred. It is further desirable to integrate the various electronic components associated with such systems (for example, the input electrical data drive circuit for an electro-optic modulator) with the optical components on the same silicon substrate. Clearly, the use of lithium niobate-based optical devices in such a situation is not an option. Moreover, it is well-known that lithium niobate-based devices have inherent performance limitations at data rates exceeding, for example, 1 GB/s, since they need to be modeled as traveling wave structures, with relatively complex electrical drive structures required to attempt to have the device operate at the requisite speed.
A significant advance has been made in the ability to provide optical modulation in a silicon-based platform, as disclosed in U.S. Pat. No. 6,845,198 issued to R. K. Montgomery et al. on Jan. 18, 2005, assigned to the assignee of this application and incorporated herein by reference. FIG. 1 illustrates one exemplary arrangement of a silicon-based modulator device as disclosed in the Montgomery et al. patent. In this case, a silicon-based optical modulator 1 comprises a doped silicon layer 2 (typically, polysilicon) disposed in an overlapped arrangement with an oppositely-doped portion of a sub-micron thick silicon surface layer 3 (often referred to in the art as an SOI layer). SOI layer 3 is shown as the surface layer of a conventional silicon-on-insulator (SOI) structure 4 , which further includes a silicon substrate 5 and a buried oxide layer 6 . Importantly, a relatively thin dielectric layer 7 (such as, for example, silicon dioxide, silicon nitride, potassium oxide, bismuth oxide, hafnium oxide, or other high-dielectric-constant electrical insulating material) is disposed along the overlapped region between SOI layer 3 and doped polysilicon layer 2 . The overlapped area defined by polysilicon layer 2 , dielectric 7 and SOI layer 3 defines the “active region” of optical modulator 1 . In one embodiment, polysilicon layer 2 may be p-doped and SOI layer 3 may be n-doped; the complementary doping arrangement (i.e., n-doped polysilicon layer 2 and p-doped SOI layer 3 ) may also be utilized.
FIG. 2 is an enlarged view of the active region of modulator 1 , illustrating the optical intensity associated with a signal propagating through the structure (in a direction perpendicular to the paper) and also illustrating the width W of the overlap between polysilicon layer 2 and SOI layer 3 . In operation, free carriers will accumulate and deplete on either side of dielectric layer 7 as a function of the voltages (i.e., the electrical data input signals) applied to doped polysilicon layer 2 (V REF2 ) and SOI layer 3 (V REF3 ). The modulation of the free carrier concentration results in changing the effective refractive index in the active region, thus introducing phase modulation of an optical signal propagating along a waveguide defined by the active region. In the diagram of FIG. 2 , the optical signal will propagate along the y-axis, in the direction perpendicular to the paper.
FIG. 3 illustrates an exemplary prior art silicon-based Mach-Zehnder interferometer (MZI) 10 that is configured to utilize silicon-based modulating devices 1 as described above. As shown, prior art MZI 10 comprises an input waveguide section 12 and an output waveguide section 14 . A pair of waveguiding modulator arms 16 and 18 are shown, where in this example waveguide arm 16 is formed to include a modulating device 1 as described above.
In operation, an incoming continuous wave (CW) light signal from a laser source (not shown) is coupled into input waveguide section 12 . The CW signal is thereafter split to propagate along waveguide arms 16 and 18 . The application of an electrical drive signal to modulator 1 along arm 16 will provide the desired phase shift to modulate the optical signal, forming a modulated optical output signal along output waveguide 14 . A pair of electrodes 20 are illustrated in association with modulator 1 and used to provide the electrical drive signals (V REF2 , V REF3 ). A similar modulating device may be disposed along waveguiding arm 18 to likewise introduce a phase delay onto the propagating optical signal. When operating in the digital domain, the electrodes may be turned “on” when desiring to transmit a logical “1” and then turned “off” to transmit a logical “0”.
FIG. 4 is a diagrammatic illustration of modulator 10 , illustrating the various electric field components associated with the prior art modulator, defining the chirp parameter which is the specific subject matter of concern in the present invention. Referring to FIG. 4 , the incoming CW optical signal is defined by the electrical field E in . Presuming a 50:50 power split into waveguide arms 16 , 18 , each waveguide will see an electric field of E in /√{square root over (2)} (also shown as E L and E R ) at their respective inputs. Each propagating signal will modulated along its respective arm, in the manner described above, and the electric fields of the output signals exiting waveguide arms 16 , 18 are expressed as follows:
E left =e iθ L E L , and
E right =e iθ R E R .
Combining these two signals along output waveguide 14 yields the following value for the output electrical field E out :
E out = 1 2 ( E left + E right ) = E i n cos ( Δ ϕ ) ⅇ ⅈ ϕ ,
where Δφ=(θ R −θ L )/2 and φ=(θ R +θ L )/2. The cos(Δφ) term is associated with the amplitude modulation imparted onto the propagating optical signal by virtue of the applied electrical input signal The e iφ term is a “pure” phase term, representative of the overall phase remaining in the output signal when compared to the input signal.
To the first order, the output power P out of a conventional modulator as shown above is given by the equation:
P out =|E out | 2 =½ |E in | 2 [1+cos(θ R −θ L )]
where the optical output power level is controlled by changing the value of the net phase difference Δφ between the two arms. FIG. 5 is a plot of this relationship, illustrating the output power as a function of phase shift between the two arms (a “1” output associated with maximum output power P out and a “0” output associated with minimum output power P out ). That is, a differential phase shift between the two arms of the modulator provides either constructive interference (e.g., “1”) or destructive interference (e.g., “0”). As will be described below, a modulator may also include a DC section to optically balance the arms and set the operating point at a desired location along the transfer curve shown in FIG. 5 .
While considered a significant advance in the state of the art over lithium niobate modulators, silicon-based optical modulators in general and the exemplary configuration of FIG. 3 in particular are known to suffer from chirp as a result of the inherent phase response and optical loss differences between the two arms of the modulator. Chirp is a time-varying optical phase that can be detrimental to the transmission behavior of an optical signal as it propagates through dispersive fiber. The chirp behavior of optical modulators is often characterized using an “alpha parameter” that is defined as the amount of phase modulation normalized to the amount of amplitude (intensity) modulation produced by the modulator. The alpha (α) parameter may be defined as follows:
α = 2 ⅆ ϕ ⅆ t 1 P ⅆ P ′ ⅆ t = - 1 tan ( Δ ϕ ) ( ⅆ θ R ⅆ t + ⅆ θ L ⅆ t ⅆ θ R ⅆ t - ⅆ θ L ⅆ t ) ,
and may exhibit a value that is zero, positive or negative, where for “zero” chirp, it is required that dθ R /dt=−dθ L /dt. In some applications, however, it is desirable to have a small amount of negative chirp (i.e., a small negative alpha parameter) to extend the transmission distance of a signal along a dispersive medium, such as an optical fiber, before dispersion limits the range. Even if “desirable”, there is still a need to control (or “know”) the amount of chirp that is associated with a particular modulator.
Conventional silicon-based optical modulators are known to exhibit non-zero chirp (even when configured in a symmetric drive arrangement) as a result of the nonlinear phase versus “applied voltage” response of their structure, as shown in FIG. 6 . Increasing either the modulation speed or the distance traveled by the modulated optical signal has been found to only exacerbate the chirp problem, since the dispersion characteristics of the transmission fiber will have an even greater impact.
Thus, a remaining need in the design of silicon-based optical modulators is a way of controlling the chirp that is created during the modulation process and, indeed, creating a “desired” value of chirp for a specific application/system configuration.
SUMMARY OF THE INVENTION
The needs remaining in the art are addressed by the present invention, which relates to semiconductor-based optical modulators including a separate phase control section to adjust the amount of chirp present in the modulated output signal.
In accordance with the present invention, at least one section is added to the modulator configuration and driven to create a pure “phase” signal that will be added to the output signal and modify the e iφ term inherent in the modulation function.
The phase modulation control section may be located within the modulator itself (with one segment on each arm, driven by the same input signal), or may be disposed “outside” of the modulator on either the input waveguiding section or the output waveguiding section. The placement of the phase modulation control section on the “outside” of the modulator having the advantage of creating a smaller capacitive load for the driver circuitry. The length of the phase modulation control section (in conjunction with the drive voltage applied to provide the modulation) then defines the amount of optical phase introduced to the propagating signal. It is important that when located inside the modulator, the segments are driven by the same polarity signal so that both segments impart the same phase delay to the signals propagating along each arm without creating a net phase difference between the two modulated signals as they are re-combined at the output of the modulator.
In one embodiment of the invention, the phase modulation control section is driven by the same signal that is used as the RF data input to the modulator itself, and provides a “fixed” phase adjustment to the output signal.
In an alternative embodiment, the phase modulation control section is driven by a separately controllable signal that allows for the phase to be adjusted for a specific application.
In yet another embodiment of the present invention, the phase modulation control section may be formed as a multi-segment arrangement, with separate ones of the segments being driven to control the amount of phase adjustment provided to the output signal.
Various ones of these embodiments may be used together and also used with other arrangements for controlling chirp in a modulator, such as controlling the voltages applied to the polysilicon layer of the modulator, as disclosed in our co-pending application Ser. No. 12/781,471, filed May 17, 2010.
Other and further embodiments and aspects of the present invention will become apparent during the course of the following discussion and by reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring now to the drawings,
FIG. 1 is a diagram of a prior art silicon-based optical modulator;
FIG. 2 is an enlarged view of the active region of the prior art optical modulator of FIG. 1 ;
FIG. 3 is a prior art Mach-Zehnder interferometer (MZI) utilizing the silicon-based optical modulator of FIG. 1 ;
FIG. 4 is a diagram of the MZI of FIG. 3 , showing the values of the electric fields at various locations along the optical signal path of the MZI;
FIG. 5 is a graph of the transfer curve of the MZI of FIG. 3 ;
FIG. 6 is a plot of voltage vs. phase for the MZI of FIG. 3 ;
FIG. 7 illustrates an exemplary chirp controlled optical modulator formed in accordance with the present invention to include a phase modulation control section;
FIG. 8 contains relevant eye diagrams for an exemplary modulator operating at 10 Gb/s, with the eye diagram of FIG. 8( a ) associated with a prior art silicon-based MZI and the eye diagram of FIG. 8( b ) associated with the chirp controlled optical modulator of FIG. 7 ;
FIG. 9 contains plots of chirp associated with the prior art modulator ( FIG. 9( a )) and the chirp controlled optical modulator of FIG. 7 (shown in FIG. 9( b ));
FIG. 10 illustrates a chirp controlled optical modulator of the present invention, utilizing a segmented phase modulation control section;
FIG. 11 illustrates an alternative chirp controlled optical modulator, where the phase modulation control section is disposed along the input waveguiding section of the modulator;
FIG. 12 illustrates yet another alternative chirp controlled optical modulator, where the phase modulation control section is disposed along the output waveguiding section of the modulator; and
FIG. 13 illustrates another embodiment of the present invention, utilizing segmented phase control modulation sections at both (or either) of the input and output waveguiding sections.
DETAILED DESCRIPTION
FIG. 7 illustrates an exemplary chirp controlled optical modulator 30 formed in accordance with the present invention. For the purposes of discussion, the components of modulator 30 that are similar to components of prior art modulator 10 carry the same reference numerals and their functionality is not discussed in detail. In this particular embodiment of the present invention, a phase modulation control section 32 is included in modulator 30 and is located “inside” the modulator with RF data modulation section 34 (which functions in the manner of the prior art as described above to impress an electrical modulating input signal on a CW optical signal propagating through the structure). In the embodiment of FIG. 7 , a separate DC bias section 36 is also shown. The use of DC bias in a modulator is well-known in the art, and is used to ensure that the modulator provides the desired phase shift around a specific operating point. The DC operating point is shown on FIG. 5 as preferably located mid-way between the maximum and minimum values of the output power.
In accordance with the present invention, each portion 33 -L and 33 -R of phase modulation control section 32 is driven by the same signal (as opposed to the use of complementary signals used to drive the RF data modulation section), so that each arm “sees” the same overall phase adjustment, noted as ψ in FIG. 7 , where as a result of the addition of this phase adjustment section, φ is now defined as follows:
ϕ = ψ + ( θ R + θ L ) 2
Thus, by controlling the value of ψ, the chirp of the overall modulator can be controlled. In particular, the length L phase of phase adjustment section 32 is optimized to provide the desired value of ψ and, as a result the desired chirp value. Moreover, the same data input signal used to drive RF data modulation section 34 can be used to drive phase adjustment section 32 .
FIG. 8 contains a pair of “eye diagram” plots (i.e., signal output as a function of time) for a data rate of 10 Gb/s, showing the improvement in performance by virtue of adding a phase adjustment section to a silicon-based optical modulator. FIG. 8( a ) is the eye diagram associated with a prior art silicon-based modulator, such as modulator of FIG. 3 , measured for a modulator length L data of 350 μm. FIG. 8( b ) is a plot of a modulator formed in accordance with the present invention, adding a phase adjustment section of L phase =250 μm. The improvement in eye opening from controlling chirp is noticeable in the eye diagram of FIG. 8( b ), especially at/near the low output power, “logic 0” value.
FIG. 9 contains plots of the chirp parameters associated with the eye diagrams of FIGS. 8( a ) and ( b ), where the chirp of the prior art shown in FIG. 9( a ) is positive in value for an extended portion of the bit period and never goes below “zero chirp. In contrast, FIG. 9( b ) illustrates the chirp associated with a modulator of the present invention, showing a substantial reduction in chirp (and, at times, a negative chirp value) within the bit period.
Various types of “segmented” optical modulators have been previously proposed. For example, U.S. Pat. No. 7,515,778, issued Apr. 7, 2009 and assigned to the assignee of this application, discloses a segmented modulator where the RF section comprises a plurality of segments to accommodate a multi-level input signal. This “segmented” approach may be used in accordance with the present invention to provide a tunable chirp control through a tunable phase modulation control section. FIG. 10 illustrates an exemplary optical modulator 40 formed in accordance with this aspect of the present invention, in this case showing the use of a single input data encoder 42 to provide inputs to both RF data modulation section 34 and phase adjustment section 32 . The ordering of components along the arms of the interferometer is not important; in this embodiment, phase adjustment section 32 is positioned before RF data modulation section 34 . As with the arrangement of FIG. 7 , a complementary signal pair is used to differentially drive segments 35 -L and 35 -R of RF data modulation section 34 .
In this particular arrangement as shown in FIG. 10 , phase modulation control section 32 comprises two separate segments along each arm, denoted as segments 44 -L and 46 -L along waveguide arm 16 , and segments 44 -R and 46 -R along waveguide arm 18 . Segments 44 -L and 44 -R are shown as having a first length L phase,1 and therefore impart a first phase delay ψ 1 to the propagating optical signal. Segments 46 -L and 46 -R are shown as having a second length L phase,2 , imparting a second phase delay ψ 2 to the propagating optical signal. In accordance with the present invention, therefore, by controlling the activation of these segments (via the input signals from encoder 42 ), the additional phase delay added to the output signal can be selected from the three different values: ψ 1 , ψ 2 , or ψ 1 +ψ 2 . Obviously, the inclusion of additional segments allows for further control of the applied phase delay.
As mentioned above, it is also possible to locate the phase modulation control section of the inventive modulator “outside” of the modulation element itself, along either one of the input and output waveguide sections. FIG. 11 is a simplified diagram of an optical modulator 50 formed in accordance with this embodiment of the present invention. In this case, a phase modulation control section 32 -I is positioned along input waveguide section 12 and is controlled by the same RF data input signal that drives arm 33 -L of RF data modulation section 34 . Phase modulation control section 32 -I is shown has having a length L phase,1 for imparting a phase of ψ 1 onto the incoming signal propagating along waveguide section 12 (before it is split along waveguide arms 16 , 18 ). The use of only a single segment to provide the phase adjustment to the propagating signal introduces less of a capacitive load than the embodiments described above with the phase modulation control section located inside of the modulator and requiring a pair of segments to introduce the phase adjustment along each waveguide arm.
FIG. 12 illustrates a similar embodiment as shown in FIG. 11 , in this case illustrating an optical modulator 60 with a phase modulation control section 32 -O disposed along output waveguide section 14 and controlled by the inverted RF data signal used to control segment 35 -R of RF data modulation section 34 . As shown, phase modulation control section 32 -O has a length of L phase,O selected to introduce a phase delay ψ O into the optical output signal. Again, the use of a single segment to provide the phase adjustment introduces less capacitance into the modulator than the embodiments requiring the use of a pair of segments.
As with the embodiment shown in FIG. 10 , it is possible to utilize a segmented phase modulation control section at either the input or output of the modulator. FIG. 13 illustrates an exemplary optical modulator 70 , showing in this particular embodiment both an input phase modulation control section 32 -I and an output phase modulation control section 32 -O (where it is to be understood that only a single segmented phase modulation control section may also be used). As with the segmented embodiment described above, input phase modulation control section 32 -I is shown as comprising a pair of segments 72 -I and 74 -I, each of a different length and thus imparting a different phase delay ψ I1 and ψ I2 to the input CW optical signal. A control element 76 is shown in this particular embodiment as providing the input drive signals to input phase modulation control section 32 -I, where either one or both (or neither) of the segments may be energized for a given application, thus providing a controlling amount of phase adjustment to the modulator to control the chirp exhibited by the output signal.
Similar control of segmented output phase modulation control section 32 -O provides the same ability to control the amount of chirp present in the output signal by controlling the phase introduced to the output signal.
In summary, by virtue of adding one or more segments to the modulator, the phase of the input signal can be controlled to provide the desired chirp behavior for a specific application/system configuration. The relatively small size of a semiconductor modulator (as compared to prior art lithium niobate modulators) allows for the “extra” phase sections to be added to the modulator without unduly increasing the size of the overall device or otherwise impacting the performance of the modulator. Indeed, it is possible to model the semiconductor modulator as “lumped elements” and thus avoid the complicated traveling-wave electrode structure associated with prior art lithium niobate modulators.
It is further to be understood that while the specific embodiments described above are associated with a silicon-based optical modulator, the same properties of phase, chirp and the like are present in other semiconductor-based modulators (i.e., III-V based modulating devices) and the principles of incorporating one or more phase modulation control sections in these other modulator configurations will provide chirp control in the same manner. Thus, the spirit and scope of the present invention is considered to be limited only by the claims appended hereto: | A semiconductor-based optical modulator is presented that includes a separate phase control section to adjust the amount of chirp present in the modulated output signal. At least one section is added to the modulator configuration and driven to create a pure “phase” signal that will is added to the output signal and modify the e iφ term inherent in the modulation function. The phase modulation control section may be located within the modulator itself, or may be disposed “outside” of the modulator on either the input waveguiding section or the output waveguiding section. The phase control section may be formed to comprise multiple segments (of different lengths), with the overall phase added to the propagating signal controlled by selecting the different segments to be energized to impart a phase delay to a signal propagating through the energized section(s). | 6 |
INTRODUCTION
This invention relates generally to isolation devices and, more particularly, to optical isolator circuits for maintaining electrical isolation between input signal sources and logic, or other, circuitry which utilize such input signals.
BACKGROUND OF THE INVENTION
In many systems, such as control systems which use computers or other appropriate control logic, it is desirable to supply such control logic with input signals of various kinds for controlling various operations or for processing input data signals. In many applications it is desirable that the utilization device, i.e., the control logic circuitry, be electrically isolated from the source of the input signals which are being supplied thereto. One type of device which provides such isolation is an optical isolator wherein the input signal is converted to a light signal, as by a light-emitting diode (LED), which light light-emitting signal is thereupon received by a photoresponsive device, such as a high speed photo-diode transistor pair. Transmission of the input signal in the form of a light signal provides appropriate electrical isolation between the input circuitry which supplies the LED and the output circuitry which is supplied from the photoresponsive device to the control logic.
Presently available optical isolator circuits are usually designed for very specific applications so as to accept input signals having particular characteristics, the design thereby being tailored to such characteristics. For example, certain isolators may be designed for accepting only AC signals, or for accepting only DC signals of a specified polarity and, in general, such design is usually responsive only to signals of a particular relatively narrow range of amplitude levels. Accordingly, such optical isolators are not generally available for widespread use in many different applications which may involve the acceptance of input signals of many different characteristics, i.e., AC signals or DC signals of either polarity, and signals having a wide dynamic range of amplitudes.
Even where such optical isolator circuitry is specifically designed for a particular use, such circuitry is subject to picking up undesirable noise signals of varying amplitudes which affect the output signal being supplied to the utilization device. A particular problem arises, for example, when extremely high amplitude noise signals are picked up by the isolator circuitry. For example, in machine tool control applications, the starting and stopping of motors which are used in the machine tool system produces extremely high amplitude oscillatory transient signls, commonly called "showering arc", sometimes as high as several thousand volts. The envelope of these signals tends to be several hundred microseconds long. Such transient signals are picked up by the input signal lines of the isolator from cables located in the general vicinity thereof. These transient noise signals normally have extremely wide bandwidths and the ability to filter them by conventional filter means is extremely difficult.
Moreover, even were the signals somehow to be filtered before being applied to the control logic circuitry at the output of the isolator device, the signals would still be present at the input circuitry to the LED. In such circumstances, while the overall system may be designed to achieve a relatively high degree of noise immunity (i.e., the output signal from the device has reduced noise levels), the input circuitry including the LED device will still be directly subject to the transient signal and the electric components used therein may be destroyed by the high amplitude transient signals. Hence, the circuitry, though having some noise immunity, often has low noise survivability to the application of such transients because the latter levels are so high that damage or destruction to the elements thereof occurs.
For example, certain present day isolator circuitry uses an LED and resistor which has a Zener diode connected in parallel therewith so as to provide a substantially constant voltage across the LED and resistor and, therefore, a substantially constant current through the LED. However, the Zener diode, apart from being costly, is subject to destruction by high amplitude transients of any polarity. Moreover, transients of negative polarity, even having relatively low amplitudes, can cause the Zener diode to be effectively destroyed by the occurrence thereof. Insofar as is known at present, no optical isolator circuitry is available which can adequately survive high transient noise signals which may occur in many applications nor do such presently available optical isolator circuits permit the acceptance of input signals over wide ranges of input amplitudes for both AC signals and DC signals of either polarity.
BRIEF SUMMARY OF THE INVENTION
This invention provides an optical isolator circuit which has a high degree of noise survivability even in the face of transient noise signals of extremely high amplitudes as discussed above. Furthermore, the circuit of the invention can accommodate signals of many different types (i.e., AC signals and DC signals of either polarity) over a wide range of input signal amplitude levels. Moreover, the system of the optical isolator of the invention can be utilized for many input signal sources without disrupting the operation thereof. For example, it can be used with many different electronic devices such as electronic sensors (e.g., proximity sensors) which require that no loading problems occur when the optical isolator is connected thereto.
In accordance with the invention, the input circuitry to a light-emitting diode utilizes a first input circuit section which, in a preferred embodiment, is in the form of a bridge circuit for providing a unidirectional voltage from the input signal. The unidirectional signal is then applied to a normalizing, or hard-limiting, circuit which converts the input voltage, which may vary over a wide range of amplitudes, to a substantially constant voltage which is then supplied to the LED and resistor to produce a relatively constant DC current therethrough.
The output of the LED is coupled to a photoresponsive device which is in turn coupled, in a preferred embodiment, to a Schmitt trigger gate circuit which further eliminates any transition noise as the signal changes state by using a fixed amount of hysteresis. The output of the Schmitt trigger circuit, in effect, shapes the input pulse from the photoresponsive device for supply to whatever control logic circuitry is being fed by the optical isolator in a utilization system. The input bridge circuit may preferably include a capacitor thereacross which, coupled with the input resistor, provides a filter circuit and permits the rectification of any AC signal which is applied to the input circuit.
In a preferred embodiment of the circuitry of the invention, the normalizing circuit is in the form of a plurality of conventional diodes arranged in series across a resistor and the light-emitting diode, the number of such diodes being selected to provide a voltage drop thereacross which is greater than that across the LED. Such diodes are selected to have a high back voltage capability.
DESCRIPTION OF THE INVENTION
The structure and operation of the optical isolator circuitry of the invention can be understood more readily with the help of the accompanying drawings wherein
FIG. 1 shows a block diagram of an embodiment of the invention;
FIG. 2 shows a more detailed schematic diagram of an embodiment of the invention of FIG. 1;
FIG. 3 shows a more detailed schematic diagram of a portion of the embodiment of FIG. 2; and
FIG. 4 shows a schematic diagram of an alternative embodiment of a portion of the invention.
As can be seen in FIGS. 1 and 2, an optical coupler device 10 which, in accordance with conventional optical isolation systems, comprises a photon-emitting source 15 which emits a light signal 16 which is representative of the input signal and a photoresponsive element 17 responsive thereto. Thus, electrical isolation occurs between the element 15 and the element 17. Elements 15 and 17, comprising a light-emitting diode device and a photoresponsive element, are available as a single packaged component sold, for example, as Model 5082-4370 by the HPA Division of Hewlett-Packard Company of Palo Alto, California. The photoresponsive element 17 of such package comprises a high speed photo-diode 30 coupled to a pair of amplifying transistors 31 and 32 as shown in FIG. 3. The optical coupler 10 provides the electrical isolation from the input signal thereto to the output signal therefrom by transmitting such signal in the form of light signal 16. As seen generally in FIG. 1, the input to the optical coupler 10 is supplied as an input signal from an appropriate source (not shown) which is fed to a unidirectional circuit 12 which supplies a unidirectional output voltage which is in turn supplied to a normalizing, or hard-limiting, circuit 11, the output of which is supplied as the input to the optical coupler 10. The output signal from optical coupler 10 may be fed in a preferred embodiment to an appropriate signal shaping circuit to produce an output signal for use by a utilization system. The latter, for example, may comprise appropriate control logic for controlling a machine in a production line, or the like. The overall signal channel of FIG. 1 from the input signal to the output signal may be one of a plurality of such channels used in an overall processing or control system, each channel handling a particular input command for supplying an output command signal to control logic of the utilization system.
In a system, such as a machine tool control system, which may include a large number of such channels, it is desirable that the optical isolation circuitry be interchangeable so that the same circuit can be produced on a mass basis and used in many different channels so as to be responsive to signals of varying characteristics supplied at the input thereto. Thus, the input signal may be an AC signal or a DC signal of either polarity. Moreover, the amplitude of the input signal may vary over a relatively wide range from a few volts to as high as 220 volts, or more. Moreover, the input signal may be from an appropriate electronics device, such as a sensing device, which, in order to operate properly, cannot be unduly overloaded. For example, the sensing device may be a proximity sensor which requires a relatively high input impedance for the optical isolation circuitry so that it is not excessively loaded thereby.
In accordance with a specific preferred embodiment of the invention, as shown in FIG. 2, the input signal is fed through an input load resistor 18 identified as R L to a unidirectional circuit 12 in the form of a bridge circuit comprising diodes 19. A capacitance 20 may be utilized across the diagonal output terminals 21, 21, as shown. The output voltage across the latter terminals is a unidirectional voltage. Thus, for a DC input signal of either polarity, such voltage will have the same polarity across terminals 21, 21. Moreover, for an AC input signal the R-C circuit comprising resistor 18 and capacitor 20 coupled with diodes 19 will effectively rectify the AC signal and provide a unidirectional voltage of the same polarity across such terminals.
Such voltage is supplied to the light-emitting diode 15 through diode resistance 22, identified as R D . The voltage across the diode 15 and the diode resistance 22 is maintained at a substantially constant level by the normalizing, or hard-limiting, circuit 11 which in the embodiment shown in FIG. 2 comprises a plurality of series-connected diodes 23. The substantilly constant voltage thereupon effectively produced across diodes 23 provides a substantially constant current through light-emitting diode 15. The forward current through the diode 15 will remain at such substantially constant level independently of the dynamic range of the input signal which is supplied to the input circuit. The series-connected diodes 23 produce a relatively small change in forward voltage with current and can be selected to be relatively low cost and highly rugged elements. For example, such diodes and diodes 19 may be of the type sold as Model No. 1N5061, made and sold by the Semiconductor Products Department of General Electric Company, of Syracuse, N.Y., or by Texas Instruments Company of Dallas, Tex. The output from photoresponsive element 17 is coupled to a Schmitt trigger gate 24 which has a fixed amount of hysteresis. The latter characteristic tends to eliminate transition noise which may result when the signal changes state and further tends to reduce the overall noise of the output signal which is supplied to a utilization system. Such a Schmitt trigger may be, for example, in the form of an integrated circuit which can be purchased as Model No. 74132, made and sold by Texas Instruments Company of Dallas, Texas. The Schmitt trigger may be disabled at its input on command by an appropriate strobe signal applied to the disabled input thereof. In some applications the presence of large transient noise signals may be anticipated and the strobe signal can be applied to disable the Schmitt trigger circuit sufficiently prior to the generation of such transients so that none of the transient signal is supplied at the output signal terminal to the utilization system. However even where the output circuitry from the photoresponsive device through the Schmitt trigger is disabled, the elements of the input circuit will still be subject to the high voltage transient signal and must, therefore, be capable of surviving the application thereof.
The configuration shown in FIG. 2 can provide low input current to the light-emitting diode for voltages which can range as high as 220 volts AC. Thus, for example, the current can be held to a relatively constant value within a range from about 1 milliamp, to about 2 milliamps, over such range.
In some applications where only DC input signals are anticipated the capacitor 20 may be omitted from the circuit. An RC circuit utilizing resistors 26 and capacitor 27 may be utilized in the output signal shaping circuit 13 to provide some filtering or high frequency input noise. The capacitor is relatively small, for example, about 0.01 microfarads in order to prevent a burst of oscillation on the transition edges which is caused by the changing input impedance of the trigger input as it goes through threshold.
The number of diodes 23 is selected so that their total voltage drop is greater than the voltage drop of the light-emitting diode which is supplied by the voltage thereacross. For the light-emitting diodes specified above, for example, four diodes 23 are found to be adequate to provide the required substantially constant voltage supplied thereto. Such diodes and the diodes used in the bridge circuit are selected to have high back-voltage capability for negative transients and will, in the case of those selected, stand up to as high as 600 volts back-voltage each.
In the configuration of FIG. 2 the stack of diodes 23 may be in some applications replaced with a Zener diode 35 as shown in the alternative embodiment of FIG. 4. The latter, however, for some applications may be too sensitive to input transients and also is a relatively high cost device and requires a relatively high bias current to operate at the appropriate part of its characteristic curve, which high current requirement results in a relatively large increase in the power dissipation of the input limiting resistance R L to the bridge circuit. Further, the Zener diode may be useful substantially only in applications where temperatures remain relatively low, that is, room temperature.
Thus, the overall system particularly in the embodiment shown in FIG. 2, provides a circuit which can utilize low cost readily available elements, particularly with respect to the diodes 23 and 19 which can be conventional silicon power diodes as mentioned above. The overall circuitry consumes substantially less power than previously used circuits and because of the low current and power requirements, the input resistance R L can be relatively higher so that the overall input impedance of the circuit is higher than that provided by prior art circuits. Moreover, unlike previously available isolation circuits, the circuitry of the invention can accept AC or DC signals of either polarity and can accept a relatively wide range of input voltages. Moreover, the elements are less subject to destruction due to large noise signals and the overall circuitry can survive high transient noise voltages of several thousands of volts, since the diode elements used therein can be selected to have higher peak reverse voltage ratings than the Zener diodes used in previously available isolator circuitry. The overall design is extremely reliable and of minimal complexity and, because of its universality, identical isolator circuits in accordance therewith can be used for a plurality of different signal channels without costly redesign tailored to fit each type of input signal. | Circuitry for providing electrical isolation between an input signal source and other circuitry which utilizes such input signal. The isolation circuitry uses an optical coupling means comprising a light-emitting diode circuit and a photo-responsive element, the input signal being supplied by a bridge circuit which provides a unidirectional voltage from the input signal which is then applied to a normalizing, or limiting, circuit which converts the unidirectional voltage to a substantially constant value which is supplied to the light-emitting diode circuit. The circuit is responsive to an input signal which can be an AC signal or a DC signal of either polarity, such circuit having a high degree of noise survivability even in the presence of transient noise signals such as "showering arcs" having extremely high amplitudes. | 7 |
BACKGROUND
1. Field of the Invention
The present invention is directed to a child cup, commonly known as a “sippy cup,” comprising a cup coupled to a lid having an opening therethrough adapted to received a straw. More specifically, the invention is directed to a sippy cup having a sliding actuator positioning a straw coupled to a lid between an erect position accessible by a child and a closed position where the actuator covers over the straw making inaccessible an open end of the straw for drawing fluid from the sippy cup.
2. Background of the Invention
Specialty child cups have been in the marketplace for a number of years. These child cups limit the availability of a fluid, typically a beverage, from entirely spilling from the cup once the cup has been overturned by the child. Prior art cups have included generally two pieces; a cup and a top lid having an opening therethrough.
The opening through these prior art lids was designed to limit the cross sectional area through which the fluid may travel, thereby keeping the amount of unintended fluid exiting the cup to a minimum when the cup is overturned. These lids have generally included a molded nipple or other similarly shaped protrusion adapted to be received by the child's mouth to create a fluidic seal between the lid and child's mouth. An example might include U.S. Pat. No. 6,568,557.
SUMMARY OF THE INVENTION
The present invention is directed to a child cup, commonly known as a “sippy cup,” comprising a cup coupled to a lid having an opening therethrough adapted to received a straw. The straw provides a means for directing a fluid contained within the cup to a child's mouth by the child depressurizing a portion of the straw and drawing the fluid through the straw. More specifically, the present invention is directed to a sippy cup having a sliding actuator positioning a straw between an erect position accessible by a child and a closed position making inaccessible an open end of the straw for drawing fluid from the sippy cup.
In an exemplary embodiment, the sippy straw cup includes a cup adapted to be coupled to a lid to create a fluidic seal therebetween. The cup includes an inner wall and an outer wall being separated by a space therebetween. The space may be occupied in part by a lenticular image providing a means of entertainment for the child. The lid includes a convex exterior and a concave interior, where the concave interior includes a conduit continuing through to the convex exterior/top. The convex exterior includes an arcuate, oblong channel receiving a sliding actuator therein. The sliding actuator is positionable between an open position where a straw riding within the conduit of the lid is in an erect position and a closed position where the straw is rendered inaccessible by the sliding actuator covering the straw and wedging the straw between the underside of the actuator and the recessed top surface of the lid. In the closed position, fluid within the cup is unable to be withdrawn through the straw.
It is a first aspect of the present invention to provide a closure for a container adapted to house a beverage therein, the closure comprising: (a) a cap having a mating feature adapted to interface with a corresponding feature of a container to secure the cap thereto, the cap also including an orifice therethrough and a channel therewithin, the channel being adapted to receive a sliding member therein; and (b) a flexible conduit adapted to be in fluid communication with a beverage within the container, wherein the sliding member is operative to position the flexible conduit between an open position and a closed position, where the open position enables fluid communication between a drinking end and an interior of the container.
In a more detailed embodiment of the first aspect, the flexible conduit biases the sliding member in the open position. In another more detailed embodiment, the sliding member includes a trench adapted to receive at least a portion of the flexible conduit when the flexible conduit is between the open position and the closed position. In yet another more detailed embodiment, the flexible conduit includes molded retention features thereon to inhibit the flexible conduit from being pulled through the orifice. In a further detailed embodiment, the trench runs parallel to the channel and parallel to a range of movement available to the sliding member. In still a further more detailed embodiment, the cap includes a trench adapted to receive at least a portion of the flexible conduit when in the closed position, wherein the trench includes a dam operative to discontinue fluid communication with the beverage in the closed position. In yet a further more detailed embodiment, the sliding member is substantially radially recessed within the channel. In another detailed embodiment, the sliding member includes at least one fin received within at least one guide groove formed within a side wall of the channel. In yet another more detailed embodiment, the flexible conduit is adapted to receive a rigid conduit for extending approximate a bottom of the container. In still a further more detailed embodiment, a bottom of the cap is substantially concave.
In a more detailed embodiment of the first aspect, the cap is substantially dome shaped. In a further detailed embodiment, the container includes a lenticular image. In yet a further detailed embodiment, the container includes concentric gripping rings. In a more detailed embodiment, the sliding member slides radially. In another more detailed embodiment, the container includes a holographic image. In yet another detailed embodiment, the cap includes circumferentially arranged gripping aids.
It is a second aspect of the present invention to provide a container comprising:
(a) a cup adapted to hold a beverage therein, the cup having a lenticular image associated therewith; and (b) a cap having a mating feature adapted to interface with a corresponding feature of the cup to secure the cap thereto, the cap also including an orifice therethrough coupled to a flexible conduit adapted to be in fluid communication with the beverage within the cup, wherein at least one of a pivoting member and a sliding member coupled to the cap is operative to position the flexible conduit between an open position and a closed position, where the open position enables fluid communication between a drinking end of the flexible conduit and an interior of the cup.
In a more detailed embodiment of the second aspect, the lenticular image is interposed between a clear outer cup and to an inner cup. In another more detailed embodiment, the clear outer cup and the inner cup are coupled together by spin molding. In yet another more detailed embodiment, the cap includes an arched channel therewithin, the arched channel being adapted to receive a sliding member therein, wherein the sliding member is operative to position the flexible conduit to protrude from an outer surface in the open position and recess the flexible conduit within the outer circumferential surface in the closed position.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of an exemplary embodiment of the present invention;
FIG. 2 is a cross-sectional view the exemplary embodiment of the present invention taken along lines 1 — 1 of FIG. 1 ;
FIG. 3 is a side view of an exemplary cup component in accordance with the exemplary embodiment of the present invention;
FIG. 4 is a cross-sectional view the exemplary cup component in accordance with the exemplary embodiment of the present invention taken along lines 3 — 3 of FIG. 3 ;
FIG. 5 is a side view of an exemplary lid component in accordance with the exemplary embodiment of the present invention;
FIG. 6 is a cross-sectional view the exemplary lid component in accordance with the exemplary embodiment of the present invention taken along lines 5 — 5 of FIG. 5 ;
FIG. 7 is a frontal view of an exemplary lid component in accordance with the exemplary embodiment of the present invention;
FIG. 8 is a cross-sectional view the exemplary lid component in accordance with the exemplary embodiment of the present invention taken along lines 7 — 7 of FIG. 7 ;
FIG. 9 is a side view of an exemplary sliding actuator component in accordance with the exemplary embodiment of the present invention;
FIG. 10 is a rearward view of the exemplary sliding actuator component in accordance with the exemplary embodiment of the present invention;
FIG. 11 is a bottom view of the exemplary sliding actuator component in accordance with the exemplary embodiment of the present invention;
FIG. 12 is a cross-sectional view, from the side, of the exemplary lid and sliding actuator components in accordance with the exemplary embodiment of the present invention providing fluid communication between the fluid within the container and an external environment; and
FIG. 13 is a cross-sectional view, from the side, of the exemplary lid and sliding actuator components in accordance with the exemplary embodiment of the present invention inhibiting fluid communication between the fluid within the container and an external environment.
DETAILED DESCRIPTION
The exemplary embodiments of the present invention are described and illustrated below as a fluid container, referred to below as a “sippy straw cup”, comprising a cup and corresponding lid having a sliding actuator to regulate fluid communication between an interior of the sippy straw cup and an external environment. The various orientational, positional, and reference terms used to describe the elements of the present invention are therefore used according to this frame of reference. However, for clarity and precision, only a single orientational or positional reference will be utilized; and, therefore it will be understood that the positional and orientational terms used to describe the elements of the exemplary embodiment of the present invention are only used to describe the elements in relation to one another.
Referring to FIGS. 1 and 2 , an exemplary embodiment of a sippy straw cup 10 includes a cup 12 , a lid 14 , a sliding actuator 16 , and a straw 18 providing a selectively sealed fluid reservoir 20 available for holding a fluid therein, that may include, without limitation, a beverage. In an open position, as shown, the straw 18 is erect and provides fluid communication between the fluid reservoir 20 and an external environment 22 . The straw 18 may include two or more sections, with a first section 24 being resilient and a second section 26 coupled to the first section 24 that is less resilient and not readily amendable to spatial deformation.
Referencing FIGS. 2–4 , the cup 12 includes a cavity 28 partially defined by an exterior wall 30 of an inner cup 32 and partially by an interior wall 34 of an outer cup 36 . The cavity 28 may be adapted to receive a graphical expression (not shown), in which case the outer cup may be transparent to facilitate visual appeal. The graphical expression may include a lenticular or holographic image on a medium positioned within the cavity 28 . Those of ordinary skill in the art are familiar with the methods of forming lenticular, holographic, or other images onto various mediums.
The inner cup 32 includes an interior wall surface 38 defining the reservoir 20 and a spout 40 having spiral protrusions 42 on an exterior surface 44 adapted to be received within corresponding grooves 70 within the lid 14 for securing the lid 14 to the cup 12 . The spout 40 includes a ledge 46 transitioning into a circumferential wall 48 forming a recess 50 between the circumferential wall 48 and the exterior wall 30 of the inner cup 32 . The recess 50 is adapted to receive a top portion 52 of the outer cup 36 , where the outer cup 36 and the inner cup 32 may be coupled together by spin sealing.
The outer cup 36 transitions from the top portion 52 into a sill 54 circumferentially thereabout that tapers inward to create a first indentation 56 . The first indentation 56 leads into a first mound 58 that gives rise to a second indentation 60 and thereafter a second mound 62 . Each indentation 56 , 60 and each mound 58 , 62 is circumferentially distributed about the outer cup 36 . The second mound 62 transitions into a smooth taper terminating at a bottom aspect 64 having a dome shaped underneath surface 66 .
Referencing FIGS. 5–8 , the lid 14 is substantially domed shaped having a plurality of raised areas 68 circumferentially distributed thereabout to facilitate gripping as the corresponding grooves 70 within an outer wall 72 receive the spiral protrusions 42 of the inner cup 32 to couple the lid 14 to the cup 12 (See FIG. 12 ). A fluidic seal is created between an interior surface 74 of the outer wall 72 and the exterior surface 42 of the inner cup 32 , as well as between an interior surface 76 of an inner lip 78 (extending from the outer wall 72 ) and the interior surface 38 of the inner cup 32 . The outer wall 72 transitions upward from the inner lip 78 in an arcuate manner until terminating at a recess 80 .
The recess 80 includes a side surface 82 being essentially square with an arcuate top surface 84 . The arcuate top surface 84 defines an orifice 86 therein and gives rise to a conduit 88 extending from the top arcuate surface 84 of the recess 80 to an underneath surface 90 of the lid 14 . The conduit 88 includes circumferential projection 92 separating a first cylindrical portion 94 and a second cylindrical portion 96 having a greater diameter than the first cylindrical portion 94 . A groove 97 , adapted to receive the straw 18 , is formed within the recess 80 and includes a finger 98 abutting the orifice 86 . The side surface 82 of the recess 80 includes a guide notch 100 cut therein following the generally arcuate shape of the recess that is adapted to receive guide pins 102 of the sliding actuator 16 (See FIGS. 9–11 ).
Referring to FIGS. 9–12 , the sliding actuator 16 is adapted to be received within the recess 80 and includes a generally arcuate shape from the side, where an underneath surface 104 is adapted to ride along the top surface 84 of the recess 80 and a top surface 106 of the actuator 98 is adapted to be substantially flush with the outer wall 72 of the lid 14 upon being seated within the recess 80 . Two guide pins 102 protrude from each side 108 of the actuator 16 and are operative to guide the actuator 16 within the recess 80 from a closed position where the straw 18 is wedged between the underneath surface 104 and the top surface 84 and an open position where the straw 18 is erect.
A contoured ridge 110 extends across the actuator 16 and includes two sliding guides 112 adapted to slide along the outer wall 72 . The contoured ridge 110 provides an actuation point for a user to push against or pull on the ridge 110 to effect motion of the actuator 16 with respect to the recess 80 . The underneath surface 104 includes a pair of rectangular projections 113 forming a mating channel 114 therebetween. The front 116 of the actuator 16 is partially open to guide the cylindrical nature of the straw 18 into the mating channel 114 when the actuator 16 is in the closed position. The straw 18 may include exterior features such as guide grooves or ridges (not shown) to further facilitate alignment within the groove 97 and the mating channel 114 .
Referencing FIG. 12 , the open position of the sippy straw cup 10 is shown having the first section 24 of the straw 18 partially received within the conduit 88 and includes an exposed section 120 with a tip 122 at the end not received within the conduit 88 . An orifice 124 defined by a wall 126 of the straw 18 provides a generally constant internal diameter providing a circular cross-sectional area available for fluid flow therethrough. This generally constant internal diameter continues for the length of the first cylindrical portion 94 and part of the second cylindrical portion 96 . The radius of orifice 124 and the radius of the wall 126 aggregate to approximate the internal diameter of the conduit 88 . The straw 18 includes an indentation 128 that receives the circumferential projection 92 seating the straw 18 within the conduit 88 . The wall 126 increases in thickness to abut an interior wall 130 of the second cylindrical portion 96 , and when teamed with the indentation 128 and the circumferential projection 92 , inhibits vertical movement of the straw 18 within the conduit 88 . Just beyond the exit of the conduit 88 , a step change within the straw is present where the orifice 124 increases in cross-section to receive the second section 26 adapted be in direct contact with the beverage occupying the reservoir 20 of the sippy straw cup 10 .
Referring to FIG. 13 , the closed position of the sippy straw cup 10 is shown having the straw 14 wedged between the underneath surface 104 of the actuator 16 and the top surface 84 of the recess 80 . In practice, as the actuator 16 is repositioned from the open position to the closed position, the front 116 of the actuator 16 contacts the external wall 126 of the exposed section 120 of the straw 18 and pushes the straw forward. The open section of the front 116 of the actuator 16 and the mating channel 114 receives the exposed section 120 of the straw 18 as the actuator 16 continues moving forward, thereby pushing the straw 18 over the finger 98 projecting outward from the conduit 88 and into the groove 97 formed within the recess 80 . As the straw 18 is received within the groove 97 and mating channel 114 , the finger 98 forces one side of the straw wall 126 against the other side of the straw wall 126 , discontinuing the orifice 124 within the straw 18 to inhibit fluid communication between the second section 26 and the tip 122 of the straw 18 . The forward movement of the actuator 16 pushes the straw 18 completely within the groove 97 and mating channel 114 while the rear section 118 of the actuator 16 covers the orifice 86 . When moving from the closed to the open position, the actuator 16 is moved backward, gradually uncovering the exposed section 120 of the straw 18 previously seated within the groove 97 and mating channel 114 such that the resiliency of first section 26 of the straw 18 gradually raises the straw 18 to an erect position abutting the front 116 of the actuator 16 .
Following from the above description and invention summaries, it should be apparent to those of ordinary skill in the art that, while the methods and apparatuses herein described constitute exemplary embodiments of the present invention, the inventions contained herein are not limited to these precise embodiments and that changes may be made to them without departing from the scope of the invention as defined by the claims. Additionally, it is to be understood that the invention is defined by the claims and it is not intended that any limitations or elements describing the exemplary embodiments set forth herein are to be incorporated into the meanings of the claims unless such limitations or elements are explicitly recited in the claims. Likewise, it is to be understood that it is not necessary to meet any or all of the identified advantages or objects of the invention disclosed herein in order to fall within the scope of any claim, since the invention is defined by the claims and since inherent and/or unforeseen advantages of the present invention may exist even though they may not have been explicitly discussed herein. | A closure for a container adapted to house a beverage therein, the closure comprising: (a) a cap having a mating feature adapted to interface with a corresponding feature of a container to secure the cap thereto, the cap also including an orifice therethrough and a channel therewithin, the channel being adapted to receive a sliding member therein; and (b) a flexible conduit adapted to be in fluid communication with a beverage within the container, wherein the sliding member is operative to position the flexible conduit between an open position and a closed position, where the open position enables fluid communication between a drinking end and an interior of the container. | 0 |
BRIEF DESCRIPTION OF THE INVENTION
The invention relates to a pattern selecting system for a sewing machine, which is simple in structure, durable and easy in operation for selecting many possible patterns which a sewing machine could generate. This invention is used in a sewing machine producing patterns by means of pattern forming devices actuated in accordance with the signals from a mechanical or electronic memory storing a plurality of pattern control data.
A conventional mechanical memory, for example a pattern cam device, stores pattern control signals and also drives the pattern forming devices of the sewing machine. It is apparent that such a pattern cam device complicates the machine mechanism and eventually make the mechanism bulky for the limited space of the machine head. With the recent development of the electronic techniques, it has become possible that the pattern cams be used only to store the pattern control signals, with the pattern forming devices electrically driven, so as to make the machine mechanism simplified. Especially the development of microcomputer techniques has made it possible to use an electronic memory for electrically driving the pattern forming devices with the increased amount of pattern data stored therein. Now it is generally desired to provide a system which could effectively read out such pattern data from the electronic memory with easy operation and a simple structure suitable for a limited space within and outside of the machine housing. This invention has been provided in response to such a desire.
Now it is a primary object of this invention to provide a pattern selecting system for selecting many patterns with a simple structure, durable and easily operated.
It is another object of this invention to provide a pattern selecting system for a sewing machine which is capable of selecting a plurality of patterns with a single manually operated switch.
It is still another object of this invention to provide a pattern selecting system which is compact and easily installed in a limited space of the sewing machine.
It is still another object of this invention to provide a pattern selecting system including a pattern selection control circuit operated by the single switch.
EXPLANATION OF THE ATTACHED DRAWINGS
FIG. 1 is a front elevational view of a sewing machine embodying the present invention,
FIG. 2 is a side view partly in section along the line II--II,
FIG. 3 is a control circuit of this invention,
FIG. 4 is a partly modified embodiment of the control circuit, and
FIG. 5 is still another embodiment of the control circuit.
DESCRIPTION OF THE INVENTION
In reference to FIGS. 1 and 2, reference numeral (1) denotes a machine housing. Numeral (2) is a front panel attached to the machine housing. Numerals (3)-(9) are pattern selection buttons mounted on the front panel. Numeral (10) is an indicating plate on which various patterns (3AC')-(9 D') are printed, though only a few of them are actually represented. Numerals (3AC)-(9D) are indicating lamps mounted on the indicating plate each adjacent to the respective pattern. Numeral (20) denotes one of plural rubber switches each having a conductor (21) and each arranged behind a respective one of the pattern selection buttons (3)-(9). Each rubber switch is operated by way of the respective pattern selection button. Numeral (22) is a printed base plate supported on the panel (2) for establishing connections among circuit components as shown in FIG. 3 including the pattern indicating lamps (3AC)-(9D), the rubber switches (20) and other elements described below, so as to control a memory and other elements connected thereto by means of a connector (23). Numerals (24)-(27) indicate adjustment dials manually operated to electrically adjust zigzag amplitude, feeding amount, upper thread tension, etc., by means of variable resistors or rotary switches. Numerals (28)(29) indicate switches for alternately selecting single needle stitching or twin needle stitching together with the changeover of stitching data, and for selectively setting the feed dog to be ineffective or to be effective by means of on electromagnet or other elements. FIG. 3 depicts a control circuit for a sewing machine including a logic circuit (30). (F/F 3 )-(F/F 5 ) indicate flip-flop circuits of the master-slave type, and these each have a reset terminal (R) connected to the complement side terminal (p) of a power-on reset circuit (P.R), and are adapted to be reset when the control power source (Vcc) is thrown. The flip-flop circuits (F/F 3 )-(F/F 5 ) have their input terminals (J)--(J) each connected to the output terminals of respective NAND circuits (NA 1 )-(NA 3 ) which encode the states of the pattern selection buttons (3)-(9) as logic values 001-111. These flip-flop circuits have their other input terminals (K) connected to the output terminals of the same NAND circuits in such a manner that the output data of the NAND circuits are inverted. (R)--(R) are ordinary limiting resistors. (MM 1 ), (MM 2 ) are monostable multivibrators. The multivibrator (MM 1 ) has a trigger terminal (T) connected to the output terminal of an OR circuit (OR) whose input terminals are connected to the output terminals of the NAND circuits (NA 1 )-(NA 3 ). The complement side terminal (Q) of the monostable multivibrator (MM 1 ) is connected to the trigger terminal (T) of the monostable multivibrator (MM 2 ) whose true side terminal (Q) is connected to the common trigger terminal (C p ) of the flip-flop circuits (F/F 3 )-(F/F 5 ), and the complement side terminal (Q) of (MM 2 ) is connected to one of the input terminals of a NOR circuit (NOR). The monostable multivibrator (MM 2 ) has a reset terminal (R) connected to the output terminal of the OR circuit (OR).
Each flip-flop circuit (F/F 3 )-(F/F 5 ) has its input terminal (J)--(J) and its respective output terminal (Q 3 )-(Q 5 ) connected to the two input terminals of a respective one of three exclusive OR circuits (Ex. OR 1 )-(Ex. OR 3 ) the output terminals the latter being connected to respective input terminals of the NOR circuit (NOR). The output terminals (Q 3 )-(Q 5 ) of the flip-flop circuits (F/F 3 )-(F/F 5 ) are furthermore connected to the input terminals of a decoder (DE 1 ) and also to the terminals (O 3 )-(O 5 ) of the connector (23) which is connected to a memory and other elements. (F/F 1 )-(F/F 2 ) are flip-flop circuits constituting a modulo-4 counter and have a reset terminal (R) connected to the complement side output terminal (p) of the power-on reset circuit (P.R), and are adapted to be reset when the voltage source (Vcc) is switched on. These flip-flop circuits have a trigger terminal (C p ) connected to the output terminal of the NOR circuit (NOR), and are operated with each pulse from the NOR circuit to repeatedly advance from 00 to 11 the code at then output terminals (Q 1 ), (Q 2 ). The output terminals (Q 1 ), (Q 2 ) of these two flip-flop circuits are connected to the input terminals of a decoder (DE 2 ) and also connected to the terminals (O 1 ), (O 2 ) of the connector (23). The pattern indicating lamps (3AC)-(9D) are luminous diodes. The luminous diodes (3AC)-(9D) are interconnected to form a row-by-column array, the leftmost column being constituted by the two light-emitting diodes (3AC) and (3BD), the second column being constituted by the four diodes (4A)-(4D), and so forth. The lowermost row is constituted by light-emitting diode (3AC) and by the light-emitting diodes (4A)-(9A), and the uppermost row is constituted by the light-emitting diodes (4D)-(9D), etc. Except for light-emitting diodes (3AC) and (3BD), the anodes of all A-row diodes are connected via a shared resistor R' to the collector of a A-row transistor (Tr A ), the anodes of all B-row diodes via another such resistor (R') to the collector a B-row transistor (Tr B ), etc. The anode of light-emitting diode (3AC) is connected via respective ones of two simple diodes (D1) and (D3) to the collectors of the transistors (Tr A ) and (Tr C ), through the intermediate of the associate resistors (R'). Likewise, the anode of light-emitting diode (3BD) is connected via respective ones of two simple diodes (D2) and (D4) to the collectors of the transistors (Tr B ) and (Tr D ), through the intermediate of the two resistors (R') associated with those two transistors. The cathodes of the two row-3 diodes (3AC), (3BD) are connected in common to the (N 3 ) output of decoder (DE 1 ); the cathodes of all the row-4 diodes (4A)-(4D) are connected in common to the (N 4 ) output of decoder (DE 1 ); and so forth. The emitters of the transistors (Tr A )-(Tr D ) are connected to the voltage source (V cc ), and their bases are connected, via respective ones of four resistors (R") to respective ones of the four outputs (N A )-(N D ) of decoder (DE 2 ). Depression of any single one of the pushbuttons (3)-(9) per se determines which output of decoder (DE 1 ) carries an output signal, and thereby per se determines which column is to have one of its light-emitting diodes illuminated; the number of times such pushbutton is depressed determines which output of decoder (DE 2 ) carries an output signal, and thereby determines which row of light-emitting diodes is to have one of its diodes light up.
FIG. 4 depicts the modified part of a modified version of the embodiment of FIG. 3. In this embodiment, the exclusive OR circuits (Ex.OR 1 )-(Ex. OR 3 ) have their output terminals connected, via a NOR circuit (NOR), to one input terminal of an AND circuit (AND) and of a NOR circuit (NOR 2 ). The AND circuit has the other input terminal connected to the true side terminal (Q) of the monostable multivibrator (MM 2 ). The AND circuit has its output terminal connected to the trigger terminal (Cp) of the flip-flop circuits (F/F 1 ), (F/F 2 ). The NOR circuit (NOR 2 ) has its other input terminal connected to the complement side terminal (Q) of the monostable multivibrator (MM 2 ). The NOR circuit (NOR 2 ) has its output terminal connected to one input terminal of a NOR circuit (NOR 3 ) whose other input terminal is connected to the true side terminal (P) of the power-on reset circuit (P.R). The N0R circuit (NOR 3 ) has its output terminal connected to the reset terminal (R) of the flip-flop circuits (F/F 1 ), (F/F 2 ).
FIG. 5 depicts a further embodiment of this invention in which a microcomputer system (40) is used in place of the logic circuit (30), the connector (23) and the memory of FIG. 3. The microcomputer system may be a MCS-80 which is a product of the INTEL company. In this case, the voltage source (Vcc) is connected, through a resistor (R'"), to all the pattern selection buttons (3)-(9) on one side thereof which are, in turn, connected to the input terminal (in) of the microcomputer system (40). These pattern selection buttons are, on the other side thereof, connected to respective ones of the pattern indicating lamps (3AC)-(9D), and are also connected to respective output terminals (OUT 1 ) of the microcomputer system (40). The transistors (TrA)-(TrD) are all connected, through the resistors (R")--(R"), to respective output terminals (OUT 2 ) of the microcomputer system (40). In FIG. 3, when the voltage source (Vcc) is switched on, the outputs (Q 1 )-(Q 5 ) of flip-flop circuits (F/F 1 )-(F/F 5 ) all become 0. If the pattern selection button (3) is firstly pushed, the outputs of the NAND circuits (NA 3 ), (NA 2 ), (NA 1 ) become 0,0,1 and these output values are compared with the outputs (Q 5 ), (Q 4 ), (Q 3 ) of the flip-flop circuits (F/F 5 )-(F/F 3 ), and then the output values of the exclusive OR circuits (EX.OR 3 ), (EX.OR 2 ), (EX.OR 1 ) become 0,0,1. On the other hand, the complement side output (Q) of the monostable multivibrator (MM 1 ) generates a negative pulse having a rising trailing flank. Subsequently the complement side output (Q) of the monostable multivibrator (MM 2 ) generates a negative pulse. However, since the other three inputs of the NOR circuit (NOR) are all in receipt of the value 1, the NOR circuit (NOR) will not generate a pulse. Therefore, the outputs (Q 2 ), (Q 1 ) of the flip-flop circuits (F/F 2 ), (F/F 1 ) maintain the values 0,0. This is because the outputs (Q 5 ), (Q 4 ), (Q 3 ) of flip-flop circuits (F/F 5 ), (F/F 4 ), (F/F 3 ) are rendered 0,0,1, thereby making the three inputs of the NOR circuit (NOR) all 0, at the time of the trailing flank of the negative pulse produced at the complement side output (Q) of the monostable multivibrator (MM2), namely at the end of the pulse produced at the true side output (Q) of the monostable multivibrator (MM 2 ), but at that time the output (Q) is 1 and there is no pulse to be applied to the trigger terminal (Cp) of the flip-flop circuits (F/F 2 ), (F/F 1 ). The data 0 0 1 will cause the first output (N 3 ) of the decoder (DE 1 ) to be 0, and the other outputs to be 1. The data 0 0 at the outputs (Q 2 ), (Q 1 ) of the flip-flop circuits (F/F 2 ), (F/F 1 ) will cause the first output (NA) of the decoder (DE 2 ) to be 0, and the other outputs to be 1. Thus the pattern indicating lamp (3AC) is lit, and the output code (O 5 )-(O 1 ) becomes 0 0 1 0 0 for producing straight stitches (3AC').
In order to select another pattern, for example, pattern (5B'), the pattern selection button (5) is once pushed. Then the outputs of the NAND circuits (NA 3 ), (NA 2 ), (NA 1 ) become 0, 1, 1 respectively, and the flip-flops (F/F 2 ), (F/F 1 ) do not count up as in the case when the button (3) was pushed. In this case, the pattern indicating lamp (5A) is lit and the output code (O 5 )-(O 1 ) becomes 0 1 1 0 0. For selecting pattern (5B'), the button (5) must be pushed again. In this case, the input data of the flip-flop circuits (F/F 5 )-(F/F 3 ) become 0, 1, 1, respectively and the three inputs of the NOR circuits (NOR) become 0, 0, 0, and then the negative pulse from the complement side terminal (Q) of the monostable multivibrator (MM 2 ) advances the output data of the flip-flop circuits (F/F 1 ) by 1 to make the data 01. Namely the second output (N 2 ) of the decoder (DE 2 ) is rendered 0 while the third output (N 5 ) of the decoder (DE 1 ) becomes 0 and the other outputs become 1 all in response to the aforementioned input data 0 1 1 of the flip-flop circuit (F/F 5 )-(F/F 3 ). As the result, the pattern indicating lamp (5B) is lit and the output code (O 5 )-(O 1 ) becomes 0 1 1 0 1, and thus pattern (5B') is stitched. In this manner, each subsequent pushing of the button (5) causes the lamps (5C), (5D), (5A), to light up in order. Therefore, the machine operator can select any of the patterns by repeatedly pushing the pattern selection button of the pattern group involved.
In case the pattern selection buttons (3)-(9) are not firmly pushed, for example, resulting in chattering, the reset terminal (R) of the monostable multivibrator (MM 2 ) becomes effective to prevent the flip-flop circuits (F/F 2 ), (F/F 1 ) from counting, thereby to prevent the erroneous operation of the pattern selection system. The control circuit in FIG. 3 is as shown so formed as to select, after the selection of the pattern (5B'), the pattern (6B') if the pattern selection button (6) is pushed, and to select, after the selection of the pattern (6B'), the pattern (7B') if the button (7) is pushed. Thus the changeover of the pattern selection buttons (3)-(9) initially selects one of the transversely aligned patterns as shown in FIG. 1.
In contrast to the control circuit in FIG. 3, the partly modified circuit as shown in FIG. 4 is so formed as to select, for example after the selection of the pattern (5B'), the pattern (6A') if the pattern selection button (6) is pushed. Namely the changeover of the selection buttons (3)-(9) initially selects the first one of the pattern groop under the control of the button. In this embodiment, each time a different one of the selection buttons (3)-(9) is pushed, one of the inputs of the NOR circuit (NOR 2 ) or the output of the NOR circuit (NOR 1 ) becomes 0, and the other input of the NOR CIRCUIT (NOR 2 ), with reception of the rising pulse from the complement side output (Q) of the monostable multivibrator (MM 1 ), resets the flip-flip circuits (F/F 2 ), (F/F 1 ) via the NOR circuit (NOR 3 ). Therefore the outputs (O 2 ), (O 1 ) of the outputs (O 5 )-(O 1 ) are rendered 0 0 and the pattern (6A') is selected.
FIG. 5 depicts another embodiment of this invention including a microcomputer (40) which is specifically programmed for a sewing machine and has seven output terminals (OUT 1 ) in such of which one is at any time grounded and the others not grounded, and the ground level is shifted with a constant increment within the terminal group. Now if one of the pattern selection buttons (3)-(9) is pushed, the input (in) of the microcomputer (40) encodes the operation of the button and compares the code with the previous code to cause a predetermined one of the four output terminals (OUT 2 ) to be grounded in the same manner as with the control circuit of FIG. 3 in which the transistors are operated in dependence upon the count of the flip-flop circuits (F/F 2 ), (F/F 1 ). The ground level will operate a predetermined one of the transistors in a timed relation with the selection button influencing the aforementioned shifted line. This is performed by the programmed operation of the microcomputer (40) so as to realize the pattern selection as well as the pattern indication just as realized in the control circuit in FIG. 3. | A rows-and-columns array of indicator lamps, each lamp associated with a selectable stitch pattern, is provided on the machine housing, with one pushbutton switch per column of indicator lamps. In a first embodiment, when a particular column and row contain the single illuminated one of the lamps, depression of the pushbutton switch associated with a different column terminates illumination of the presently lighted lamp and instead effects illumination of the lamp of the same row but in the column associated with the newly depressed pushbutton switch, whereupon repeated pressing of the newly pressed switch causes the illuminated state to shift, lamp by lamp, along such column. Alternatively, when the illuminated-lamp indication is located in a particular row and column, depression of the pushbutton switch associated with a different column causes the illuminated-lamp indication to jump to that column, and in particular always to a predetermined lamp within that column, e.g., the first therein. In this way, when the number of selectable stitch patterns is large, a comparatively small number of pushbutton switches can be utilized to control pattern selection in a way involving a regular and predetermined rule of displacement of the illuminated-lamp indication from column to column. | 3 |
This application is a continuation of application Ser. No. 09/289,222, filed on Apr. 9, 1999, now U.S. Pat. No. 6,193,918 B1.
FIELD OF THE INVENTION
The present invention relates to processes and equipment for embossing and applying adhesive to thin film webs.
BACKGROUND OF THE INVENTION
Three-dimensional sheet materials which include a thin layer of pressure-sensitive adhesive protected from inadvertent contact, as well as methods and apparatus for manufacturing them, have been developed and are described in detail in commonly-assigned U.S. Pat. No. 5,662,758, issued Sep. 2, 1997 to Hamilton and McGuire, entitled “Composite Material Releasably Sealable to a Target Surface When Pressed Thereagainst and Method of Making”, and U.S. Pat. No. 5,871,607, issued Feb. 16, 1999 to Hamilton and McGuire, entitled “Material Having A Substance Protected by Deformable Standoffs and Method of Making”, and commonly-assigned, co-pending U.S. patent application Ser. No. 08/745,339, filed Nov. 8, 1996 in the names of McGuire, Tweddell, and Hamilton, entitled “Three-Dimensional, Nesting-Resistant Sheet Materials and Method and Apparatus for Making Same”, now U.S. Pat. No. 5,695,235, 08/745,340, filed Nov. 8, 1996 in the names of Hamilton and McGuire, entitled “Improved Storage Wrap Materials”, all of which are hereby incorporated herein by reference.
While the processes and equipment for manufacturing such materials described in these applications/patents are suitable for manufacturing such materials on a comparatively small scale, the nature of the processes and equipment have been found to be rate-limiting by design. Said differently, the maximum speed at which such processes and equipment can be operated to produce such materials is limited by the size or weight of moving components, the rate at which heat can be applied to deformable substrate materials, the rate at which forces can be imparted to the substrate to deform it into the desired configuration, and/or the rate at which adhesive can be applied to the substrate and/or intermediate apparatus elements. The speed at which such processes and apparatus can be operated is a major factor in the economics of producing such materials on a commercial scale.
Accordingly, it would be desirable to provide a process and apparatus suitable for forming such three-dimensional sheet materials and applying adhesive at high speed.
SUMMARY OF THE INVENTION
The present invention provides a process which in a preferred embodiment includes the steps of. (a) applying a hot melt adhesive to a heated roll rotating at an initial tangential speed; (b) milling the adhesive to a reduced thickness and accelerating said adhesive through a series of metering gaps between a plurality of adjacent heated glue rolls; (c) applying the adhesive to a conformable glue application roll rotating at a tangential line speed which is higher than the initial tangential speed; (d) applying the adhesive to a first patterned embossing roll which is engaged with a second patterned embossing roll having a complementary pattern to the first embossing roll, the embossing rolls being heated; (e) passing a web of sheet material between the first and second embossing rolls at the tangential line speed to simultaneously emboss the web and apply the adhesive to the web, such that the adhesive forms an adhesive pattern between embossments; (f) transferring the web from the second embossing roll to the first embossing roll; (g) stripping the web from the first embossing roll; and (h) cooling the web.
BRIEF DESCRIPTION OF THE DRAWINGS
While the specification concludes with claims which particularly point out and distinctly claim the present invention, it is believed that the present invention will be better understood from the following description of preferred embodiments, taken in conjunction with the accompanying drawings, in which like reference numerals identify identical elements and wherein:
FIG. 1 is a schematic illustration of the process and apparatus according to the present invention;
FIG. 2 is an enlarged partial view of the apparatus of FIG. 1 illustrating the adhesive transfer step between the embossing rolls;
FIG. 3 is a plan view of four identical “tiles” of a representative embodiment of an amorphous pattern useful with the present invention;
FIG. 4 is a plan view of the four “tiles” of FIG. 3 moved into closer proximity to illustrate the matching of the pattern edges;
FIG. 5 is a schematic illustration of dimensions referenced in the pattern generation equations useful with the present invention; and
FIG. 6 is a schematic illustration of dimensions referenced in the pattern generation equations useful with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Process and Apparatus
FIG. 1 illustrates in schematic form the process and apparatus 10 of the present invention. The apparatus is composed fundamentally of two mated embossing rolls 15 and 16 , multiple glue metering/application rolls 11 - 14 , a pressure roll 17 , a strip-off roll 18 , and a chilled S-wrap 19 . The embossing rolls are steel, with a matched embossing pattern etched into them which interlocks to emboss a web of sheet material passed therebetween. The roll with pockets and raised lands is referred to as the female embossing roll 15 , while the roll with raised nubs and recessed lands is referred to as the male embossing roll 16 . The female embossing roll preferably has a release coating applied to its surface. The glue application/metering rolls 11 - 14 typically alternate between being plain steel or rubber-coated steel. The glue application roll 14 (the last roll in the glue system) is always rubber coated steel. The pressure roll 17 and strip off roll 18 are also rubber coated steel. The chilled S-wrap is composed of hollow steel rolls 19 with a release coating on their outside surfaces and coolant flowing through the rolls. The direction of roll rotation is shown in FIG. 1 with arrows.
More specifically, with reference to FIG. 1, an adhesive (such as a hot melt pressure sensitive adhesive) 40 is extruded onto the surface of the first rotating roll 11 via a heated slot die 9 . The slot die is supplied by a hot melt supply system (with a heated hopper and variable speed gear pump, not shown) through a heated hose. The surface speed of the first of the glue metering rolls 11 is considerably slower than the nominal tangential line speed of the web of sheet material 50 to be embossed and adhesive-coated. The metering nips are shown in FIG. 1 as stations 1 , 2 , and 3 . The remaining glue metering rolls 12 - 14 rotate progressively faster so that the glue application nip, station 4 , is surface speed matched. The glue 40 is transferred from the glue application roll 14 to the female embossing roll 15 at station 4 . The glue 40 travels with the female embossing roll surface to station 5 , where it is combined with the polymer web 50 which is carried into station 5 via male embossing roll 16 .
At station 5 , the polymer web 50 is embossed and combined with the glue 40 simultaneously to form an adhesive coated web 60 . The web 60 , glued to the surface of roll 15 , travels with the roll surface to station 6 , where a rubber coated pressure roll 17 applies pressure to the glued portion of the web. The web 60 , still glued to the female embossing roll 15 , travels to station 7 , where it is stripped off the female embossing roll 15 via strip-off roll 18 . The finished adhesive-coated web 60 then travels to the chilled S-wrap 19 at station 8 , where it is cooled to increase its strength.
The adhesive (or glue) 40 is applied to the land areas of the female embossing roll 15 only. This is accomplished by carefully controlling the female embossing roll to glue application roll clearance and runout at station 4 . The gap between these rolls is controlled such that the glue covered rubber roll 14 applies glue to the lands only, without pressing the glue into the recesses or pockets between lands.
The glue application roll 14 is a rubber coated steel roll. The rubber coating is ground in a special process to achieve approximately 0.001 inches TIR runout tolerance. The nip is controlled in the machine with precision wedge blocks. A rubber coating is utilized to (1) protect the coating on the female embossing roll 15 from damage due to metal-to-metal contact and (2) to allow the glue application roll to be very lightly pressed against the female embossing roll, so that the deflection of the rubber compensates for the actual runout of the embossing roll and glue application roll, allowing glue to be applied everywhere evenly on the female embossing roll lands.
The glue application roll 14 is lightly pressed against the female embossing roll 15 such that the deflection of the rubber surface compensates for embossing roll and glue application roll runout, but the deflection is not so high as to press glue into the pockets in the surface of the female embossing roll 15 . Deposition of glue exclusively onto the lands of the female embossing roll 15 is essential to prevent glue from being transferred onto the tops of the embossments in the web. Adhesive present on the tops of the embossments would cause them to exhibit adhesive properties prior to activation of the web via crushing of the embossments.
The adhesive or glue utilized is highly elastic in nature, and a transition from a stationary slot die 9 to full tangential line speed can result in the glue being extended and fractured, or in non-adhesion to the first metering roll. To reduce the extension rate of the glue, it is applied first to a slow moving roll and then through a series of metering gaps (stations 1 , 2 , and 3 ) it is milled down to a very thin glue film and accelerated at the desired tangential line speed.
The glue rolls must be ground to exacting tolerances for diameter and runout to maintain the precise inter-roll gap dimensions required for glue metering and acceleration. Typical runout tolerance is 0.00005 inches TIR. The glue rolls must be heated uniformly circumferentially and across the machine direction to avoid thermally-induced crown or runout of the rolls. It has been found that, in the case of electrically heated rolls, a single heater failure can create enough runout to prevent uniform glue printing onto the web. In such a case, ammeters are used to indicate heater failures. Heat loss through bearings and roll shafts can create roll crown, which also prevents uniform glue printing. Often the roll's bearing blocks must be heated to prevent temperature gradients in the cross machine direction.
The female embossing roll 15 preferably includes a release coating applied to both the land surfaces and to the surfaces of the pockets or recesses therebetween. The release coating and the glue properties must be carefully balanced to provide the best combination of adhesion and release. The coating must allow the very hot (typically 300-350° F.) glue to transfer to the female embossing roll and yet allow the adhesive-coated polymer film web to release at the embossing roll temperature (typically 160-180° F.). If the release coating promotes too little adhesion, the glue will not transfer from the glue application roll to the female embossing roll, while if the release coating promotes too much adhesion, the final adhesive-coated web cannot be removed from the surface of the female embossing roll without tearing or stretching the polymer film.
The film should be embossed at the highest possible embossing temperature to promote crisp, high-caliper embossments and allow the glued film web to release from the female embossing roll with lower strip-off force. However, the temperature of the embossing rolls must be kept below the softening point of the film web so that the final adhesively-coated web will have sufficient tensile strength to be removed from the female embossing roll. A balance between release temperature and film softening temperature has been found to be a critical parameter in defining successful operating conditions for operating at high speeds.
The strip-off roll assists in removing the final product from the female embossing roll without damaging the film. Since the product (film web) is glued to the surface of the female embossing roll, very high forces can be developed at the strip-off point. The strip off roll localizes these high forces to a very short length of web, resulting in less distortion of the web and more control over the strip-off angle. Preventing distortion of the final product is essential to provide consistent film properties and prevent the film from having regions which are prematurely activated to exhibit adhesive properties.
The amount or degree of engagement between the male and female embossing rolls must be carefully controlled to prevent damage to the rolls or to the film web. The outside surfaces of the embossing rolls are ground to a 0.00005 inch TIR runout tolerance. The engagement is controlled in the machine with precision wedge blocks. The engagement of the embossing rolls governs the final caliper of the film (i.e., the final height of the embossments).
Another important criteria is the fit or correspondence between the male and female embossing rolls. One useful technique is to form one roll via a photoetching process and utilize this roll as a “master” to form the other roll as a negative image. The equipment must also be designed so as to maintain precise synchronization of the mating embossing rolls.
The embossing and glue rolls are all individually heated and controlled to allow precise control of glue transfer temperatures and embossing roll release temperature.
The use of mating male and female embossing rolls of complementary pattern shapes fully supports the thin film web during the embossing and adhesive process step to ensure that the forces are properly distributed within the film material. Full support of the web, as opposed to thermoforming or vacuum forming a film with an open support structure such as an apertured belt or drum wherein the portion of the web being deformed into the apertures or recesses is unsupported, is believed to allow an increase in the rate at which strains are imparted to the web without damage to the web and thus allow for higher production speeds. The simultaneous application of the adhesive to the film during the embossing step provides precise registration of the adhesive on the undeformed portions of the web between embossments.
Precise control over the adhesive, particularly the thickness and uniformity of the adhesive layer applied to the female embossing roll, is an important factor in producing a high quality product at high speed. Especially in the case of very low add-on levels of adhesive, even slight variations in the thickness of the adhesive during transfers from roll to roll can result in coverage gaps by the time the adhesive is applied to the embossing roll. At the same time, such variations can lead to excess adhesive in certain regions of the embossing roll which could either contaminate the recesses in the roll or result in incomplete adhesive transfer to the web and a buildup of adhesive on the embossing roll.
Pattern Generation
FIGS. 3 and 4 show a pattern 20 created using an algorithm described in greater detail in commonly-assigned, co-pending U.S. patent application Ser. No. 09/288,786, filed Apr. 9, 1999, in the name of Kenneth S. McGuire, entitled “Method of Seaming and Expanding Amorphous Patterns”, the disclosure of which is hereby incorporated herein by reference. It is obvious from FIGS. 3 and 4 that there is no appearance of a seam at the borders of the tiles 20 when they are brought into close proximity. Likewise, if opposite edges of a single pattern or tile were brought together, such as by wrapping the pattern around a belt or roll, the seam would likewise not be readily visually discernible.
As utilized herein, the term “amorphous” refers to a pattern which exhibits no readily perceptible organization, regularity, or orientation of constituent elements. This definition of the term “amorphous” is generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in Webster's Ninth New Collegiate Dictionary. In such a pattern, the orientation and arrangement of one element with regard to a neighboring element bear no predictable relationship to that of the next succeeding element(s) beyond.
By way of contrast, the term “array” is utilized herein to refer to patterns of constituent elements which exhibit a regular, ordered grouping or arrangement. This definition of the term “array” is likewise generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in Webster's Ninth New Collegiate Dictionary. In such an array pattern, the orientation and arrangement of one element with regard to a neighboring element bear a predictable relationship to that of the next succeeding element(s) beyond.
The degree to which order is present in an array pattern of three-dimensional protrusions bears a direct relationship to the degree of nestability exhibited by the web. For example, in a highly-ordered array pattern of uniformly-sized and shaped hollow protrusions in a close-packed hexagonal array, each protrusion is literally a repeat of any other protrusion. Nesting of regions of such a web, if not in fact the entire web, can be achieved with a web alignment shift between superimposed webs or web portions of no more than one protrusion-spacing in any given direction. Lesser degrees of order may demonstrate less nesting tendency, although any degree of order is believed to provide some degree of nestability. Accordingly, an amorphous, non-ordered pattern of protrusions would therefore exhibit the greatest possible degree of nesting-resistance.
Three-dimensional sheet materials having a two-dimensional pattern of three-dimensional protrusions which is substantially amorphous in nature are also believed to exhibit “isomorphism”. As utilized herein, the terms “isomorphism” and its root “isomorphic” are utilized to refer to substantial uniformity in geometrical and structural properties for a given circumscribed area wherever such an area is delineated within the pattern. This definition of the term “isomorphic” is generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in Webster's Ninth New Collegiate Dictionary. By way of example, a prescribed area comprising a statistically-significant number of protrusions with regard to the entire amorphous pattern would yield statistically substantially equivalent values for such web properties as protrusion area, number density of protrusions, total protrusion wall length, etc. Such a correlation is believed desirable with respect to physical, structural web properties when uniformity is desired across the web surface, and particularly so with regard to web properties measured normal to the plane of the web such as crush-resistance of protrusions, etc.
Utilization of an amorphous pattern of three-dimensional protrusions has other advantages as well. For example, it has been observed that three-dimensional sheet materials formed from a material which is initially isotropic within the plane of the material remain generally isotropic with respect to physical web properties in directions within the plane of the material. As utilized herein, the term “isotropic” is utilized to refer to web properties which are exhibited to substantially equal degrees in all directions within the plane of the material. This definition of the term “isotropic” is likewise generally in accordance with the ordinary meaning of the term as evidenced by the corresponding definition in Webster's Ninth New Collegiate Dictionary. Without wishing to be bound by theory, this is presently believed to be due to the non-ordered, non-oriented arrangement of the three-dimensional protrusions within the amorphous pattern. Conversely, directional web materials exhibiting web properties which vary by web direction will typically exhibit such properties in similar fashion following the introduction of the amorphous pattern upon the material. By way of example, such a sheet of material could exhibit substantially uniform tensile properties in any direction within the plane of the material if the starting material was isotropic in tensile properties.
Such an amorphous pattern in the physical sense translates into a statistically equivalent number of protrusions per unit length measure encountered by a line drawn in any given direction outwardly as a ray from any given point within the pattern. Other statistically equivalent parameters could include number of protrusion walls, average protrusion area, average total space between protrusions, etc. Statistical equivalence in terms of structural geometrical features with regard to directions in the plane of the web is believed to translate into statistical equivalence in terms of directional web properties.
Revisiting the array concept to highlight the distinction between arrays and amorphous patterns, since an array is by definition “ordered” in the physical sense it would exhibit some regularity in the size, shape, spacing, and/or orientation of protrusions. Accordingly, a line or ray drawn from a given point in the pattern would yield statistically different values depending upon the direction in which the ray extends for such parameters as number of protrusion walls, average protrusion area, average total space between protrusions, etc. with a corresponding variation in directional web properties.
Within the preferred amorphous pattern, protrusions will preferably be non-uniform with regard to their size, shape, orientation with respect to the web, and spacing between adjacent protrusion centers. Without wishing to be bound by theory, differences in center-to-center spacing of adjacent protrusions are believed to play an important role in reducing the likelihood of nesting occurring in the face-to-back nesting scenario. Differences in center-to-center spacing of protrusions in the pattern result in the physical sense in the spaces between protrusions being located in different spatial locations with respect to the overall web. Accordingly, the likelihood of a “match” occurring between superimposed portions of one or more webs in terms of protrusions/space locations is quite low. Further, the likelihood of a “match” occurring between a plurality of adjacent protrusions/spaces on superimposed webs or web portions is even lower due to the amorphous nature of the protrusion pattern.
In a completely amorphous pattern, as would be presently preferred, the center-to-center spacing is random, at least within a designer-specified bounded range, such that there is an equal likelihood of the nearest neighbor to a given protrusion occurring at any given angular position within the plane of the web. Other physical geometrical characteristics of the web are also preferably random, or at least non-uniform, within the boundary conditions of the pattern, such as the number of sides of the protrusions, angles included within each protrusion, size of the protrusions, etc. However, while it is possible and in some circumstances desirable to have the spacing between adjacent protrusions be non-uniform and/or random, the selection of polygon shapes which are capable of interlocking together makes a uniform spacing between adjacent protrusions possible. This is particularly useful for some applications of the three-dimensional, nesting-resistant sheet materials of the present invention, as will be discussed hereafter.
As used herein, the term “polygon” (and the adjective form “polygonal”) is utilized to refer to a two-dimensional geometrical figure with three or more sides, since a polygon with one or two sides would define a line. Accordingly, triangles, quadrilaterals, pentagons, hexagons, etc. are included within the term “polygon”, as would curvilinear shapes such as circles, ellipses, etc. which would have an infinite number of sides.
When describing properties of two-dimensional structures of non-uniform, particularly non-circular, shapes and non-uniform spacing, it is often useful to utilize “average” quantities and/or “equivalent” quantities. For example, in terms of characterizing linear distance relationships between objects in a two-dimensional pattern, where spacings on a center-to-center basis or on an individual spacing basis, an “average” spacing term may be useful to characterize the resulting structure. Other quantities that could be described in terms of averages would include the proportion of surface area occupied by objects, object area, object circumference, object diameter, etc. For other dimensions such as object circumference and object diameter, an approximation can be made for objects which are non-circular by constructing a hypothetical equivalent diameter as is often done in hydraulic contexts.
A totally random pattern of three-dimensional hollow protrusions in a web would, in theory, never exhibit face-to-back nesting since the shape and alignment of each frustum would be unique. However, the design of such a totally random pattern would be very time-consuming and complex proposition, as would be the method of manufacturing a suitable forming structure. In accordance with the present invention, the non-nesting attributes may be obtained by designing patterns or structures where the relationship of adjacent cells or structures to one another is specified, as is the overall geometrical character of the cells or structures, but wherein the precise size, shape, and orientation of the cells or structures is non-uniform and non-repeating. The term “non-repeating”, as utilized herein, is intended to refer to patterns or structures where an identical structure or shape is not present at any two locations within a defined area of interest. While there may be more than one protrusion of a given size and shape within the pattern or area of interest, the presence of other protrusions around them of non-uniform size and shape virtually eliminates the possibility of an identical grouping of protrusions being present at multiple locations. Said differently, the pattern of protrusions is non-uniform throughout the area of interest such that no grouping of protrusions within the overall pattern will be the same as any other like grouping of protrusions. The beam strength of the three-dimensional sheet material will prevent significant nesting of any region of material surrounding a given protrusion even in the event that that protrusion finds itself superimposed over a single matching depression since the protrusions surrounding the single protrusion of interest will differ in size, shape, and resultant center-to-center spacing from those surrounding the other protrusion/depression.
Professor Davies of the University of Manchester has been studying porous cellular ceramic membranes and, more particularly, has been generating analytical models of such membranes to permit mathematical modeling to simulate real-world performance. This work was described in greater detail in a publication entitled “Porous cellular ceramic membranes: a stochastic model to describe the structure of an anodic oxide membrane”, authored by J. Broughton and G. A. Davies, which appeared in the Journal of Membrane Science, Vol. 106 (1995), at pp. 89-101, the disclosure of which is hereby incorporated herein by reference. Other related mathematical modeling techniques are described in greater detail in “Computing the n-dimensional Delaunay tessellation with application to Voronoi polytopes”, authored by D. F. Watson, which appeared in The Computer Journal, Vol. 24, No. 2 (1981), at pp. 167-172, and “Statistical Models to Describe the Structure of Porous Ceramic Membranes”, authored by J. F. F. Lim, X. Jia, R. Jafferali, and G. A. Davies, which appeared in Separation Science and Technology, 28(1-3) (1993) at pp. 821-854, the disclosures of both of which are hereby incorporated herein by reference.
As part of this work, Professor Davies developed a two-dimensional polygonal pattern based upon a constrained Voronoi tessellation of 2-space. In such a method, again with reference to the above-identified publication, nucleation points are placed in random positions in a bounded (pre-determined) plane which are equal in number to the number of polygons desired in the finished pattern. A computer program “grows” each point as a circle simultaneously and radially from each nucleation point at equal rates. As growth fronts from neighboring nucleation points meet, growth stops and a boundary line is formed. These boundary lines each form the edge of a polygon, with vertices formed by intersections of boundary lines.
While this theoretical background is useful in understanding how such patterns may be generated and the properties of such patterns, there remains the issue of performing the above numerical repetitions step-wise to propagate the nucleation points outwardly throughout the desired field of interest to completion. Accordingly, to expeditiously carry out this process a computer program is preferably written to perform these calculations given the appropriate boundary conditions and input parameters and deliver the desired output.
The first step in generating a pattern useful in accordance with the present invention is to establish the dimensions of the desired pattern. For example, if it is desired to construct a pattern 10 inches wide and 10 inches long, for optionally forming into a drum or belt as well as a plate, then an X-Y coordinate system is established with the maximum X dimension (x max ) being 10 inches and the maximum Y dimension (y max ) being 10 inches (or vice-versa).
After the coordinate system and maximum dimensions are specified, the next step is to determine the number of “nucleation points” which will become polygons desired within the defined boundaries of the pattern. This number is an integer between 0 and infinity, and should be selected with regard to the average size and spacing of the polygons desired in the finished pattern. Larger numbers correspond to smaller polygons, and vice-versa. A useful approach to determining the appropriate number of nucleation points or polygons is to compute the number of polygons of an artificial, hypothetical, uniform size and shape that would be required to fill the desired forming structure. If this artificial pattern is an array of regular hexagons 30 (see FIG. 5 ), with D being the edge-to-edge dimension and M being the spacing between the hexagons, then the number density of hexagons, N, is: N = 2 3 3 ( D + M ) 2
It has been found that using this equation to calculate a nucleation density for the amorphous patterns generated as described herein will give polygons with average size closely approximating the size of the hypothetical hexagons (D). Once the nucleation density is known, the total number of nucleation points to be used in the pattern can be calculated by multiplying by the area of the pattern (80 in 2 in the case of this example).
A random number generator is required for the next step. Any suitable random number generator known to those skilled in the art may be utilized, including those requiring a “seed number” or utilizing an objectively determined starting value such as chronological time. Many random number generators operate to provide a number between zero and one (0-1), and the discussion hereafter assumes the use of such a generator. A generator with differing output may also be utilized if the result is converted to some number between zero and one or if appropriate conversion factors are utilized.
A computer program is written to run the random number generator the desired number of iterations to generate as many random numbers as is required to equal twice the desired number of “nucleation points” calculated above. As the numbers are generated, alternate numbers are multiplied by either the maximum X dimension or the maximum Y dimension to generate random pairs of X and Y coordinates all having X values between zero and the maximum X dimension and Y values between zero and the maximum Y dimension. These values are then stored as pairs of (X,Y) coordinates equal in number to the number of “nucleation points”.
It is at this point, that the invention described herein differs from the pattern generation algorithm described in the previous McGuire et al. application. Assuming that it is desired to have the left and right edge of the pattern “mesh”, i.e., be capable of being “tiled” together, a border of width B is added to the right side of the 10″ square (see FIG. 6 ). The size of the required border is dependent upon the nucleation density; the higher the nucleation density, the smaller is the required border size. A convenient method of computing the border width, B, is to refer again to the hypothetical regular hexagon array described above and shown in FIG. 5 . In general, at least three columns of hypothetical hexagons should be incorporated into the border, so the border width can be calculated as:
B= 3( D +H )
Now, any nucleation point P with coordinates (x,y) where x<B will be copied into the border as another nucleation point, P′, with a new coordinate (x max +x,y).
If the method described in the preceding paragraphs is utilized to generate a resulting pattern, the pattern will be truly random. This truly random pattern will, by its nature, have a large distribution of polygon sizes and shapes which may be undesirable in some instances. In order to provide some degree of control over the degree of randomness associated with the generation of “nucleation point” locations, a control factor or “constraint” is chosen and referred to hereafter as β (beta). The constraint limits the proximity of neighboring nucleation point locations through the introduction of an exclusion distance, E, which represents the minimum distance between any two adjacent nucleation points. The exclusion distance E is computed as follows: E = 2 β λπ
where λ (lambda) is the number density of points (points per unit area) and β ranges from 0 to 1.
To implement the control of the “degree of randomness”, the first nucleation point is placed as described above. β is then selected, and E is calculated from the above equation. Note that β, and thus E, will remain constant throughout the placement of nucleation points. For every subsequent nucleation point (x,y) coordinate that is generated, the distance from this point is computed to every other nucleation point that has already been placed. If this distance is less than E for any point, the newly-generated (x,y) coordinates are deleted and a new set is generated. This process is repeated until all N points have been successfully placed. Note that in the tiling algorithm useful in accordance with the present invention, for all points (x,y) where x<B, both the original point P and the copied point P′ must be checked against all other points. If either P or P′ is closer to any other point than E, then both P and P′ are deleted, and a new set of random (x,y) coordinates is generated.
If β=0, then the exclusion distance is zero, and the pattern will be truly random. If β=1, the exclusion distance is equal to the nearest neighbor distance for a hexagonally close-packed array. Selecting β between 0 and 1 allows control over the “degree of randomness” between these two extremes.
In order to make the pattern a tile in which both the left and right edges tile properly and the top and bottom edges tile properly, borders will have to be used in both the X and Y directions.
Once the complete set of nucleation points are computed and stored, a Delaunay triangulation is performed as the precursor step to generating the finished polygonal pattern. The use of a Delaunay triangulation in this process constitutes a simpler but mathematically equivalent alternative to iteratively “growing” the polygons from the nucleation points simultaneously as circles, as described in the theoretical model above. The theme behind performing the triangulation is to generate sets of three nucleation points forming triangles, such that a circle constructed to pass through those three points will not include any other nucleation points within the circle. To perform the Delaunay triangulation, a computer program is written to assemble every possible combination of three nucleation points, with each nucleation point being assigned a unique number (integer) merely for identification purposes. The radius and center point coordinates are then calculated for a circle passing through each set of three triangularly-arranged points. The coordinate locations of each nucleation point not used to define the particular triangle are then compared with the coordinates of the circle (radius and center point) to determine whether any of the other nucleation points fall within the circle of the three points of interest. If the constructed circle for those three points passes the test (no other nucleation points falling within the circle), then the three point numbers, their X and Y coordinates, the radius of the circle, and the X and Y coordinates of the circle center are stored. If the constructed circle for those three points fails the test, no results are saved and the calculation progresses to the next set of three points.
Once the Delaunay triangulation has been completed, a Voronoi tessellation of 2-space is then performed to generate the finished polygons. To accomplish the tessellation, each nucleation point saved as being a vertex of a Delaunay triangle forms the center of a polygon. The outline of the polygon is then constructed by sequentially connecting the center points of the circumscribed circles of each of the Delaunay triangles, which include that vertex, sequentially in clockwise fashion. Saving these circle center points in a repetitive order such as clockwise enables the coordinates of the vertices of each polygon to be stored sequentially throughout the field of nucleation points. In generating the polygons, a comparison is made such that any triangle vertices at the boundaries of the pattern are omitted from the calculation since they will not define a complete polygon.
If it is desired for ease of tiling multiple copies of the same pattern together to form a larger pattern, the polygons generated as a result of nucleation points copied into the computational border may be retained as part of the pattern and overlapped with identical polygons in an adjacent pattern to aid in matching polygon spacing and registry. Alternatively, as shown in FIGS. 3 and 4, the polygons generated as a result of nucleation points copied into the computational border may be deleted after the triangulation and tessellation are performed such that adjacent patterns may be abutted with suitable polygon spacing.
Once a finished pattern of interlocking polygonal two-dimensional shapes is generated, in accordance with the present invention such a network of interlocking shapes is utilized as the design for one web surface of a web of material with the pattern defining the shapes of the bases of the three-dimensional, hollow protrusions formed from the initially planar web of starting material. In order to accomplish this formation of protrusions from an initially planar web of starting material, a suitable forming structure comprising a negative of the desired finished three-dimensional structure is created which the starting material is caused to conform to by exerting suitable forces sufficient to permanently deform the starting material.
From the completed data file of polygon vertex coordinates, a physical output such as a line drawing may be made of the finished pattern of polygons. This pattern may be utilized in conventional fashion as the input pattern for a metal screen etching process to form a three-dimensional forming structure. If a greater spacing between the polygons is desired, a computer program can be written to add one or more parallel lines to each polygon side to increase their width (and hence decrease the size of the polygons a corresponding amount).
While particular embodiments of the present invention have been illustrated and described, it will be obvious to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, and it is intended to cover in the appended claims all such modifications that are within the scope of the invention. | The present invention provides a process which in a preferred embodiment includes the steps of. (a) applying a hot melt adhesive to a heated roll rotating at an initial tangential speed; (b) milling the adhesive to a reduced thickness and accelerating said adhesive through a series of metering gaps between a plurality of adjacent heated glue rolls; (c) applying the adhesive to a conformable glue application roll rotating at a tangential line speed which is higher than the initial tangential speed; (d) applying the adhesive to a first patterned embossing roll which is engaged with a second patterned embossing roll having a complementary pattern to the first embossing roll, the embossing rolls being heated; (e) passing a web of sheet material between the first and second embossing rolls at the tangential line speed to simultaneously emboss the web and apply the adhesive to the web, such that the adhesive forms an adhesive pattern between embossments; (f) transferring the web from the second embossing roll to the first embossing roll; (g) stripping the web from the first embossing roll; and (h) cooling the web. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] The following patent applications, all of which were filed on the same day as this patent application, are hereby incorporated by reference into this patent application as if set forth herein in full: (1) U.S. patent application Ser. No. ______, entitled “Injection Molded PTC-Ceramics”, Attorney Docket No. 14219-186001, Application Ref. P2007,1179USE; (2) U.S. patent application Ser. No. ______, entitled “Feedstock And Method For Preparing The Feedstock”, Attorney Docket No. 14219-187001, Application Ref. P2007,1180USE; (3) U.S. patent application Ser. No. ______, entitled “Mold Comprising PTC-Ceramic”, Attorney Docket No. 14219-184001, Application Ref. P2007,1181USE; (4) U.S. patent application Ser. No. ______, entitled “Injection Molded Nozzle And Injector And Injector Comprising The Injection Molded Nozzle”, Attorney Docket No. 14219-183001, Application Ref. P2007,1183USE; and (5) U.S. patent application Ser. No. ______, entitled “PTC-Resistor”, Attorney Docket No. 14219-185001, Application Ref. P2007,1184USE.
TECHNICAL FIELD
[0002] This disclosure relates to a process of heating fluids using a ceramic PTC heater. The abbreviation PTC stands for Positive Temperature Coefficient. These are therefore heaters which, at least within a limited temperature interval, have a positive temperature coefficient of the electrical resistance. This disclosure also relates to an injection molded molding.
BACKGROUND
[0003] Ceramic PTC heaters for heating fluids are in general made in the form of compressed pills or simple geometrical structures like a cube. The ceramic PTC element is placed inside a tube for heating the fluid which passes along the PTC element. The ratio of the volume to the heating surface of these simple geometrical ceramic PTC structures was found to be insufficient for certain applications.
SUMMARY
[0004] By using non simple structures entirely made of ceramic PTC material for heating fluids such as gases or liquids advantages can be obtained. Complex geometrical forms which cannot be formed by compression or extrusion molding can be formed by injection molding. Injection molded structures obtain for every straight line through the injection molded molding at least two cross sectional areas perpendicular to this line, which cannot be accommodated on each other by a translation along this line.
[0005] In contrast, geometrical structures formed by extrusion molding comprise one line through the structure, whereby the whole structure comprises the same cross-section along this line.
[0006] It is therefore not possible to obtain a geometrical structure by extrusion molding which comprises a section which can not be formed by extrusion through a die.
[0007] The feedstock used for injection molding comes in the form of granules. These granules contain powdered ceramic material comprising BaTiO 3 together with an organic binder. The feedstock is melted at high pressure into a mold, which is the inverse shape of the product's shape.
[0008] The injection moldable feedstock may comprise a ceramic filler, a matrix for binding the filler and a content of, e.g., less than 10 ppm of metallic impurities.
[0009] The ceramic may for example be based on Bariumtitanate (BaTiO 3 ), which is a ceramic of the perovskite-type (ABO 3 ).
[0010] For the injection molding process a feedstock could be used comprising a ceramic filler, a matrix for binding the filler and a content of less than 10 ppm of metallic impurities. One possible ceramic filler can be denoted by the structure:
[0000] Ba 1-x-y M x D y Ti 1-a-b N a Mn b O 3
[0000] wherein the parameters are x=0 to 0.5, y=0 to 0.01, a=0 to 0.01 and b=0 to 0.01. In this structure M stands for a cation of the valency two, like for example Ca, Sr or Pb, D stands for a donor of the valency three or four, for example Y, La or rare earth elements, and N stands for a cation of the valency five or six, for example Nb or Sb. Thus, a high variety of ceramic materials can be used wherein the composition of the ceramic may be chosen in dependency of the required electrical features of the later sintered ceramic.
[0011] The ceramic filler of the feedstock is convertible to a PTC-ceramic with low resistivity and a steep slope of the resistance-temperature curve. The resistivity of a PTC-ceramic made of such a feedstock can comprise a range from 3 Ωcm to 30000 Ωcm at 25° C. in dependence of the composition of the ceramic filler and the conditions during sintering the feedstock. The characteristic temperature Tb at which the resistance begins to increase comprises a range of −30° C. to 340° C. As higher amounts of impurities could impede the electrical features of the molded PTC-ceramic the content of the metallic impurities in the feedstock is lower than 10 ppm.
[0012] The metallic impurities in the feedstock may comprise Fe, Al, Ni, Cr and W. Their content in the feedstock, in combination with one another or each respectively, is less than 10 ppm due to abrasion from tools employed during the preparation of the feedstock.
[0013] The preparation of the feedstock comprises using tools having such a low degree of abrasion that a feedstock comprising less than 10 ppm of impurities caused by said abrasion is obtained. Thus, preparation of injection moldable feedstocks with a low amount of abrasion caused metallic impurities is achieved without the loss of desired electrical features of the molded PTC-ceramic.
[0014] The tools used for preparation of the feedstock comprise coatings of a hard material. The coating may comprise any hard metal, such as, for example, Tungsten Carbide (WC). Such a coating reduces the degree of abrasion of the tools when in contact with the mixture of ceramic filler and matrix and enables the preparation of a feedstock with a low amount of metallic impurities caused by said abrasion. Metallic impurities may be Fe, but also Al, Ni or Cr. When the tools are coated with a hard coating such as WC, impurities of W may be introduced into the feedstock. However, these impurities have a content of less than 50 ppm. It was found that in this concentration, they do not influence the desired electrical features of the sintered PTC-ceramic.
[0015] Where injection molding is used to form the mold, care must be taken regarding the metallic impurities in the mold to ensure that the efficiency of the PTC-ceramic is not reduced. The PTC-effect of ceramic materials comprises a change of the electric resistivity ρ as a function of the temperature T. While in a certain temperature range the change of the resistivity ρ is small with a rise of the temperature T, starting at the so-called Curie-temperature T c the resistivity ρ rapidly increases with a rise of temperature. In this second temperature range, the temperature coefficient, which is the relative change of the resistivity at a given temperature, can have a value of 100%/K. If there is no rapidly increase at the Curie-temperature the self regulating property of the mold is unsatisfactory.
[0016] Features of the injection molded molding for heating a fluid are shown in more detail with the following detailed description when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] FIG. 1 is a view of a first embodiment of a ceramic PTC heater;
[0018] FIG. 2 is a view of a second embodiment of a ceramic PTC heater;
[0019] FIG. 3 is a view of a third embodiment of a ceramic PTC heater;
[0020] FIG. 4 is a view of a fourth embodiment of a ceramic PTC heater;
[0021] FIG. 5 is a view of a fourth embodiment of a ceramic PTC heater of FIG. 4 from another perspective; and
[0022] FIG. 6 is a view of a fifth embodiment of a ceramic PTC heater.
DETAILED DESCRIPTION
[0023] FIG. 1 is a perspective view showing an embodiment of a ceramic PTC heater used for heating fluids. The ceramic PTC heater of FIG. 1 shows a main tubular body 1 which comprises a least one flange 2 on one end of the tubular body. The flange 2 can also be located anywhere in lateral direction of the ceramic PTC heater. The flange 2 comprises two holes 3 . The holes 3 can be used for fastening the ceramic PTC heater to a tube or something else. The flange 2 can comprise any number of holes 3 , the flange 2 is not limited to two holes 3 . The ceramic PTC heater shown in FIG. 1 may be used as a heating section for fluids circulating through a tube.
[0024] The tubular body 1 comprises one or more protrusions. In FIG. 1 , the protrusion has the form of a fin 4 . At least one fin 4 is placed inside the tubular body 1 of the ceramic PTC heater. The ceramic PTC heater shows four fins 4 inside the tubular body 1 .
[0025] In another embodiment, the fins 4 inside the tubular body 1 can extend in a lateral direction, whereby the fins of the extended section can no longer be surrounded by a tubular body 1 .
[0026] The first embodiment of the ceramic PTC heater shown in FIG. 1 is used for heating fluids such as gas or a liquid which circulate through the tubular body 1 of the ceramic PTC heater. The fins 4 inside the tubular section 1 offer a larger surface area for heating the fluid circulating along these fins 4 .
[0027] The entire structure of the ceramic PTC heater is formed by injection molding of a ceramic PTC feedstock, e.g., in one single step. The ceramic PTC feedstock may contain less than 10 ppm (parts per million) of metallic impurities. Metallic impurities in ceramic PTCs affect the characteristics of the ceramic PTC in an unwanted manner.
[0028] Complex geometrical forms which cannot be formed by compression or extrusion molding can be formed by injection molding. Injection molded structures exhibit for every straight line through the injection molded molding at least two cross sectional areas perpendicular to this line, which cannot be superimposed on each other with a flush overlap by a translation along this line.
[0029] The ceramic PTC heater comprises at least one region comprising a conductive coating. The conductive coating may be used for electrically contacting of the ceramic PTC heater. The conductive coating can for example comprise Cr, Ni, Al, Ag or any other suitable material. For larger moldings the electric coating is advantageously applied on two opposite regions of the ceramic PTC heater.
[0030] It is advantageous for larger moldings to apply the electric coating on the inside and on the outside surface of the ceramic PTC heater. Heating effects may appear around regions of the electrically conductive coating. Thus, for larger moldings, like the one shown in FIG. 1 , one electrical coating may be applied on the complete inside surface including the tubular body 1 and the fins 4 and another on the complete outer surface of the tubular body 1 . For smaller moldings the electric coating can be applied as small strips on the surface of the ceramic PTC heater.
[0031] To obtain a protection of the ceramic PTC heater from corrosive or harmful substances, the surface of the molding, which is in contact to a fluid, may include a passivation coating. In an embodiment, the passivation coating comprises a corrosion protection. The corrosion protection can be carried out by a low melting glass or nano-composite lacquer coating, or by any other coating which protects the ceramic surface of the molding from the fluid circulating along or through the ceramic PTC heater. The nano-composite lacquer can comprise one or more of the following composites: SiO 2 -polyacrylate-composite, SiO 2 -polyether-composite, SiO 2 -silicone-composite.
[0032] In another embodiment of the ceramic PTC heater, the fins inside the tubular body can be provided in a twisted shape to obtain a velocity of the fluid circulating through the ceramic PTC heater. Thus, a more effective heating of the fluid can be achieved. The twisted fins cause a turbulence of the fluid, which leads to a higher degree of efficiency of heat transfer from the ceramic PTC heater to the fluid.
[0033] FIG. 2 is a perspective view showing a second embodiment of a ceramic PTC heater. The ceramic PTC heater of FIG. 2 is designed to be placed into an external tube. The ceramic PTC heater comprises at least one flange 2 comprising a form similar to a cross according to the center of the cross-section. The cross is formed by the front face of four protrusions in form of fins 4 . The fins 4 are arranged perpendicular to each other. The number of fins 4 is not limited to four fins. Any other number of fins 4 is possible.
[0034] The ceramic PTC heater comprises a least one flange 2 , e.g., on one end of the ceramic PTC heater. The flange 2 can also be placed between the two ends of the ceramic PTC heater. Thus, the ceramic PTC heater can be placed between two tubes for heating of the fluid flowing through them.
[0035] It is also possible that the ceramic PTC heater comprises two flanges 2 , one with a small cross section to fit inside a tube, and one bigger flange 2 . The smaller flange 2 can be used for connecting the ceramic PTC heater inside a tube, and the bigger flange 2 for connecting on the outside of the tube. The flange 2 shown in FIG. 2 comprises two holes 3 . The flange 2 can comprise any number of holes 3 . The holes 3 can be used for connecting the ceramic PTC heater to another flange of a tube. The electrical contact of the ceramic PTC heater is achieved by an electrical coating that may be on the fins 4 of the PTC heater.
[0036] To obtain a protection of the ceramic PTC heater from corrosive or other harmful substances, the surface of the molding, which is in contact to a fluid, may include a passivation coating. The passivation coating comprises a corrosion protection which can for example be carried out by a glass coating, or by any other coating which protects the ceramic surface of the molding from the fluid circulating along or through the ceramic PTC heater.
[0037] The third embodiment shown in FIG. 3 is similar to the second embodiment shown in FIG. 2 . The fins 4 of the ceramic PTC heater are twisted similar to the thread of a screw. The fluid circulating along the fins 4 is vortexed by the twisted fins 4 . Thus, a higher degree of efficiency of heat transfer from the ceramic PTC heater to the fluid is achieved. These complex geometrical forms may be formed by injection molding cannot be formed by extrusion molding. Injection molded complex geometrical structures obtain for every straight line through the injection molded molding at least two cross sectional areas perpendicular to this line, which cannot be superimposed on one another with a flush overlap by a translation along this line. At least one flange 2 with holes 3 can be placed at an end of the ceramic PTC heater or at a position between the ends.
[0038] The embodiment shown in FIG. 4 is a front view of a propeller shaped body. The body is formed of PTC ceramic by injection molding. The propeller comprises four protrusions in the form of blades 5 which are regularly arranged around a driving collar 6 . The blades 5 may be swiveled backwards.
[0039] It is also possible that the propeller comprises a driving collar 6 with any reasonable number or form of protrusions. The propeller can comprise two, three, four, five or more blades 5 around the driving collar 6 . The embodiment in FIG. 4 only shows a propeller with four blades 5 , but almost any other quantity of blades 5 is possible. The backwards swiveled blades 5 cause a turbulent flow of the fluid circulating along the propeller. Thus, heat transfer with an high degree of efficiency and transport of the fluid can be achieved simultaneously. With a propeller of a ceramic PTC an efficient continuous heating of fluids can be obtained.
[0040] An electrical coating may be applied to the main surfaces of the propeller blades 5 . Thus, a maximum area of the surface of the blades 5 can be used for heating the fluid. The electrical contacts are implemented by electrical coatings, which extend to the driving collar 6 of the propeller. The edge of the blades 5 may be devoid of an electrical coating. Thus, each blade 5 may act as one heating element by itself, with electrical coating on each side. The propeller may comprise a passivation coating for corrosion protection.
[0041] The embodiment in FIG. 5 is rotated in the perspective but otherwise corresponds to FIG. 4 . The blades 5 of the propeller are arranged along the axis of the driving collar 6 . The blades 5 are swiveled backwards to obtain a more effective heating and hauling of the air.
[0042] FIG. 6 is a perspective view showing a further embodiment of a ceramic PTC heater. The ceramic PTC heater in FIG. 6 has the form of a propeller. The propeller may be placed inside a tubular body 1 with a bearing on the outside of the tubular body 1 . The blades 5 of the propeller are swiveled backwards to obtain a more efficient heating and transport of the fluid streaming through the molding. The ceramic PTC heater may be formed by injection molding.
[0043] The embodiment in FIG. 6 is also referred to as an impeller. Impellers are used within tubes or conduits to increase the pressure and flow of a fluid. Impellers are usually short cylinders with protrusions forming blades to push or propel the fluid and a splined center to accept a driveshaft. To work efficiently, there must be a close fit between the impeller and the housing. The housing can be a tube or conduit, in which the impeller is applied.
[0044] The embodiments described in FIG. 1 to FIG. 6 can be applied for heating of fluids within an air conditioning system of an automobile.
[0045] Other implementations are within the scope of the following claims. Elements of different implementations, including elements from applications incorporated herein by reference, may be combined to form implementations not specifically described herein. | A process for heating a fluid includes providing an injection molded molding made of a ceramic material with a positive temperature coefficient containing less than 10 ppm of metallic impurities, and using the injection molded molding to heat a fluid. For a straight line through the injection molded molding, at least two cross sectional areas perpendicular to the line cannot be superimposed on each other via a translation along the line, | 7 |
CLAIM OF PRIORITY UNDER 35 U.S.C. §119
The present Application for Patent claims priority to Provisional Application No. 61/527,968 entitled “IN-BAND SIGNALING TO INDICATE END OF DATA STREAM AND UPDATE USER CONTEXT” filed Aug. 26, 2011, and assigned to the assignee hereof and hereby expressly incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
Embodiments of the invention relate to in-band signaling to indicate an end of incoming stream of data for real-time, or near real-time and user-context update.
2. Description of the Related Art
Wireless communication systems have developed through various generations, including a first-generation analog wireless phone service (1G), a second-generation (2G) digital wireless phone service (including interim 2.5G and 2.75G networks) and a third-generation (3G) high speed data/Internet-capable wireless service. There are presently many different types of wireless communication systems in use, including Cellular and Personal Communications Service (PCS) systems. Examples of known cellular systems include the cellular Analog Advanced Mobile Phone System (AMPS), and digital cellular systems based on Code Division Multiple Access (CDMA), Frequency Division Multiple Access (FDMA), Time Division Multiple Access (TDMA), the Global System for Mobile access (GSM) variation of TDMA, and newer hybrid digital communication systems using both TDMA and CDMA technologies.
The method for providing CDMA mobile communications was standardized in the United States by the Telecommunications Industry Association/Electronic Industries Association in TIA/EIA/IS-95-A entitled “Mobile Station-Base Station Compatibility Standard for Dual-Mode Wideband Spread Spectrum Cellular System,” referred to herein as IS-95. Combined AMPS & CDMA systems are described in TIA/EIA Standard IS-98. Other communications systems are described in the IMT-2000/UM, or International Mobile Telecommunications System 2000/Universal Mobile Telecommunications System, standards covering what are referred to as wideband CDMA (W-CDMA), CDMA2000 (such as CDMA2000 1xEV-DO standards, for example) or TD-SCDMA.
In W-CDMA wireless communication systems, user equipments (UEs) receive signals from fixed position Node Bs (also referred to as cell sites or cells) that support communication links or service within particular geographic regions adjacent to or surrounding the base stations. Node Bs provide entry points to an access network (AN)/radio access network (RAN), which is generally a packet data network using standard Internet Engineering Task Force (IETF) based protocols that support methods for differentiating traffic based on Quality of Service (QoS) requirements. Therefore, the Node Bs generally interact with UEs through an over the air interface and with the RAN through Internet Protocol (IP) network data packets.
In wireless telecommunication systems, Push-to-Talk (PTT) capabilities are popular with service sectors and consumers. PTT can support a “dispatch” voice service that operates over standard commercial wireless infrastructures, such as W-CDMA, CDMA, FDMA, TDMA, GSM, etc. In a dispatch model, communication between endpoints (e.g., UEs) occurs within virtual groups, wherein the voice of one “talker” is transmitted to one or more “listeners.” A single instance of this type of communication is commonly referred to as a dispatch call, or simply a PTT call. A PTT call is an instantiation of a group, which defines the characteristics of a call. A group in essence is defined by a member list and associated information, such as group name or group identification.
Applications, which are receiving one or more incoming streams of data (e.g., audio, video, etc), need to update a user context when the steam of data ends. Some applications may have real-time (e.g., minimum latency) requirements for the user context update, and therefore these applications require precise and instantaneous knowledge regarding when the stream of data ends. Conventionally, the end of the stream of data can be inferred after a period of traffic inactivity, or can be expressly indicated via the use of out-of-band signaling (e.g., via an “END” signal). Generally, out-of-band signaling can be delayed and can be complex to implement. Also, relying on out-of-band signaling for indicating the end of a stream of data may leave a gap in time where the “END” signal arrives either too early or too late, which results in the possibility of truncating the stream short (e.g., if “END” signal arrives early) or permitting the stream to continue in a starved mode (e.g., if “END” signal arrives late, such that RTP packets stop arriving but there is no user-context update).
In addition, the use of inactivity timers involves updating the user context after a threshold period where no streaming packets associated with the stream of data are received. Inferring the end of a session based on an inactivity timer can be difficult because the inactivity timer must accommodate temporary network disruptions as well as actual stream termination, and a single timer value is unlikely to be appropriate for both scenarios.
SUMMARY
An embodiment of the disclosure relates to indicating an end of a stream of data using in-band signaling. An embodiment transmits the stream of data, the stream of data comprising multiple packets, each packet of the multiple packets including a header with a marker bit field and a payload, configures the marker bit field and/or the payload of at least one packet of the multiple packets to indicate the end of the stream of data, wherein the marker bit field being set in the at least one packet indicates that the payload of the at least one packet is less than payloads of other packets of the multiple packets and/or setting a field in the payload indicating a countdown to a last packet of the stream of data, detects at a server, out-of-band signaling indicating the end of the stream of data before detecting the configuring the marker bit field and the payload of the at least one packet, wherein the server performs the configuring of the marker bit field and the payload in response to the detecting the out-of-band signaling, transmits the configured at least one packet to at least one target device, and in event that no marker bit and no out-of-band signaling is detected, the server generates a packet comprising a new marker bit and transmits the generated packet with the new marker bit to the at least one target device, wherein the new marker bit indicates the end of the stream of data.
An embodiment of the disclosure relates to detecting an end of a stream of data using in-band signaling. An embodiment receives the stream of data, the stream of data comprising multiple packets, each packet of the multiple packets including a header with a marker bit field and a payload, detects that at least one packet of the multiple packets is configured to indicate the end of the stream of data, that the payload of the at least one packet contains an amount of data less than payloads of other packets of the multiple packets, and/or that the payload of the at least one packet contains a field indicating a countdown to a last packet of the stream of data,detects at a server, out-of-band signaling indicating the end of the stream of data before detecting the configuring of the at least one packet, wherein the server performs the configuring in response to the detecting the out-of-band signaling, transmits the configured at least one packet to at least one target device, and in event that no marker bit and no out-of-band signaling is detected, the server generates a packet comprising a new marker bit and transmits the generated packet with the new marker bit to the at least one target device, wherein the new marker bit indicates the end of the data stream.
Further scope of the applicability of the described methods and apparatuses will become apparent from the following detailed description, claims, and drawings. The detailed description and specific examples, while indicating specific examples of the disclosure and claims, are given by way of illustration only, since various changes and modifications within the spirit and scope of the description will become apparent to those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete appreciation of embodiments of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings which are presented solely for illustration and not limitation of the invention, and in which:
FIG. 1 is a diagram of a wireless network architecture that supports access terminals and access networks in accordance with at least one embodiment of the invention.
FIG. 2A illustrates the core network of FIG. 1 according to an embodiment of the present invention.
FIG. 2B illustrates the core network of FIG. 1 according to another embodiment of the present invention.
FIG. 2C illustrates an example of the wireless communications system of FIG. 1 in more detail.
FIG. 3 is an illustration of an access terminal in accordance with at least one embodiment of the invention.
FIG. 4 is an illustration of in-band signaling to indicate end of incoming data stream in accordance with at least one embodiment of the invention.
FIG. 5 is an illustration of conventional out-of-band signaling to indicate end of incoming data stream.
FIG. 6 illustrates an example of in-band signaling with two incoming streams in accordance with at least one embodiment of the invention.
FIGS. 7A-7B illustrate examples of in-band signaling with the server detecting the marker bit.
FIG. 8 illustrates an example of generating in-band signaling at the server when an end of media/floor release is detected.
FIG. 9 illustrates a communication device that includes logic configured to perform functionality.
DETAILED DESCRIPTION
Aspects of the invention are disclosed in the following description and related drawings directed to specific embodiments. Alternate embodiments may be devised without departing from the scope of the invention. Additionally, well-known elements of the embodiments will not be described in detail or will be omitted so as not to obscure the relevant details of the embodiments.
The words “exemplary” and/or “example” are used herein to mean “serving as an example, instance, or illustration.” Any embodiment described herein as “exemplary” and/or “example” is not necessarily to be construed as preferred or advantageous over other embodiments. Likewise, the term “embodiments of the invention” does not require that all embodiments include the discussed feature, advantage or mode of operation.
Further, many embodiments are described in terms of sequences of actions to be performed by, for example, elements of a computing device. It will be recognized that various actions described herein can be performed by specific circuits (e.g., application specific integrated circuits (ASICs)), by program instructions being executed by one or more processors, or by a combination of both. Additionally, these sequence of actions described herein can be considered to be embodied entirely within any form of computer readable storage medium having stored therein a corresponding set of computer instructions that upon execution would cause an associated processor to perform the functionality described herein. Thus, the various aspects of the embodiments may be embodied in a number of different forms, all of which have been contemplated to be within the scope of the claimed subject matter. In addition, for each of the embodiments described herein, the corresponding form of any such embodiments may be described herein as, for example, “logic configured to” perform the described action.
A High Data Rate (HDR) subscriber station, referred to herein as user equipment (UE), may be mobile or stationary, and may communicate with one or more access points (APs), which may be referred to as Node Bs. A UE transmits and receives data packets through one or more of the Node Bs to a Radio Network Controller (RNC). The Node Bs and RNC are parts of a network called a radio access network (RAN). A radio access network can transport voice and data packets between multiple access terminals.
The radio access network may be further connected to additional networks outside the radio access network, such core network including specific carrier related servers and devices and connectivity to other networks such as a corporate intranet, the Internet, public switched telephone network (PSTN), a Serving General Packet Radio Services (GPRS) Support Node (SGSN), a Gateway GPRS Support Node (GGSN), and may transport voice and data packets between each UE and such networks. A UE that has established an active traffic channel connection with one or more Node Bs may be referred to as an active UE, and can be referred to as being in a traffic state. A UE that is in the process of establishing an active traffic channel (TCH) connection with one or more Node Bs can be referred to as being in a connection setup state. A UE may be any data device that communicates through a wireless channel or through a wired channel. A UE may further be any of a number of types of devices including but not limited to PC card, compact flash device, external or internal modem, or wireless or wireline phone. The communication link through which the UE sends signals to the Node B(s) is called an uplink channel (e.g., a reverse traffic channel, a control channel, an access channel, etc.). The communication link through which Node B(s) send signals to a UE is called a downlink channel (e.g., a paging channel, a control channel, a broadcast channel, a forward traffic channel, etc.). As used herein the term traffic channel (TCH) can refer to either an uplink/reverse or downlink/forward traffic channel.
FIG. 1 illustrates a block diagram of one exemplary embodiment of a wireless communications system 100 in accordance with at least one embodiment. System 100 can contain UEs, such as cellular telephone 102 , in communication across an air interface 104 with an access network or radio access network (RAN) 120 that can connect the access terminal 102 to network equipment providing data connectivity between a packet switched data network (e.g., an intranet, the Internet, and/or core network 126 ) and the UEs 102 , 108 , 110 , 112 . As shown here, the UE can be a cellular telephone 102 , a personal digital assistant 108 , a pager 110 , which is shown here as a two-way text pager, or even a separate computer platform 112 that has a wireless communication portal. The various embodiments can thus be realized on any form of access terminal including a wireless communication portal or having wireless communication capabilities, including without limitation, wireless modems, PCMCIA cards, personal computers, telephones, or any combination or sub-combination thereof. Further, as used herein, the term “UE” in other communication protocols (i.e., other than W-CDMA) may be referred to interchangeably as an “access terminal”, “AT”, “wireless device”, “client device”, “mobile terminal”, “mobile station” and variations thereof.
Referring back to FIG. 1 , the components of the wireless communications system 100 and interrelation of the elements of the exemplary embodiments are not limited to the configuration illustrated. System 100 is merely exemplary and can include any system that allows remote UEs, such as wireless client computing devices 102 , 108 , 110 , 112 to communicate over-the-air between and among each other and/or between and among components connected via the air interface 104 and RAN 120 , including, without limitation, core network 126 , the Internet, PSTN, SGSN, GGSN and/or other remote servers.
The RAN 120 controls messages (typically sent as data packets) sent to a RNC 122 . The RNC 122 is responsible for signaling, establishing, and tearing down bearer channels (i.e., data channels) between a Serving General Packet Radio Services (GPRS) Support Node (SGSN) and the UEs 102 / 108 / 110 / 112 . If link layer encryption is enabled, the RNC 122 also encrypts the content before forwarding it over the air interface 104 . The function of the RNC 122 is well-known in the art and will not be discussed further for the sake of brevity. The core network 126 may communicate with the RNC 122 by a network, the Internet and/or a public switched telephone network (PSTN). Alternatively, the RNC 122 may connect directly to the Internet or external network. Typically, the network or Internet connection between the core network 126 and the RNC 122 transfers data, and the PSTN transfers voice information. The RNC 122 can be connected to multiple Node Bs 124 . In a similar manner to the core network 126 , the RNC 122 is typically connected to the Node Bs 124 by a network, the Internet and/or PSTN for data transfer and/or voice information. The Node Bs 124 can broadcast data messages wirelessly to the UEs, such as cellular telephone 102 . The Node Bs 124 , RNC 122 and other components may form the RAN 120 , as is known in the art. However, alternate configurations may also be used and the various embodiments are not limited to the configuration illustrated. For example, in another embodiment the functionality of the RNC 122 and one or more of the Node Bs 124 may be collapsed into a single “hybrid” module having the functionality of both the RNC 122 and the Node B(s) 124 .
FIG. 2A illustrates the core network 126 according to an embodiment. In particular, FIG. 2A illustrates components of a General Packet Radio Services (GPRS) core network implemented within a W-CDMA system. In the embodiment of FIG. 2A , the core network 126 includes a Serving GPRS Support Node (SGSN) 160 , a Gateway GPRS Support Node (GGSN) 165 and an Internet 175 . However, it is appreciated that portions of the Internet 175 and/or other components may be located outside the core network in alternative embodiments.
Generally, GPRS is a protocol used by Global System for Mobile communications (GSM) phones for transmitting Internet Protocol (IP) packets. The GPRS Core Network (e.g., the GGSN 165 and one or more SGSNs 160 ) is the centralized part of the GPRS system and also provides support for W-CDMA based 3G networks. The GPRS core network is an integrated part of the GSM core network, provides mobility management, session management and transport for IP packet services in GSM and W-CDMA networks.
The GPRS Tunneling Protocol (GTP) is the defining IP protocol of the GPRS core network. The GTP is the protocol which allows end users (e.g., access terminals) of a GSM or W-CDMA network to move from place to place while continuing to connect to the internet as if from one location at the GGSN 165 . This is achieved transferring the subscriber's data from the subscriber's current SGSN 160 to the GGSN 165 , which is handling the subscriber's session.
Three forms of GTP are used by the GPRS core network; namely, (i) GTP-U, (ii) GTP-C and (iii) GTP′ (GTP Prime). GTP-U is used for transfer of user data in separated tunnels for each packet data protocol (PDP) context. GTP-C is used for control signaling (e.g., setup and deletion of PDP contexts, verification of GSN reach-ability, updates or modifications such as when a subscriber moves from one SGSN to another, etc.). GTP′ is used for transfer of charging data from GSNs to a charging function.
Referring to FIG. 2A , the GGSN 165 acts as an interface between the GPRS backbone network (not shown) and the external packet data network 175 . The GGSN 165 extracts the packet data with associated packet data protocol (PDP) format (e.g., IP or PPP) from the GPRS packets coming from the SGSN 160 , and sends the packets out on a corresponding packet data network. In the other direction, the incoming data packets are directed by the GGSN 165 to the SGSN 160 which manages and controls the Radio Access Bearer (RAB) of the destination UE served by the RAN 120 . Thereby, the GGSN 165 stores the current SGSN address of the target UE and his/her profile in its location register (e.g., within a PDP context). The GGSN is responsible for IP address assignment and is the default router for the connected UE. The GGSN also performs authentication and charging functions.
The SGSN 160 is representative of one of many SGSNs within the core network 126 , in an example. Each SGSN is responsible for the delivery of data packets from and to the UEs within an associated geographical service area. The tasks of the SGSN 160 includes packet routing and transfer, mobility management (e.g., attach/detach and location management), logical link management, and authentication and charging functions. The location register of the SGSN stores location information (e.g., current cell, current VLR) and user profiles (e.g., IMSI, PDP address(es) used in the packet data network) of all GPRS users registered with the SGSN 160 , for example, within one or more PDP contexts for each user or UE. Thus, SGSNs are responsible for (i) de-tunneling downlink GTP packets from the GGSN 165 , (ii) uplink tunnel IP packets toward the GGSN 165 , (iii) carrying out mobility management as UEs move between SGSN service areas and (iv) billing mobile subscribers. As will be appreciated by one of ordinary skill in the art, aside from (i)-(iv), SGSNs configured for GSM/EDGE networks have slightly different functionality as compared to SGSNs configured for W-CDMA networks.
The RAN 120 (e.g., or UTRAN, in Universal Mobile Telecommunications System (UMTS) system architecture) communicates with the SGSN 160 via a Radio Access Network Application Part (RANAP) protocol. RANAP operates over a Iu interface (Iu-ps), with a transmission protocol such as Frame Relay or IP. The SGSN 160 communicates with the GGSN 165 via a Gn interface, which is an IP-based interface between SGSN 160 and other SGSNs (not shown) and internal GGSNs, and uses the GTP protocol defined above (e.g., GTP-U, GTP-C, GTP′, etc.). In the embodiment of FIG. 2 , the Gn between the SGSN 160 and the GGSN 165 carries both the GTP-C and the GTP-U. While not shown in FIG. 2A , the Gn interface is also used by the Domain Name System (DNS). The GGSN 165 is connected to a Public Data Network (PDN) (not shown), and in turn to the Internet 175 , via a Gi interface with IP protocols either directly or through a Wireless Application Protocol (WAP) gateway.
FIG. 2B illustrates the core network 126 according to another embodiment. FIG. 2B is similar to FIG. 2A except that FIG. 2B illustrates an implementation of direct tunnel functionality.
Direct Tunnel is an optional function in Iu mode that allows the SGSN 160 to establish a direct user plane tunnel between RAN and GGSN within the Packet Switched (PS) domain. A direct tunnel capable SGSN, such as SGSN 160 in FIG. 2B , can be configured on a per GGSN and per RNC basis whether or not the SGSN can use a direct user plane connection. The SGSN 160 in FIG. 2B handles the control plane signaling and makes the decision when to establish Direct Tunnel. When the Radio Bearer (RAB) assigned for a PDP context is released (i.e. the PDP context is preserved) the GTP-U tunnel is established between the GGSN 165 and SGSN 160 in order to be able to handle the downlink packets.
The optional Direct Tunnel between the SGSN 160 and GGSN 165 is not typically allowed (i) in the roaming case (e.g., because the SGSN needs to know whether the GGSN is in the same or different PLMN), (ii) where the SGSN has received Customized Applications for Mobile Enhanced Logic (CAMEL) Subscription Information in the subscriber profile from a Home Location Register (HLR) and/or (iii) where the GGSN 165 does not support GTP protocol version 1. With respect to the CAMEL restriction, if Direct Tunnel is established then volume reporting from SGSN 160 is not possible as the SGSN 160 no longer has visibility of the User Plane. Thus, since a CAMEL server can invoke volume reporting at anytime during the life time of a PDP Context, the use of Direct Tunnel is prohibited for a subscriber whose profile contains CAMEL Subscription Information.
The SGSN 160 can be operating in a Packet Mobility Management (PMM)-detached state, a PMM-idle state or a PMM-connected state. In an example, the GTP-connections shown in FIG. 2B for Direct Tunnel function can be established whereby the SGSN 160 is in the PMM-connected state and receives an Iu connection establishment request from the UE. The SGSN 160 ensures that the new Iu connection and the existing Iu connection are for the same UE, and if so, the SGSN 160 processes the new request and releases the existing Iu connection and all RABs associated with it. To ensure that the new Iu connection and the existing one are for the same UE, the SGSN 160 may perform security functions. If Direct Tunnel was established for the UE, the SGSN 160 sends an Update PDP Context Request(s) to the associated GGSN(s) 165 to establish the GTP tunnels between the SGSN 160 and GGSN(s) 165 in case the Iu connection establishment request is for signaling only. The SGSN 160 may immediately establish a new direct tunnel and send Update PDP Context Request(s) to the associated GGSN(s) 165 and include the RNC's Address for User Plane, a downlink Tunnel Endpoint Identifier (TEID) for data in case the Iu connection establishment request is for data transfer.
The UE also performs a Routing Area Update (RAU) procedure immediately upon entering PMM-IDLE state when the UE has received a RRC Connection Release message with cause “Directed Signaling connection re-establishment” even if the Routing Area has not changed since the last update. In an example, the RNC will send the RRC Connection Release message with cause “Directed Signaling Connection re-establishment” when it the RNC is unable to contact the Serving RNC to validate the UE due to lack of Iur connection (e.g., see TS 25.331[52]). The UE performs a subsequent service request procedure after successful completion of the RAU procedure to re-establish the radio access bearer when the UE has pending user data to send.
The PDP context is a data structure present on both the SGSN 160 and the GGSN 165 which contains a particular UE's communication session information when the UE has an active GPRS session. When a UE wishes to initiate a GPRS communication session, the UE must first attach to the SGSN 160 and then activate a PDP context with the GGSN 165 . This allocates a PDP context data structure in the SGSN 160 that the subscriber is currently visiting and the GGSN 165 serving the UE's access point.
FIG. 2C illustrates an example of the wireless communications system 100 of FIG. 1 in more detail. In particular, referring to FIG. 2C , UEs 1 . . . N are shown as connecting to the RAN 120 at locations serviced by different packet data network end-points. The illustration of FIG. 2C is specific to W-CDMA systems and terminology, although it will be appreciated how FIG. 2C could be modified to confirm with a 1xEV-DO system. Accordingly, UEs 1 and 3 connect to the RAN 120 at a portion served by a first packet data network end-point 162 (e.g., which may correspond to SGSN, GGSN, PDSN, a home agent (HA), a foreign agent (FA), etc.). The first packet data network end-point 162 in turn connects, via the routing unit 188 , to the Internet 175 and/or to one or more of an authentication, authorization and accounting (AAA) server 182 , a provisioning server 184 , an Internet Protocol (IP) Multimedia Subsystem (IMS)/Session Initiation Protocol (SIP) Registration Server 186 and/or the application server 170 . UEs 2 and 5 . . . N connect to the RAN 120 at a portion served by a second packet data network end-point 164 (e.g., which may correspond to SGSN, GGSN, PDSN, FA, HA, etc.). Similar to the first packet data network end-point 162 , the second packet data network end-point 164 in turn connects, via the routing unit 188 , to the Internet 175 and/or to one or more of the AAA server 182 , a provisioning server 184 , an IMS/SIP Registration Server 186 and/or the application server 170 . UE 4 connects directly to the Internet 175 , and through the Internet 175 can then connect to any of the system components described above.
Referring to FIG. 2C , UEs 1 , 3 and 5 . . . N are illustrated as wireless cell-phones, UE 2 is illustrated as a wireless tablet-PC and UE 4 is illustrated as a wired desktop station. However, in other embodiments, it will be appreciated that the wireless communication system 100 can connect to any type of UE, and the examples illustrated in FIG. 2C are not intended to limit the types of UEs that may be implemented within the system. Also, while the AAA 182 , the provisioning server 184 , the IMS/SIP registration server 186 and the application server 170 are each illustrated as structurally separate servers, one or more of these servers may be consolidated in at least one embodiment.
Further, referring to FIG. 2C , the application server 170 is illustrated as including a plurality of media control complexes (MCCs) 1 . . . N 170 B, and a plurality of regional dispatchers 1 . . . N 170 A. Collectively, the regional dispatchers 170 A and MCCs 170 B are included within the application server 170 , which in at least one embodiment can correspond to a distributed network of servers that collectively functions to arbitrate communication sessions (e.g., half-duplex group communication sessions via IP unicasting and/or IP multicasting protocols) within the wireless communication system 100 . For example, because the communication sessions arbitrated by the application server 170 can theoretically take place between UEs located anywhere within the system 100 , multiple regional dispatchers 170 A and MCCs are distributed to reduce latency for the arbitrated communication sessions (e.g., so that a MCC in North America is not relaying media back-and-forth between session participants located in China). Thus, when reference is made to the application server 170 , it will be appreciated that the associated functionality can be enforced by one or more of the regional dispatchers 170 A and/or one or more of the MCCs 170 B. The regional dispatchers 170 A are generally responsible for any functionality related to establishing a communication session (e.g., handling signaling messages between the UEs, scheduling and/or sending announce messages, etc.), whereas the MCCs 170 B are responsible for hosting the communication session for the duration of the call instance, including conducting an in-call signaling and an actual exchange of media during an arbitrated communication session.
Referring to FIG. 3 , a UE 200 , (here a wireless device), such as a cellular telephone, has a platform 202 that can receive and execute software applications, data and/or commands transmitted from the RAN 120 that may ultimately come from the core network 126 , the Internet and/or other remote servers and networks. The platform 202 can include a transceiver 206 operably coupled to an application specific integrated circuit (“ASIC” 208 ), or other processor, microprocessor, logic circuit, or other data processing device. The ASIC 208 or other processor executes the application programming interface (“API”) 210 layer that interfaces with any resident programs in the memory 212 of the wireless device. The memory 212 can be comprised of read-only or random-access memory (RAM and ROM), EEPROM, flash cards, or any memory common to computer platforms. The platform 202 also can include a local database 214 that can hold applications not actively used in memory 212 . The local database 214 is typically a flash memory cell, but can be any secondary storage device as known in the art, such as magnetic media, EEPROM, optical media, tape, soft or hard disk, or the like. The internal platform 202 components can also be operably coupled to external devices such as antenna 222 , display 224 , push-to-talk button 228 and keypad 226 among other components, as is known in the art.
Accordingly, an embodiment can include a UE including the ability to perform the functions described herein. As will be appreciated by those skilled in the art, the various logic elements can be embodied in discrete elements, software modules executed on a processor or any combination of software and hardware to achieve the functionality disclosed herein. For example, ASIC 208 , memory 212 , API 210 and local database 214 may all be used cooperatively to load, store and execute the various functions of the In-band Signaling Application 250 as disclosed herein and thus the logic to perform these functions may be distributed over various elements. Alternatively, the functionality could be incorporated into one discrete component. Therefore, the features of the UE 200 in FIG. 3A are to be considered merely illustrative and the various embodiments are not limited to the illustrated features or arrangement.
The wireless communication between the UE 102 or 200 and the RAN 120 can be based on different technologies, such as code division multiple access (CDMA), W-CDMA, time division multiple access (TDMA), frequency division multiple access (FDMA), Orthogonal Frequency Division Multiplexing (OFDM), the Global System for Mobile Communications (GSM), or other protocols that may be used in a wireless communications network or a data communications network. For example, in W-CDMA, the data communication is typically between the client device 102 , Node B(s) 124 , and the RNC 122 . The RNC 122 can be connected to multiple data networks such as the core network 126 , PSTN, the Internet, a virtual private network, a SGSN, a GGSN and the like, thus allowing the UE 102 or 200 access to a broader communication network. As discussed in the foregoing and known in the art, voice transmission and/or data can be transmitted to the UEs from the RAN using a variety of networks and configurations. Accordingly, the illustrations provided herein are not intended to limit the various embodiments and are merely to aid in the description of aspects of the embodiments.
Multimedia can be exchanged over any of the above-noted communication networks via data packets that use the Real-time Transport Protocol (RTP). RTP supports a range of multimedia formats (such as H.264, MPEG-4, MJPEG, MPEG, etc.) and allows new formats to be added without revising the RTP standard. An example of a header portion of a 40-octet overhead RTP packet may be configured as follows:
TABLE 1
Example of a RTP packet header
0 1
2 3
4 5
6 7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Octet 1, 5, 9 . . .
Octet 2, 6, 10 . . .
Octet 3, 7, 11 . . .
Octet 4, 8, 12 . . .
1-4
Version
IHL
Type of service
Total length
5-8
Identification
Flags
Fragment offset
9-12
Time to live
Protocol
Header checksum
13-16
Source address
17-20
Destination address
21-24
Source port
Destination port
25-28
Length
Checksum
29-32
V = 2
P X
CC
M
PT
Sequence number
33-36
Timestamp
37-40
Synchronization source (SSRC) number
Referring to Table 1, the general fields of the RTP packet header portion are well-known in the art. After the RTP header portion, the RTP packet includes a data payload portion. The data payload portion can include digitized samples of voice and/or video. The length of the data payload can vary for different RTP packets. For example, in voice RTP packets, the length of the voice sample carried by the data payload may correspond to 20 milliseconds (ms) of sound. Generally, for longer media durations (e.g., higher-rate frames), the data payload either has to be longer as well, or else the quality of the media sample is reduced.
Generally, the RTP sender captures multimedia data (e.g., from a user of the RTP sender), which is then encoded, framed and transmitted as RTP packets with appropriate timestamps and increasing sequence numbers. The RTP packets transmitted by the RTP sender can be conveyed to a target RTP device (or RTP receiver) via a server arbitrating a session between the RTP sender and receiver, or alternatively directly from the RTP sender to the RTP receiver via peer-to-peer (P2P) protocols. The RTP receiver receives the RTP packets, detects missing packets and may perform reordering of packets. The frames are decoded depending on the payload format and presented to the user of the RTP receiver.
FIG. 4 illustrates a process of terminating an RTP-based communication in accordance with an embodiment. Referring to FIG. 4 , device A 401 (e.g., a UE, such as UE 200 described above) is recording audio into frame buffer 402 which contains frames 110 - 113 of audio data. The audio data from the frame buffer 402 are formatted into a payload of one or more RTP packets (in FIG. 4 , these frames are shown as part of the payload for RTP packet 9 ) and transmitted during an audio transmission (or stream). At the end of the audio transmission, the user of device A 401 may affirmatively indicate an end of the audio transmission or stream (e.g., by releasing of the PTT button 403 ). This will cause a marker bit (MB) 404 to be set in the Real-time Transport Protocol (RTP) header of packet 9 . The MB 404 is a well-known RTP header field but is not conventionally used to indicate the end of a stream of data. In fact, the MB 404 is typically used to indicate the beginning (not the end) of a stream or talk-spurt. In addition, Packet 9 contains a table of contents (TOC) and audio payload (frames 110 - 113 ). It will be noted in the illustrated example, that the packet 9 is part of a stream of packets 407 that contain the streaming audio data in various frames in packets 7 , 8 and 9 . In this illustrated example, packets 7 and 8 , each have RTP headers, TOCs and 6 frames (frames 98 - 103 and frames 104 - 109 , respectively). Packet 9 has only four frames due to the truncated audio transmission. However, the last packet in the stream 407 could have 0-6 frames, in this example, since the end of the audio transmission may occur at any arbitrary position. Further, it will be appreciated that the various embodiments are not limited to a bundling factor of 6 frames per packet, as any number of frames may be used. Regardless of the number of frames in the last packet containing the audio transmission, the last packet includes a marker bit in the RTP header to affirmatively indicate an end of the audio transmission. Also, while the MB 404 is leveraged in the embodiment of FIG. 4 for indicating the end of the stream of data (or audio transmission), it will be appreciated that other RTP header fields could be leveraged for this purpose in other embodiments.
The media stream 407 may optionally go through a server (e.g., application server 170 ) and be buffered and/or reordered at the network level. Additionally, network reordering 420 in a negative sense may occur (e.g., putting the packets out of order) due to path delays, routing problems, network congestion, and the like. The network reordering 420 makes it difficult to determine when the real end of the stream occurs. The various embodiments make it easier to detect the real end of the stream. Specifically, a marker-bit packet that is delivered out of order will get automatically “re-ordered” as part of the de-jitter/re-ordering buffer, meaning that it will be outputted/processed in the order it was transmitted, something that cannot easily be done with out-of-band signaling.
However, regardless if the packets are buffered and/or reordered at the network, the stream 407 will be received at device B 411 in dejitter buffer 408 and will be buffered and optionally reordered, if needed. The frames are then played out at device B and device B is in a state 409 where device A is speaking and has the floor in the PTT context. After, frame 113 is played, since the marker bit was set in the RTP header of packet 9 , device B will be affirmatively notified that the stream has ended. Device B can then immediately note that the floor is now open 410 (e.g., available for audio transmission from device B or another device), and need not wait for an out-of-band signaling indication of floor availability from the application server 170 . It will be appreciated that by using the in-band signaling, the end of the stream and floor state can be updated immediately, without delays due to waiting for out-of-band signaling. However, it should be noted that the floor will be “open” from the local perspective as the server may not yet be informed if it is not monitoring the in-band signaling (additional discussion on this aspect is provided in the following paragraphs).
In another aspect, to address the possibility that packet 9 is dropped and the marker bit is lost and thus the in-band end of the stream indicator is also missed, a configurable number of RTP packets including the marker bit can be sent to increase the probability that the in-band end of stream indicator (e.g., marker bit) is received. For example, the last N RTP packets of the audio transmission can carry the MB 404 with a marker bit set to indicate the end of the audio transmission (or stream). In a further example, N “empty” RTP packets (i.e., empty of audio payload data) can be transmitted after the last substantive RTP packet to ensure that the target device(s) are aware that device A's user has stopped talking.
In another aspect to address the possibility that packet 9 is dropped and the marker bit is lost and thus the in-band end of the stream indicator is also missed, the last few packets of the data stream can be configured to count down to the last packet. When the user releases the PTT button, there may still be buffered packets at device A 401 . These packets can be configured with a field or byte in the payload or a header extension indicating a “countdown” to the last packet. For example, assuming packets 7 - 9 were still buffered at device A 401 when the user releases the PTT button, the field in packet 7 could be set to “3” to indicate that there are three more packets in the stream. Alternatively, the field in packet 7 could be set to “2” to indicate that there are two more packets before the last packet. Likewise, the field in packet 8 could be set to “2” or “1.” The field in packet 9 , as the last packet, could be set to “1” or “0.” Alternatively, packet 9 may not include a field like packets 7 and 8 , but rather have its marker bit set or a special payload, as discussed herein. Note that the field in the payload is a field in an audio payload, and not a field in a separate end-of-stream packet's payload.
Because several packets at the end of the stream of data are configured to count down to the last packet, as long as the target receives at least one of these packets, it will be able to determine which packet is or should be the last. For example, assuming device B 411 gives each packet 120 ms to be received, if device B 411 receives packet 7 but does not receive packets 8 and 9 within 240 ms, it will know that it does not need to keep waiting for a packet 10 because packet 9 was the last packet. It can instead immediately switch to another incoming stream, if there is one.
Although FIG. 4 has been described in terms of transmitting audio data, it will be apparent that device A 401 may additionally or alternatively record and transmit video and/or opaque data (e.g., x-y coordinates of a pointer being moved across the user interface of device A 401 ). In such a case, frames 98 - 103 , 104 - 109 , and 110 - 113 of packets 7 , 8 , and 9 , respectively, would contain audio, video, and/or opaque data. Opaque data is data that has a hidden representation, or format, and therefore can only be manipulated by calling subroutines that have access to the representation of the opaque data.
In another aspect, device 401 may be transmitting synced audio and video streams. Since the two streams are synced, the end of the audio stream can also be determined. Accordingly, the end of one or both of the audio and video streams can be marked as in the various embodiments. It is preferable to mark the end of both streams so that if the last packet or last few packets of one stream is lost, the end of the other stream, and thus the end of the stream with the lost packets, is still known. Alternatively, only the end of one stream can be marked, and the receiver can determine the end of the other stream based on the marked stream.
As will be appreciated by one of ordinary skill in the art in view of the above-disclosure, in-band signaling has the potential to indicate a more precise point of time when the stream has truly ended from the receiver's perspective due to the difficulty in syncing out-of-band signaling with in-band media transfers. If not synchronized correctly, the out-of-band signaling may leave a gap in time, where the “END” signal arrives either too early or too late, which results in the possibility of truncating the stream short or permitting the stream to continue in a starved mode (e.g., RTP packets stop arriving but no user-context update). In-band “signaling” alleviates other additional complexity to synchronize the stream with the signaling to a server or other controlling entity. Also, the use of in-band signaling can convey the end-point of a stream of data as soon as the last (or near-last) packet in the stream of data is received and thereby can convey the end-of-session status faster than a traffic inactivity timer which would only recognize the end-of-session status a threshold period of time after the last packet in the stream was received.
FIG. 5 illustrates a process of terminating an RTP-based communication session via conventional out-of-band signaling. The process of FIG. 5 is similar in some respects to the process of FIG. 4 , whereby a device A 501 having a frame buffer 502 including frames of audio data, and a stream 507 containing various packets is transmitted to dejitter buffer 508 of device B 511 . Additional common elements with the system of FIG. 4 will not be recited to avoid redundancy. However, in the process illustrated in FIG. 5 , there is no marker bit to indicate the end of the media content (e.g. audio in a PTT call). Instead, in conventional out-of-band signaling-based session termination, device A 501 sends out-of-band signaling 504 to the application server 170 indicating that device A 501 has released the floor (e.g., stream from device A has ended). The application server 170 then processes the out-of-band signaling 504 from device A 501 and notifies the other device(s) (e.g., device B 511 ) using out-of-band signaling 505 that the floor has been released (which indicates both an end of stream and also indicates that the floor is open 510 ). Depending on the various latencies in the in-band buffers (e.g., dejitter buffer 508 or other buffers) and/or other delays, the out-of-band signaling 505 of the floor release may arrive at the target devices too early (e.g., leading to a premature release of the floor and a truncation of some of the device A 501 's audio), as shown by reference 509 , or alternatively may arrive too late (e.g., resulting in extended periods with no audio/media, prior to the floor being released, not shown explicitly in FIG. 5 ).
Referring to FIG. 6 , an example of in-band signaling with two incoming streams is illustrated. Device A 601 may capture media 602 (e.g., video, audio, opaque data, etc.) that can be streamed 607 in a series of packets. Likewise, device B 611 may capture B media 612 (e.g., video, audio, opaque data, etc.) that can be streamed 617 in a series of packets. Each stream can be received at device C 621 in dejitter buffer A and dejitter buffer B, respectively. Each stream has a distinct Synchronization Source (SSRC) contained in the headers of their respective RTP packets, so that device C 621 can identify and distinguish between the streams. Similar to the foregoing discussion, stream 607 contains a packet 9 that also contains a marker bit indicating the end of media or a point at which the sending device (e.g., device A) wants the media to switch. This allows for device C to immediately cutover source 630 to the second stream, which is contained in dejitter buffer 618 from the first stream dejitter buffer 608 . This also results in the cutover of media 631 from A media 602 to B media 612 which can be reflected at 622 (e.g., a media player, display, etc.) on device C 621 . Accordingly, a precise cutover time is provided which cannot be easily achieved using out-of-band signaling, as discussed in the foregoing.
While the foregoing provided some basic examples of the use and implementation of in-band signaling to mark and end of stream or stream transmission, it will be appreciated that the various embodiments are not limited by the foregoing examples.
For example, FIG. 7A illustrates a process of terminating an RTP-based communication session in accordance with an embodiment that further includes the server interaction with the in-band signaling. The process is similar to that disclosed in relation to FIG. 4 , with media, such as audio, video, or opaque data, being streamed from device A to the application server 170 for transmission to device B (e.g., packets 7 and 8 ) in 710 . The PTT button can be released in 712 and a marker bit can be added to the last packet (e.g., packet 9 ), which is then transmitted to the application server 170 , 714 . In an alternative example, if device A is streaming opaque data such as the x-y coordinates of a pointer moving across device A's screen, the user's end-of-session input at 712 , i.e. PTT release, need not correspond to a PTT release but can correspond to other user input including lifting the pointer, such as a finger or a stylus, off the screen, which can signal device A to add the marker bit to the last packet of opaque data 714 . In the illustrated embodiment of FIG. 7A , the application server 170 receives the media stream (e.g., packets 7 and 8 ) and then forwards the media stream 720 to the intended target(s) (e.g., device B). At 722 , the application server 170 optionally receives and detects the packet with the marker bit. The application server 170 may actively update the context of device A and/or the floor status (e.g., open). Alternatively, the application server 170 may take no action other than detecting the marker bit. The rest of the media is streamed to the target(s) in 724 . At this point the application server 170 may do nothing and await out-of-band signaling to confirm the end of media/floor release from device A.
Device B is operating in a listen mode 730 since device A has the floor. Upon receiving the streaming media (e.g., packets 7 and 8 ) at 732 , device B will play/process these in a conventional manner. In contrast, when the last packet with the marker bit is received, 734 , the user context of originating device A and floor status is changed to an open state, 736 (locally at device B).
Although illustrated only with respect to device B, it will be appreciated that there can be multiple target devices and that each may have different latencies, such as illustrated in FIG. 7B , so that coordinating the floor status or other transitions using the in-band signaling and a positive acknowledgment of the in-band signaling from the targets could enhance system performance and user experience. For example, it could prevent a premature grant of the floor to faster devices.
Referring to FIG. 7B , the media from originating device A is considered to be the same as in FIG. 7A , so it is not illustrated again. Further, the illustration starts with the transmission of the last packet with the marker bit, 724 , to the various targets (e.g., device B to device N). Each device receives the last packet with the marker bit, 734 , 744 and the user context of originating device A and floor status is changed to an open state, 736 , 746 . A positive acknowledgment of the floor release (floor open) from device B, is transmitted in 738 to the application server 170 . Then, at a later time, a positive acknowledgment of the floor release (floor open), 748 , is transmitted from device N. Further, in this embodiment the application server 170 can await a positive confirmation from the target(s), such as illustrated in 726 before designating the floor as being open at the application server 170 . This alternative embodiment is different from the conventional PTT model. In the conventional PTT model, the server does not wait until devices receiving streams Ack the end of the stream. However, in this alternative embodiment, the server doesn't reflect a floor open state until it receives an Ack ( 738 , 748 ) from each target/listener in order to avoid false positives. It will be appreciated that the notion that the “floor is open” in 736 and 746 is from the device/user's perspective. Further, it will be appreciated that in FIG. 7A , the application server 170 optionally evaluated the RTP header fields of the incoming RTP packets from device A so that the application server 170 can recognize the RTP packet from device A with the marker bit set to indicate the end of the stream of data at 722 of FIG. 7A . However, the application server 170 in FIG. 7B is notified of the device A's intent to give up the floor upon receipt of the ACKs at 738 and/or 748 in FIG. 7B . Thus, in FIG. 7B , it is assumed that the optional operation of 722 from FIG. 7A is not performed.
In another aspect, the device A may end its media and provide the marker bit to indicate as such. However, shortly after, device A may want to reacquire the floor to continue. In this scenario, if the packet with the marker bit is still buffered at the application server 170 when the request/medial from device A is received, application server 170 can strip out the marker bit from the buffered packets, so there is no change in the floor state perceived by the target devices.
FIG. 8 illustrates a flowchart 800 of an embodiment where the server can detect the marker bit. At 810 , the process starts with the server receiving the last RTP packet for a particular stream of data from a transmitting device. If the server determines that the last-packet status is positively indicated by the marker bit in 820 , then the process can continue as discussed in the foregoing (e.g. at 722 of FIG. 7 ). However, if there is no marker bit detected then alternative methods can be employed by the server to determine the end of media (e.g., out-of-band signaling, traffic inactivity timer expiration, etc.). For example, the server determines whether out-of-band signaling indicates the transmitting device's intent to stop transmitting media and/or to release the floor at 830 , and the server can also determine whether a traffic inactivity timer for the connection to the transmitting device has timed out, 840 . If either 830 or 840 indicate the end of the media stream (or transmission session) from the transmitting device, the server can generate a packet containing a marker bit, 850 , and transmit that packet to the target device(s), 860 . Accordingly, this hybrid configuration allows for conventional processing for the receiving out-of-band signaling, yet still can leverage the in-band signaling once the media end and/or floor release is determined. This can be helpful for interfacing to legacy devices or non-native systems that do not support recognition of the marker bit as an indicator of the last media packet. Finally, a watchdog (or traffic inactivity) timer can be configured to time out as an indication of the end of media and/or floor release, in 840 . In the event that no media packets and no signaling is received, the server can generate a packet containing a marker bit 850 and transmit that packet to the target device(s) 860 . This also can function as a backup for devices that do include a marker bit in the event that the packet or packets with the marker bit are lost or corrupted. Accordingly, detecting the marker bit at the server can allow for additional flexibility in leveraging the in-band signaling for cases where the marker bit is not received.
As noted in the foregoing the marker bit was used to describe an affirmative in-band signaling to mark the end of the media stream. However, it will be appreciated that other mechanisms can be used for in-band signaling. For example, erasure frames, null/blank rate frames, RTP packet with no payload, RTP packet with partial payload, and the like, can be used as in-band signaling to mark the end of the stream. Additionally, the in-band signaling of the end of the media stream may be indicated by any packet that doesn't conform to a full and audible packet that conforms to the rest of the streams packaging and bundling factor. Further, it will be appreciated that combinations of the foregoing can be used (e.g., marker bit and RTP packet with no payload). Accordingly, the various embodiments are not limited to any specific in-band signaling technique.
While the various embodiments are primarily described with respect to one-to-one communication sessions between UEs/devices, it will be appreciated that other embodiments can be directed to group communication sessions that can include three or more UEs, as evidenced by FIG. 7B .
FIG. 9 illustrates a communication device 900 that includes logic configured to perform functionality. The communication device 900 can correspond to any of the above-noted communication devices, including but not limited to UEs 102 , 108 , 110 , 112 or 200 , Node Bs or base stations 120 , the RNC or base station controller 122 , a packet data network end-point (e.g., SGSN 160 , GGSN 165 , a Mobility Management Entity (MME) in Long Term Evolution (LTE), etc.), any of the servers 170 through 186 , etc. Thus, communication device 900 can correspond to any electronic device that is configured to communicate with (or facilitate communication with) one or more other entities over a network.
Referring to FIG. 9 , the communication device 900 includes logic configured to receive and/or transmit information 905 . In an example, if the communication device 900 corresponds to a wireless communications device (e.g., UE 200 , Node B 124 , etc.), the logic configured to receive and/or transmit information 905 can include a wireless communications interface (e.g., Bluetooth, WiFi, 2G, 3G, etc.) such as a wireless transceiver and associated hardware (e.g., an RF antenna, a MODEM, a modulator and/or demodulator, etc.). In another example, the logic configured to receive and/or transmit information 905 can correspond to a wired communications interface (e.g., a serial connection, a USB or Firewire connection, an Ethernet connection through which the Internet 175 can be accessed, etc.). Thus, if the communication device 900 corresponds to some type of network-based server (e.g., SGSN 160 , GGSN 165 , application server 170 , etc.), the logic configured to receive and/or transmit information 905 can correspond to an Ethernet card, in an example, that connects the network-based server to other communication entities via an Ethernet protocol. In a further example, the logic configured to receive and/or transmit information 905 can include sensory or measurement hardware by which the communication device 900 can monitor its local environment (e.g., an accelerometer, a temperature sensor, a light sensor, an antenna for monitoring local RF signals, etc.). The logic configured to receive and/or transmit information 905 can also include software that, when executed, permits the associated hardware of the logic configured to receive and/or transmit information 905 to perform its reception and/or transmission function(s). However, the logic configured to receive and/or transmit information 905 does not correspond to software alone, and the logic configured to receive and/or transmit information 905 relies at least in part upon hardware to achieve its functionality.
Referring to FIG. 9 , the communication device 900 further includes logic configured to process information 910 . In an example, the logic configured to process information 910 can include at least a processor. Example implementations of the type of processing that can be performed by the logic configured to process information 910 includes but is not limited to performing determinations, establishing connections, making selections between different information options, performing evaluations related to data, interacting with sensors coupled to the communication device 900 to perform measurement operations, converting information from one format to another (e.g., between different protocols such as .wmv to .avi, etc.), and so on. For example, the processor included in the logic configured to process information 910 can correspond to 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. 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. The logic configured to process information 910 can also include software that, when executed, permits the associated hardware of the logic configured to process information 910 to perform its processing function(s). However, the logic configured to process information 910 does not correspond to software alone, and the logic configured to process information 910 relies at least in part upon hardware to achieve its functionality.
Referring to FIG. 9 , the communication device 900 further includes logic configured to store information 915 . In an example, the logic configured to store information 915 can include at least a non-transitory memory and associated hardware (e.g., a memory controller, etc.). For example, the non-transitory memory included in the logic configured to store information 915 can correspond to RAM memory, flash memory, ROM memory, EPROM memory, EEPROM memory, registers, hard disk, a removable disk, a CD-ROM, or any other form of storage medium known in the art. The logic configured to store information 915 can also include software that, when executed, permits the associated hardware of the logic configured to store information 915 to perform its storage function(s). However, the logic configured to store information 915 does not correspond to software alone, and the logic configured to store information 915 relies at least in part upon hardware to achieve its functionality.
Referring to FIG. 9 , the communication device 900 further optionally includes logic configured to present information 920 . In an example, the logic configured to present information 920 can include at least an output device and associated hardware. For example, the output device can include a video output device (e.g., a display screen, a port that can carry video information such as USB, HDMI, etc.), an audio output device (e.g., speakers, a port that can carry audio information such as a microphone jack, USB, HDMI, etc.), a vibration device and/or any other device by which information can be formatted for output or actually outputted by a user or operator of the communication device 900 . For example, if the communication device 900 corresponds to UE 200 as shown in FIG. 3 , the logic configured to present information 920 can include the display 224 . In a further example, the logic configured to present information 920 can be omitted for certain communication devices, such as network communication devices that do not have a local user (e.g., network switches or routers, remote servers, etc.). The logic configured to present information 920 can also include software that, when executed, permits the associated hardware of the logic configured to present information 920 to perform its presentation function(s). However, the logic configured to present information 920 does not correspond to software alone, and the logic configured to present information 920 relies at least in part upon hardware to achieve its functionality.
Referring to FIG. 9 , the communication device 900 further optionally includes logic configured to receive local user input 925 . In an example, the logic configured to receive local user input 925 can include at least a user input device and associated hardware. For example, the user input device can include buttons, a touch-screen display, a keyboard, a camera, an audio input device (e.g., a microphone or a port that can carry audio information such as a microphone jack, etc.), and/or any other device by which information can be received from a user or operator of the communication device 900 . For example, if the communication device 900 corresponds to UE 200 as shown in FIG. 3 , the logic configured to receive local user input 925 can include the display 224 (if implemented a touch-screen), keypad 226 , etc. In a further example, the logic configured to receive local user input 925 can be omitted for certain communication devices, such as network communication devices that do not have a local user (e.g., network switches or routers, remote servers, etc.). The logic configured to receive local user input 925 can also include software that, when executed, permits the associated hardware of the logic configured to receive local user input 925 to perform its input reception function(s). However, the logic configured to receive local user input 925 does not correspond to software alone, and the logic configured to receive local user input 925 relies at least in part upon hardware to achieve its functionality.
Referring to FIG. 9 , while the configured logics of 905 through 925 are shown as separate or distinct blocks in FIG. 9 , it will be appreciated that the hardware and/or software by which the respective configured logic performs its functionality can overlap in part. For example, any software used to facilitate the functionality of the configured logics of 905 through 925 can be stored in the non-transitory memory associated with the logic configured to store information 915 , such that the configured logics of 905 through 925 each performs their functionality (i.e., in this case, software execution) based in part upon the operation of software stored by the logic configured to transmit information 905 . Likewise, hardware that is directly associated with one of the configured logics can be borrowed or used by other configured logics from time to time. For example, the processor of the logic configured to process information 910 can format data into an appropriate format before being transmitted by the logic configured to receive and/or transmit information 905 , such that the logic configured to receive and/or transmit information 905 performs its functionality (i.e., in this case, transmission of data) based in part upon the operation of hardware (i.e., the processor) associated with the logic configured to process information 910 .
It will be appreciated that the configured logic or “logic configured to” in the various blocks are not limited to specific logic gates or elements, but generally refer to the ability to perform the functionality described herein (either via hardware or a combination of hardware and software). Thus, the configured logics or “logic configured to” as illustrated in the various blocks are not necessarily implemented as logic gates or logic elements despite sharing the word “logic.”
Those of skill in the art will appreciate that information and signals may be represented using any of a variety of different technologies and techniques. For example, data, instructions, commands, information, signals, bits, symbols, and chips that may be referenced throughout the above description may be represented by voltages, currents, electromagnetic waves, magnetic fields or particles, optical fields or particles, or any combination thereof.
Further, those of skill in the art will 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 various 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. 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.
The methods, sequences and/or algorithms 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 RAM memory, flash memory, ROM memory, EPROM memory, EEPROM memory, 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 (e.g., access 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. 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.
While the foregoing disclosure shows illustrative embodiments of the invention, it should be noted that various changes and modifications could be made herein without departing from the scope of the invention as defined by the appended claims. The functions, steps and/or actions of the method claims in accordance with the embodiments of the invention described herein need not be performed in any particular order. Furthermore, although elements of the invention may be described or claimed in the singular, the plural is contemplated unless limitation to the singular is explicitly stated. | The disclosure relates to indicating or detecting an end of a stream of data using in-band signaling. An embodiment transmits the stream of data, the stream of data comprising multiple packets, each packet of the multiple packets including a header with a marker bit field and a payload, and configures the marker bit field and/or the payload of at least one packet of the multiple packets to indicate the end of the stream of data, wherein the configuring the payload comprises reducing an amount of data contained in the payload from payloads of other packets of the multiple packets and/or setting a field in the payload indicating a countdown to a last packet of the stream of data. An embodiment receives the stream of data and detects that at least one packet of the multiple packets is configured to indicate the end of the stream of data. | 7 |
FIELD OF THE INVENTION
The invention relates to a quick-action rolling shutter door and to modules thereof.
BACKGROUND OF THE INVENTION
Quick-action rolling shutter doors are used for closing openings in the walls of warehouses or factory buildings. Here, it is very important that the quick-action rolling shutter door can be opened and closed fast, only leaving the opening in the wall open for the actual passage of a person or a vehicle there-through. This will, on the one hand, restrict any loss of energy from heated or cooled rooms, and, on the other hand, protect the environment by keeping escaping noise, odours and dust emissions to a minimum.
From practical applications, two types of quick-action rolling shutter door are known. A first type of quick-action rolling shutter door, usually referred to as sectional door, uses rigid door elements which are guided on their sides and, when opened, assume a position parallel to a building wall or ceiling. Said door elements generally include a frame with plural filling inserts of a sandwich construction, similar to the kind used in window or door systems. The K-value of said doors which is between 1.0 to 1.4 can in itself be regarded as good from an energy saving point of view. What is disadvantageous about these doors, however, are their low opening and closing speeds and the high technical effort, amongst other things due to the problems involved in foam-filling the filling inserts with construction material. This construction is not only very problematic when it comes to recycling, but does not afford sufficient protection from burglary, either, since the filling inserts do not offer any resistance.
Another type of quick-action rolling shutter door which is known from practice as the socalled hanging or curtain door, uses a thin-walled plastic tarpaulin which is guided on the sides and can be wound up onto a roller. The high opening and closing speeds of this type of quick-action rolling shutter door are obtained at the expense of insufficient thermal insulation, with K-values ranging from 4.0 to 5.75, as well as insufficient safety from burglary.
Both types of quick-action rolling shutter door have disadvantages in relation to heat insulation. The disadvantage of sectional doors in this respect is the formation of cold bridges in the region of the joints interconnecting the individual door elements. The insufficient heat insulation of hanging doors is due to the insufficient insulation properties of the material of the hanging.
Another disadvantage of the prior art quick-action rolling shutter doors is the labor-intensive repair of collision damage. With both types of quick-action rolling shutter door, due to the prior art guiding devices used in them, maintenance work is only possible in the raised, opened state. What makes this shortcoming especially serious is the fact that collisions of vehicles and quick-action rolling shutter door hangings or door elements occur very frequently with quick-action rolling shutter doors. Another disadvantage of the prior art types of quick-action rolling shutter door resides in their insufficient safety from burglarly, as already mentioned.
SUMMARY OF THE INVENTION
It is the object of the invention to provide an improved quick-action rolling shutter door with corresponding modules for improving prior art quick-action rolling shutter doors.
This object is solved according to the invention by the features of claims 1 and 2 .
In accordance with claim 1 , the flexible hanging of the quick-action rolling shutter door, which is wound up onto a roller and guided on at least one side by a guiding device, should have at least one thick-walled insulating layer consisting of foamed plastic material. The fact that foamed plastic material is used, which has pores and chambers with small air cushions preventing any heat exchange through the quick-action rolling shutter door hanging, results in good heat and cold insulation. To achieve such insulation does not require a major constructional effort since the quick-action rolling shutter door hanging is flexible and can thus be readily wound up onto a roller. This allows high-speed opening and closing actions. Consequently, there will be no hinges, either, which would require special insulation measures.
The hanging of the quick-action rolling shutter door which constitutes a module for a quick-action rolling shutter door and for which protection is also sought separately, independently of claim 1 , preferably exhibits some reinforcement onto which the thick-walled insulation layer has been laminated. Said reinforcement, which may comprise a fabric or web of steel wires, steel strands, glass or carbon fibres, or cotton, serves as a barrier preventing any cutting through said quick-action rolling shutter door hanging, thus preventing burglary. A particular good cost-effectiveness ratio is obtained when a steel fabric is used for reinforcement.
For facilitating the winding up of the quick-action rolling shutter door hanging, one of its external sides preferably has expansion slots. In the case of a quick-action rolling shutter door hanging with first and second insulation layers, such layers are preferably glued or welded together along contact lines extending transversely to the direction of travel of said quick-action rolling shutter door. Particularly suitable for glueing together insulating layers of polyethylene foam is cyanoacrylate.
Another quick-action rolling shutter door module for which independent protection is sought, is the anti-push-up device. This anti-push-up device, which is provided especially for quick-action rolling shutter doors, is characterized by at least one detent latch which will latch in the guiding device whenever the distance between adjacent track rollers or sliding elements decreases during opening of the quick-action rolling shutter door. The distance between adjacent track rollers or sliding elements will always decrease when the bottom edge of a quick-action rolling shutter door hanging, or of door elements which are slidable relative to each other, is to be lifted. The fact that said at least one detent latch latches in said guiding device will prevent any further lifting of the quick-action rolling shutter door hanging or the door elements in such a case, thus preventing any burglary attempts in this manner. A bracing spring which will force two detent latches apart whenever the quick-action rolling shutter door hanging or the door elements is/are lifted, facilitates the latching process.
Yet another quick-action rolling shutter door module which is very advantageous when used together with a quick-action rolling shutter door hanging of the present invention, is a guiding device for quick-action rolling shutter doors, comprising a guide rail which is essentially U-shaped in cross-section and has a guide space for accommodating track rollers or sliding elements, wherein said guide rail is composed of plural parts. The two legs of the guide rail, which extend essentially in parallel in operation, can be shifted relative to each other, making the guide space freely accessible in its opened state. The fact that the guide space is freely accessible in its opened state allows the maintenance of a quick-action rolling shutter door equipped with such a guiding device in its closed state, which in particular makes an exchange or the cleaning of track rollers or sliding elements of a quick-action rolling shutter door possible. As the quick-action rolling shutter door can be kept closed during maintenance, any energy losses and emissions will be minimal. Moreover, this will facilitate maintenance work since the quick-action rolling shutter hanging and its guiding device are easily accessible.
Another way of minimizing the maintenance and repair work involved in operating a quick-action rolling shutter door is to provide a crash protection device. Such crash protection device for quick-action rolling shutter doors, for which independent protection is also sought, will ensure that the full operativeness of the quick-action rolling shutter door is restored in as short a time as possible after a vehicle has crashed into the hanging or the door elements of the quick-action rolling shutter door. While with quick-action rolling shutter doors of the prior art, parts of the guiding device will become destroyed in a collision, the crash protection device of the invention overcomes this problem in that, in case of a collision with a vehicle, it allows for the releasing of a coupling, thus avoiding the destruction of an element of the guiding device. Preferably, said coupling is designed such that coupling elements which were decoupled or disengaged during the raising of the hanging or door elements of the quick-action rolling shutter door will automatically be coupled or engaged again at funnel-like guide means.
BRIEF DESCRIPTION OF THE DRAWINGS
Other advantageous embodiments and further developments of the invention will become apparent from the subclaims as well as the description which follows in which reference is made to the drawings, of which:
FIG. 1 is a view of a first embodiment of a quick-action rolling shutter door according to the invention, with the roller cover removed;
FIG. 2 is a simplified perspective view of the top part of the quick-action rolling shutter door of FIG. 1;
FIG. 3 is a cut-off perspective view of a hanging for a quick-action rolling shutter door of FIGS. 1 and 2;
FIG. 4 is an enlarged perspective view of a first section of the quick-action rolling shutter door hanging of FIG. 3;
FIG. 5 is an enlarged perspective view of a second section of the quick-action rolling shutter door hanging of FIG. 3;
FIG. 6 is a guiding device according to the invention for a quick-action rolling shutter door of FIGS. 1 and 2;
FIG. 7 is one view of an anti-push-up device according to the invention for a quick-action rolling shutter door of FIGS. 1 and 2;
FIG. 8 is a simplified view of a pair of detent latches of the anti-push-up device of FIG. 6;
FIG. 8 a is a pair of detent latches for a second embodiment of an anti-push-up device, including a torsion spring for forcing said detent latches apart;
FIG. 9 is one view of a section of a crash protection device according to the invention;
FIG. 10 is a sectional view, taken along lines IX—IX of FIG. 8, of said crash protection device of FIG. 8 with a quick-action rolling shutter door hanging;
FIG. 11 is a simplified perspective view of a coupling of the crash protection device of FIGS. 8 and 9;
FIG. 11 a is a simplified view of another embodiment of a coupling for a crash protection device of FIGS. 8 and 9;
FIG. 11 b is a view of the coupling of FIG. 11 a as indicated by arrow XI therein, in the coupled state;
FIG. 12 is a simplified view of a second embodiment of the quick-action rolling shutter door of the invention;
FIG. 13 is a view of a second embodiment of the quick-action rolling shutter door hanging of the invention;
FIG. 14 is a view of the reinforcement of the quick-action rolling shutter door hanging of FIG. 13;
FIG. 15 is a sectional view of a variant of the quick-action rolling shutter door hanging of FIG. 13 including expansion slots;
FIG. 16 is a cut-open view of a portion of the quick-action rolling shutter door hanging of the invention including a transverse girder which can be partitioned longitudinally in operation according to yet another embodiment and a longitudinal strip of a reinforcement;
FIG. 17 is a cut-open view of a portion of the quick-action rolling shutter door hanging of the invention including a transverse girder according to yet another embodiment and a longitudinal strap of a reinforcement.
DETAILED DESCRIPTION OF THE INVENTION
The first embodiment of a quick-action rolling shutter door 10 according to the invention, shown in FIGS. 1 to 6 , consists of plural quick-action rolling shutter door modules. A first quick-action rolling shutter door module is the quick-action rolling shutter door hanging 12 which is guided on the side and at the top by a guiding device 14 . Said guiding device 14 includes a roller 16 which can be driven to rotate in either direction by a motor 18 . Said motor 18 is controlled,by controlling means 20 which will also process signals from contact rails and light barriers supplied via signal lines 22 .
FIG. 2 shows the top part 24 of the guiding device 14 . It can clearly be seen in this Figure that the guiding device 14 essentially comprises two lateral guide rails 26 , 28 as well as a head beam 30 maintaining the distance between said two guide rails. Extending in parallel to said head beam 30 is a roller 16 supported in roller support means 32 .
Crucial for the quick-action rolling shutter door 10 is the quick-action rolling shutter door hanging 12 , a first embodiment of which is shown in detail in FIGS. 3 to 5 and further embodiments of which are shown in FIGS. 13 to 17 . Like parts are marked with like reference numerals, but increased by 1,000 or 2,000. The quick-action rolling shutter door hanging 12 of the first embodiment illustrated in FIGS. 3 to 5 has a continuous reinforcement 34 of a steel wire fabric, one side of which is laminated with a first insulating layer 36 of a thickness of 25 mm and the other side of which is laminated with a second insulating layer 38 , likewise 25 mm thick. For use as a burglary-proof door on the outside, a steel fabric is laminated into the foamed material. The steel fabric may be of a thickness of between 0.3 mm to 1 mm. The first and second insulating layers comprise a closed-pore polyurethane foam of a density of 30 kg/m 3 . The first insulating layer is intended to be the external layer and has a smooth fair-faced side 40 which is of the same colour as the actual building. The likewise smooth fair-faced side 42 of the insulating layer 38 intended to face inside, by contrast, which may also be customized, is in a glaring colour.
The thick first insulating layer, however, may also be structured on the outside, which creates the visual impression of a sectional door.
The quick-action rolling shutter door hanging 1012 partially shown in sectional view in FIG. 13, whose reinforcement is not shown therein to keep the drawing simple, has two insulating layers 1036 , 1038 , which—as opposed to the quick-action rolling shutter door hanging 12 of the first embodiment—are not glued onto each other over their entire surfaces, but merely along contact or glue lines 1002 . Said insulating layers 1036 , 1038 are made of a cross-linked foamed polyethylene material marked by HT-Troplast AG under the trade name Trocellen® under the specification 3015 SWB F4 UV. This cross-linked foamed polyethylene material has a raw density of 33±3 kg/m 3 , a longitudinal tensile strength of 0.42 N/mm 2 , a transverse tensile strength of 0,29 N/mm 2 , a ductile yield, in the transverse and longitudinal directions, of approx. 200 per cent, a temperature application range in the bending test of up to minus 40° C., a dimensional stability up to plus 95° C., a thermal conductivity at 30° C. of 0.038 w/m K and a water vapour diffusion current density of <3 g/m 2 d with a thickness of 10 mm.
Further materials suitable for insulating layers are available from ALVEO under the trade name Alveolit®. The properties of these materials may be noted from the table below:
ISO
Properties
Standard
Unit
TA
TA FR
Raw Density
845
kg/m 3
25
25
Tensile Strength
1926
longitudinal
kPa
280
235
transverse
kPa
180
155
Ductile Yield
1926
longitudinal
%
125
115
transverse
%
105
95
Upsetting hardness
844
Upsetting 10%
kPa
12
13
Upsetting 25%
kPa
32
32
upsetting 50%
kPa
92
92
Pressure Deformation
1856-C
Remainder, 22 h
strain, 23° C.,
Upsetting 25%
0.5 h after strain
%
22
21
relieve
24 h after strain
%
13
13
relieve
Thermal Conductivity
2581
at 10° C.
W/mK
0.034
0.034
at 40° C.
W/mK
0.038
0.039
Operating Temperature
in-house
° C.
−80/+100
−80/+100
Range
Water Absorption
in-house
% v/v
<1
<1
(7 days)
Water Vapour
1663
g/m 2 ×
3.8
Permeability
24 h
(2 mm)
(Thickness)
μ value (23° C.,
1663
5500
0-85% r.F)
Shore Hardness 0/00
in-house
17/33
15/34
ISO
Stan-
Properties
dard
Unit
TA FRS
TA FRB
TA FM1
Raw Density
845
kg/m 3
25
25
25
Tensile
1926
Strength
longitudinal
kPa
225
235
225
transverse
kPa
140
150
145
Ductile Yield
1926
longitudinal
%
100
110
100
transverse
%
80
100
90
Upsetting
844
Hardness
Upsetting 10%
kPa
12
12
12
upsetting 25%
kPa
31
32
32
upsetting 50%
kPa
80
95
93
Pressure
1856-C
Deformation
Remainder, 22 h
strain, 23° C.,
Upsetting 25%
0.5 h after
%
22
21
21
strain relieve
24 h after
%
13
13
14
strain relieve
Thermal
2581
Conductivity
at 10° C.
W/mK
0.034
0.033
0.033
at 40° C.
W/mK
0.039
0.037
0.037
operating
in-
° C.
−80/+100
−80/+100
−80/+100
Temperature
house
Range
Water
in-
% v/v
<1
<1
<1
Absorption
house
(7 days)
Water Vapour
1663
g/m 2 ×
1.8
Permeability
24 h
(5, 5mm)
(Thickness)
μ value (23° C.,
1663
4100
0-85% r.F)
Shore Hardness
in-
16/29
18/29
17/27
0/00
house
FIG. 15 shows a variant of the quick-action rolling shutter door hanging 1012 of FIG. 13 . This variant of a quick-action rolling shutter door hanging 2012 has expansion slots 2004 on its external side which expand to form notches 2006 during the winding up of the quick-action rolling shutter door hanging 2012 , thus contributing to a strain reduction within the material of the quick-action rolling shutter door hanging 2012 and facilitating the winding up onto rollers.
FIG. 14 shows a reinforcement 1034 for the quick-action rolling shutter door hanging which comprises first and second transverse girders 1300 , 1302 as well as longitudinal strips 1304 . The first transverse girders 1300 are simple aluminium profiles of rectangular cross-section which extend transversely to the direction of travel of the quick-action rolling shutter door hanging and are connected to longitudinal strips at regular intervals by means of through bolts. The longitudinal strips 1304 are flexible metal strips which may easily be wound up, but present a strong resistance towards being cut by knives or other cutting tools. FIG. 17 shows a first transverse girder 1300 and longitudinal strip 1304 together with first and second insulating layers 1036 , 1038 , respectively.
FIG. 16 shows a portion of a quick-action rolling shutter door hanging 1012 with a second transverse girder 1302 which consists of two parts. Said second transverse girder comprises a first transverse girder part 1306 and a second transverse girder part 1308 , which two parts are slid into each other such that they can be slidingly separated along a parting line 1310 . Said first and second transverse girder parts 1306 , 1308 each have two insertion channels 1312 , 1314 accommodating the insulation layers 1036 , 1038 . For interconnection or, if necessary, for connection to first transverse girders 1300 , longitudinal strips 1304 are again provided. Said longitudinal strips 1304 are bent U-shaped around holding means 1316 so as to ensure a safe connection of said longitudinal strips 1304 to said transverse girder parts 1306 , 1308 via a screwed connection of said longitudinal holding means 1316 . For use of the quick-action rolling shutter door hanging 1012 in an environment where heat or cold insulation is important, the second transverse girders 1302 should be designed such that they will not form cold bridges. To this end, the profiles from which the transverse girder parts 1306 , 1308 are made may be provided with insulating ribs. As an alternative, second transverse girders 1302 need not be provided altogether since, if first transverse girders 1300 are used exclusively, as shown in FIG. 17, there will not be any cold bridges.
As an alternative to the insulating layer material described, ollier materials may also be used in the insulating layers, comprising a flexible open- or closed-cell foamed material of a chemically or physically cross-linked type. A closed skin is advantageous. Materials of foamed polyolefins of a temperature stability up to at least −35° C., preferably −40° C., and a K-value of <2.5 are particularly suited.
Foamed materials which are especially well suited are:
PE—Polyethylene:
Reusable—UV proof—available in any colour, behaviour in fire: DIN 4102 B1, B2 class—temperature application range −40° C. up to 105° C.,
K-value of between 1 and 1.4—raw density of between 30 and 250 kg/m 2
Foam thickness of between 10 mm and 40 mm for the door insert.
PU—Polyurethane:
Recyclable, UV proof, extremely sound absorbing, temperature stability −40° C. up to, for a short time, 170° C.,
K-value 1 to 1.4, raw density between 30 and 250 kg/m 2 Behaviour in fire: DIN 4102 B1, B2 class
Foam thickness of between 10 mm and 40 mm for the door insert.
EPDM—Synthetic Rubber:
Recyclable and suitable for disposal in household rubbish, UV proof,
fire behaviour DIN 4102 B1, B2 class
Temperature stability from −57° C. to 150° C.
Foam thickness of between 10 mm and 40 mm for the door insert.
PVC—Polyvinylchloride.
For absorbing the wind forces acting on the quick-action rolling shutter door hanging (FIG. 3 ), antibuckling profiles 44 are provided. These profiles 44 extend on either side of the reinforcement 34 transversely to the direction of travel of the door, bridging the distance between the guide rails 26 , 28 of the guiding device 14 , and may also serve as the transverse girders of a reinforcement. Said antibuckling profiles 44 extend essentially Z-shaped and have one leg engaging said reinforcement. Their respective other leg engages the external side of the respective insulating layer 36 , 38 , thus subdividing said insulating layer 36 , 38 into individual portions. Since said insulating layers 36 , 38 are flexible, as is notable from FIG. 3, and said antibuckling profiles 44 are of low height, the quick-action rolling shutter door hanging 12 of FIGS. 3 to 5 may be wound up onto roller 16 .
In order not only to prevent any strong bending or deflection of the quick-action rolling shutter door hanging 12 , but to ensure a reliable support of the quick-action rolling shutter door hanging 12 at the same time, track roller means 46 are provided at the ends of said antibuckling profiles 44 which are opposite each other, with said reinforcement 34 in-between. Said track roller means 46 —which is also illustrated in FIG. 6 —includes an axle body 48 on which two roller bodies 52 , spaced from each other by means of a sleeve 50 , are rotatably mounted. One of said roller bodies 52 contacts support screw means 54 provided at one end thereof. The second roller body is supported by a grab body 58 , screwed onto said axle body 48 and including a slot 56 , so as to loosely contact said sleeve 50 . In this state, said grab body 58 also encompasses (FIG. 5) a leg each of two opposing antibuckling profiles 44 to which it is at the same time glued, soldered or welded, depending on the material of said antibuckling profiles 44 .
FIG. 6 illustrates how said roller bodies 52 , which are supported on their respective axle body 48 and may also be referred to as tandem rollers, are guided in their respective guide rail 26 .
The guide rail 26 shown in FIG. 6 includes a support body 60 made of a rectangular square profile. Mounted on said support body 60 by means of a hinge 62 is a swivelling part 64 made of an equal angle profile. The edge length of said swivelling part 64 is somewhat longer than that of the support body, enabling said swivelling part 64 to encompass said support body 60 , with a reference edge 66 of said swivelling part and a reference surface 68 of said support body 60 being essentially on one plane at the same time so as to define an oblong aperture 70 therebetween for the quick-action rolling shutter door hanging 12 .
In the state illustrated in FIG. 6, the free leg 72 of the swivelling part 64 extends essentially in parallel to a longitudinal wall 74 of the support body 60 so that these two elements, i.e. the longitudinal wall 74 of said support body 60 and the free leg 72 of said swivelling part 64 , function almost like parallel legs of a U profile. In order to maintain said support body 60 and said swivelling part 64 in this relative position and thus to prevent this constellation from coming apart in operation, a screwed connection 76 is provided which extends through said swivelling part 64 and engages a threaded bore in said support body 60 .
The guide rail shown in FIG. 6 is intended for assembly within a refrigerating chamber. In order to prevent the roller bodies 52 from freezing up and thus blocking, the guide chamber 78 defined by the longitudinal wall 74 and the free leg 72 is lined with heat insulation elements 80 which have at least one heating coil 82 on their internal side for heating said guide chamber 78 . Brush bodies 84 provided on either longitudinal side of said aperture 70 will prevent any excessive heat loss from said guide chamber 78 .
In order to prevent the rolling shutter door hanging from being pushed up, said quick-action rolling shutter door 10 may be equipped with an anti-push-up device 84 . Such an anti-push-up device 84 , which is shown in FIGS. 7 and 8, includes two detent latches 86 , 88 which are rotatably mounted on the axle body 48 of lower track roller means 46 . In this construction, the centre of gravity of said two detent latches 86 , 88 is above the axis of rotation of said axle body 48 , in an off-centre position. As a consequence, under the influence of gravity, both detent latches 86 , 88 would therefore rotate about the axis of rotation of said axle body 48 in opposite directions, if such movement were not prevented for the moment by a retaining belt 90 . If the rolling shutter door hanging 12 were pushed up, however, the retaining belt 90 , which is suspended from the axle body 48 above the axle body 48 bearing the detent latches 86 , 88 , would become relieved, resulting in said two detent latches 86 , 88 rotating until they are stopped by the walls of the guide chamber 78 of the guide rail 26 .
FIG. 8 a shows a variant of an anti-push-up device in which the detent latches 86 ′, 88 ′ are prebiased by a twisting spring 89 .
FIGS. 9 to 11 illustrate a crash protection device 92 preventing the destruction of track roller means in the case of a collision of a vehicle with the quick-action rolling shutter door hanging 12 . The crash protection device 92 , which may be provided as an alternative to the anti-push-up device 84 , includes track roller means 94 guiding a coupling 96 . Said coupling 96 includes a clamp roller 98 which is accommodated in a support channel 100 of a clamp body 102 . Said clamp body 102 is screwed to a floor rail 104 forming the bottom end of the quick-action rolling shutter door hanging 12 . In this construction, the support channel 100 of the clamp body 102 is oriented so as to extend transversely to the extension of the quick-action rolling shutter door hanging 102 . A minimum holding force between clamp roller 98 and clamp body 102 is obtained in that clamp roller 98 has a rubber-elastic running surface and in that the support channel 100 within said clamp body 102 is concavely shaped both at the top and at the bottom.
So as to enable the clamp roller 98 to become decoupled from the clamp body 102 in the case of a collision, the quick-action rolling shutter door hanging 12 , in the region of the crash protection device 92 , is cut such that it will not project into the guide rail 26 . In order to safeguard a tight closing nonetheless, a cover 106 is provided where the crash protection device 92 is, which cover 106 is of a design corresponding to the laminated construction of the quick-action rolling shutter door hanging 12 and connects the bottom-most track roller device 94 with the track roller device 108 above it. Besides this cover 106 , coupling belts 110 are provided which keep track roller device 94 and track roller device 108 at a fixed distance from each other.
In order to accomplish a good sealing between said cover 106 and said quick-action rolling shutter door hanging 12 , the opposing edges 112 and 114 of said cover and said quick-action rolling shutter door hanging 12 , resp., are curved complementary towards each other, leaving merely a small sealing gap 116 between them. Since both the quick-action rolling shutter door hanging 12 and the cover 106 are made of an elastic material, the quick-action rolling shutter door hanging 12 and the cover 106 will overlap. During decoupling of the crash protection device 92 , some material of the quick-action rolling shutter door hanging 12 and of the cover 106 will be compressed, leaving the lower portion of the quick-action rolling shutter door hanging 12 free.
FIGS. 11 a and 11 b illustrate a clamp body 102 ′ for a second embodiment of a coupling for a crash protection device. Said clamp body 102 ′ is in two parts, i.e. it comprises upper and lower clamp body halves 1400 , 1402 ′ which are both inserted in a recession of a profile 1404 extending transversely to the direction of travel of the door. The (common) end 1406 of said upper and lower clamp body halves 1400 , 1402 which faces a clamp roller 98 ′ is shaped like the clamp body 102 of FIGS. 9 to 11 , with the only exception that no wheel-like projection is being encompassed here.
The upper and lower clamp body halves 1400 , 1402 support each other at a contact surface 1408 and each have bevel or chamfered portions on the side opposing the clamp roller so as to leave a free portion 1410 between them, allowing a pincer-like movement of the two clamp body halves 1400 , 1402 towards each other, either to release or to reaccommodate the clamp roller 98 ′. For prebiasing the two clamp body halves 1400 , 1402 in their holding position, a helical spring 1412 is provided at the end of the clamp body opposing the clamp roller 98 ′, with a pressure load acting on said spring 1412 along its longitudinal axis, said spring 1412 being guided in chambers 1414 , 1416 of the upper or lower clamp body halves 1400 , 1402 , respectively.
The quick-action rolling shutter door 10 shown in FIGS. 1 to 6 can be readily assembled within a very short time according to a scheme known from the furniture industry including assembly instructions in the form of illustrations (FIG. 2 ). The guide rails 26 , 28 and the top 24 , which are manufactured according to specifications of the clear dimensions, are prefabricated in production in such a way that the user will not have to perform major measurements owing to the specified screwed connections and mountings, and that these parts allow easy assembly according to the unitized construction principle. First of all, the guide rails 26 , 28 are laid out on the floor, screwed to transverse girders and mounted in the wall opening. The screwed connections of the roller support means to the shaft, hanging, motor and the transverse girders were already provided by the manufacturer. Using a forklift truck, the user will lift the prefabricated roller support means and insert it in the mountings intended for this purpose. Subsequently, the top part is secured (in position) by means of screws.
It should further be noted that—in view of the bending behaviour of the foamed material and the steel fabric contained therein—the shaft diameter should be 200 mm at least.
A second embodiment of a quick-action rolling shutter door 210 according to the invention is illustrated in FIG. 12 . This quick-action rolling shutter door 210 has a quick-action rolling shutter door hanging 212 which is vertically divided at the centre. The upper end of said hanging 212 extends in a guide rail 226 of a guiding device 214 , and said hanging 212 may be laterally wound up onto a first roller 216 and a second roller 217 . The quick-action rolling shutter door hanging 212 has two mutually complementary magnet rails at its centre which keep the quick-action rolling shutter door hanging 212 together at its centre in its closed state. For increasing safety around the quick-action rolling shutter door 210 , two windows 213 are provided in said quick-action rolling shutter door hanging 212 , which windows 213 are of a transparent plastic material and are welded onto the material of the quick-action rolling shutter door hanging 212 . A quick-action rolling shutter door hanging of this design is also advantageous in a quick-action rolling shutter door of the first embodiment. The quick-action rolling shutter door hanging 212 which is identical in construction to the hanging 12 of the quick-action rolling shutter door 10 of the first embodiment, may readily be provided with windows 213 since its closed-pore insulating layers do not require any sealing or bordering. | A quick-action rolling shutter door and to modules thereof. Quick-action rolling shutter doors are used for closing openings in tie walls of warehouses or factory buildings in order to restrict the loss of energy from heated or cooled rooms, and to protect the environment by keeping escaping noise, odours and dust emissions to a minimum. Known quick-action rolling shutter doors have disadvantages in relation to heat insulation. The object is to provide an improved quick-action rolling shutter door with corresponding modules. According to a first aspect, a flexible quick-action rolling shutter door hanging ( 12 ) can be wound up onto a roller, is guided on at least one side by a guiding device and has at least one thick-walled insulating layer ( 36, 38 ) consisting of plastic foam material. | 4 |
This application is a continuation of application Ser. No. 10/404,354, now allowed, which is a continuation of application Ser. No. 09/847,876, now U.S. Pat. No. 6,659,681, which is a continuation-in-part of application Ser. No. 09/247,217, filed on Feb. 10, 1999, and now U.S. Pat. No. 6,402,422.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to traffic safety devices and, more specifically, to vertical panel display systems.
2. Description of the Related Art
Highway signs are generally used for promoting the safe passage of motor vehicles and/or pedestrians by advising of, for example, approaching unsafe driving conditions. These highway signs are generally provided with various highway legends, and are generally configured to flex in response to prevailing winds and wind gusts created by motor vehicles and the like.
It is known in the art to use a vertical panel system as a highway sign. In a typical vertical panel system, a vertical panel is on a collapsible support so that it folds down when impacted by a vehicle. This mitigates damage to the panel and the vehicle. A common example is an A-frame design consisting of two sides which are hinged together at the top. Each side has a panel attached to it. For support, the A-frame design is weighed down by sandbags. Upon impact, the A-frame folds flat. This design, while simple to build, is relatively unpredictable and requires at least two components, the A-frame and a sandbag, and maybe more than one sandbag.
An improvement on this idea is disclosed in U.S. Pat. No. 4,792,258 to Goff entitled “Collapsible Warning Barricade Apparatus” (“Goff”), which is incorporated herein in its entirety. Goff discloses a vertical panel pivotally attached to a base. The panel was maintained in a vertical position, with the use of a compression spring device that exerted a force on an automatic locking means at the pivot point. The automatic locking means has multiple elements that are coordinated to maintain the panel in an upright position until impact. Unfortunately, the design as disclosed in Goff is complicated to build and requires many parts.
It is also a problem with vertical panel systems that when they are impacted, the systems are dragged with the vehicle. As the base or support of the system is attached to the panel, both the panel and the base are damaged. Further, as the vehicle is dragging both the panel and the base, the vehicle incurs increased damage than if the panel was being dragged alone.
The prior art discloses a vertical panel system with a breakaway safety feature such that the panel separates from the base when impacted. This system is available under the trade name WindBreakers from Trafcon Industries Inc, 81 Texaco Road, Mechanicsburg, Pa. 17055. The WindBreakers' panel is attached to the rubber base via a breakaway pin that is inserted through the width of the panel. A disadvantage of the WindBreaker is that a replacement pin must be used to reattached the panel to the base as the original pin shears upon separation. Another disadvantage is that the WindBreaker panel flexes in the wind. An additional disadvantage is that the panel does not easily release to stack the bases and panels flat.
Another prior art system is disclosed in U.S. Pat. No. 5,670,954 to Junker. This system is similar to WindBreakers system discussed supra, in that a vertical panel 4 is secured to a base using a bolt and nut mechanical fastening combination. A disadvantage of this system is complexity. Additionally, the base securement is designed to be permanent, so there is no ability for the panel to break away from the base, short of the destruction of the system.
Still another prior art system is disclosed in U.S. Pat. No. 5,484,225 to Warner. This patent discloses a vertical panel system wherein a vertical panel is secured to a base without the use of mechanical fasteners, by means of a friction/compression fit. However, although this approach is an improvement over the systems discussed supra, it still has a number of problems. For example, to effect the panel/base attachment, the bottom edge of the panel is merely inserted into a slot in the base. There is no structure to prevent the vertical panel from rocking from side to side, and the engagement between the panel and base is subject to wear of the interior surface of the base slot over time, until at a particular point in time the friction/compression fit will be inadequate to properly support the panel. Additionally, there is no structure to assist a user in inserting the panel into the slot.
Therefore, it is desirable to have a vertical panel system which is collapsible upon impact, the panel is separable from the base during impact, is easily stacked, and made from relatively few parts. It is also desirable to have a panel that can be reattached to the base without replacing parts. It is also desirable to have the panel surface protected from scratches and mars while it is being hit or dragged. It is also desirable to have a panel that does not flex from the wind force.
SUMMARY OF THE INVENTION
The present invention provides an advantageous improved vertical panel system, which comprises a vertical panel having a panel with opposing first and second panel surfaces and a base edge. The system further comprises a base having a slot for engaging the base edge of the panel. Advantageously, an aperture is disposed in the panel in proximity to the base edge, which is of sufficient size to receive a foot of a user, for assisting in the engagement of the panel and the base.
In another aspect of the invention, there is provided a base for a vertical panel system, which comprises a center zone fabricated of vulcanized rubber, and an outer zone fabricated of recycled rubber. A slot is disposed in the center zone for receiving a base end of a vertical panel in engagement therewith. This arrangement solves a need to be environmentally responsible and cost effective by recycling rubber which would otherwise fill our landfills, yet provides great durability by using virgin vulcanized rubber in the zone of the base which includes the engagement slot.
In still another aspect of the invention, there is disclosed a method of assembling a vertical panel system comprised of a vertical panel having a base end and an aperture sufficiently large to accommodate a user's foot disposed adjacent to the base end. A base comprising a part of the system for ballasting the vertical panel has a slot for receiving the vertical panel base end. The inventive method comprises the steps of positioning the vertical panel over the base, so that the base end is in proximity to and just above the slot. Then, a user's foot is placed through the aperture, whereupon the user presses downwardly with his or her foot to apply downward force on the vertical panel, so that the base end of the vertical panel is inserted into and becomes engaged with the slot. This innovative method avoids the problem of using one's arms to press down from the top of the vertical panel, which can be a tiring and difficult job.
The invention, together with additional features and advantages thereof, may best be understood by reference to the following description taken in conjunction with the accompanying illustrative drawing.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows an exploded perspective view of a vertical panel system with one panel according to an embodiment of the invention;
FIGS. 2 and 3 are perspective and plan views, respectively, showing details of assembly of the vertical panel system of FIG. 1 ;
FIG. 4 shows an exploded perspective view of a dual vertical panel system according to an alternative embodiment of the invention;
FIG. 5 is a plan view showing details of the engagement portion of the vertical panel system of FIG. 4 ;
FIGS. 6 and 7 are plan views showing details and positioning of reflective portions of Type I and Type II barricades, respectively;
FIG. 8 is a plan view of another alternative embodiment of the present invention;
FIG. 9 is a perspective view of the base portion of the vertical panel system illustrated in FIG. 8 ;
FIG. 10 is a perspective view of the vertical panel portion of the system of FIG. 8 ;
FIG. 11 is a view similar to FIG. 10 showing the application of reflective material to a front panel of the vertical panel portion; and
FIG. 12 is a view similar to FIG. 10 illustrating an alternative embodiment wherein a sign panel is attached to the vertical panel portion.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the figures, wherein like reference numerals refer to like elements throughout the figures, and referring specifically to FIG. 1 , a vertical panel system 10 according to an embodiment of the invention comprises a vertical panel 12 and a base 14 . When a tab 16 extending from a lower end of the vertical panel 12 is inserted into a slot 46 in the base 14 , the assembled vertical panel system 10 resembles an inverted T with the base 14 being the cross member. The vertical panel system 10 is designed to remain standing in wind and gusts from bypassing vehicles while being able to separate into the panel 12 and base 14 upon impact. Because the vertical panel system 10 is able to separate, the damage to the impacting vehicle and the system is mitigated.
The vertical panel 12 is comprised of a panel 20 with opposing panel first and second surfaces 22 (only one panel surface shown). The panel 20 has a base edge 24 proximate to the base 14 and from which the tab 16 extends. The panel 20 also has a top edge 26 that opposes the base edge 24 . Two opposing side edges 28 of the vertical panel 12 extend between top edge 26 and the base edge 24 .
In the illustrated embodiment of the invention, the edges 24 , 26 , and 28 are raised above the panel surfaces, so that the first and second panel surfaces 22 are recessed into the panel 20 . Because the edges 24 , 26 , and 28 are raised, the edges get scraped during normal usage and wear and tear, rather than the panel surfaces 22 or anything on the panel surfaces. Examples of causes of scraping includes the system 10 being struck or the panel 20 skidding across the ground. The panel surfaces 22 may be reflective, either by having reflective material, such as sheeting, disposed thereon or the panel surfaces comprise reflective material. The panel surfaces 22 may have other indicia thereon. Whether it is reflective material or other indica on the panel surfaces, it is protected by the raised edges 24 , 26 , and 28 .
In a preferred embodiment of the invention, the raised edges 24 , 26 , and 28 protrude in a direction normal to the panel surfaces 22 . In other embodiments of the invention, the raised edges 24 , 26 , and 28 may extend above the panel surfaces in a direction other than normal to the panel surfaces. In some instances, it may be advantageous for only a portion of the edges 24 , 26 , and 28 to be raised, or the edges 24 , 26 , and 28 may be raised above only one of the panel surfaces. The edges 24 , 26 , and 28 may be integral to the panel 20 or may be a separate but attached component of the panel 20 .
In the illustrated embodiment of the invention, the vertical panel 20 is rectangular. Other embodiments of the invention may have vertical panels of other shapes. In the preferred embodiment of the invention, the vertical panel 12 is comprised of double wall blow molded plastic. Other embodiments of the invention may have a vertical panel comprised of other materials.
The tab 16 extends from a base edge 24 of the panel 20 and terminates at a tab bottom edge 30 . The tab 16 comprises two opposing side surfaces 32 (only one side surface is shown) that extend between two opposing side edges 34 . Each of the tab side surfaces 32 have two tab grooves 36 extending from the tab bottom edge 30 and towards the panel base edge 24 . In the preferred and shown embodiment of the invention, the tab bottom edge 30 is parallel to the panel base edge 24 and the tab grooves 36 extend perpendicularly to the bottom edge and the base edge. Other embodiments of the invention may have other relationships between edges 24 and 30 and the tab grooves 36 . The tab bottom edge 30 extends a length 31 that is shorter than the width 50 of the panel 20 .
In other embodiments of the invention, only one of the tab surfaces 32 may have tab grooves 36 . In other embodiments of the invention, there may be more or fewer than two tab grooves 36 on a tab side surface 32 . In the illustrated embodiment of the invention, the tab grooves 36 have a generally U-shaped profile (see FIG. 2 ). Other embodiments of the invention may have tab grooves with other suitable profiles. In the illustrated embodiment of the invention, the tab 16 and the panel 20 reside in generally the same plane. In other embodiments of the invention, the tab 16 may be oriented at a different angle to the panel 20 , such as a plane extending through the tab side edges 34 defines a plane that is normal to the panel 20 . In the illustrated embodiment of the invention, the panel 20 has one tab 16 . Other embodiments of the invention may have more than one tab. In the illustrated embodiment of the invention, the tab 16 is of a rectangular cube shape. Other embodiments of the invention may have tabs of other shapes. In the illustrated embodiment of the invention, the tab 16 is integral to the panel 20 . Other embodiments of the invention may have the tab 16 separably attached to the panel 20 .
The base 14 has a top surface 40 , a major axis 42 extending along the length of the base and a minor axis 44 extending along the width of the base. At the intersection of the axes 42 and 44 is a slot 46 . The slot 46 extends from the top surface 40 and into the base 14 . The slot 46 complements the tab 16 and the tab grooves 36 . The fit of the slot 46 with the tab 16 may be loose, snug, or it may be an interference fit. An interference fit of the slot 46 and the tab 16 may be suitable for embodiments of the invention in which the base is made of an elastomeric material, such as rubber. The slot 46 may extend through the base 14 or terminate in the base.
To assemble the vertical panel system 10 , the tab 16 is inserted into the slot 46 . In the illustrated embodiment of the invention, the vertical panel 12 is oriented along the minor axis 44 . Other embodiments of the invention may have the vertical panel oriented in other directions.
In the illustrated embodiment of the invention, the base 14 has a length 48 that is long enough to inhibit the vertical panel system 10 from tumbling in the direction of the major axis 42 when wind or gusts catches the vertical panel 20 . The panel base edge 24 extends a width 50 that is substantially equal to a width 52 of the base 14 .
Referring now to FIGS. 2 and 3 , the tab 16 is shown partially and fully inserted into the slot 46 , respectively. The complementing slot 46 is shown with projections 47 extending into the grooves 36 in FIG. 3 . It is clearly shown in FIG. 3 that the width 50 of the panel 20 is approximately the same of the width 52 of the base 14 . Further, when the tab 16 is fully inserted into the slot 46 , the base edge 24 of the panel 20 is in contact with the upper surface 40 of the base 14 across the width 52 of the upper surface. This contact provides a stable fitting of the panel vertical panel 12 and the base 14 that resists the tab 16 from coming out of the slot 46 through repeated lateral movements of the vertical panel 12 in the direction of the minor axis 44 .
A significant advantage of the present invention over the prior art is that this “button” or “tongue and groove” engagement between the tab grooves 36 and the base projections 47 is a vast improvement over the mere friction/compression fit disclosed in the prior art, such as in the Warner '225 patent discussed supra. The advantages include increased durability, because wear and tear to the interface over time does not as severely affect the positive interface between the projections and grooves as it does a mere friction/compression fit, and improved stability, or, more specifically, the ability to resist rocking of the panel to the left or right side because of wind gusts due to passing traffic.
The base 14 is made of rubber in a preferred embodiment of the invention. The rubber base 14 provides ballast for the system 10 to inhibit tipping or moving the system while in use. Other embodiments of the invention may use any suitable ballasting type device as a base, such as a hollow plastic container filled with sand or another ballast or a frame that is secured in place with sand bags.
Referring now to FIG. 4 , a dual paneled vertical panel system 100 has a vertical panel 112 with a lower panel 120 and an upper panel 121 that is mounted in a base 114 . In the illustrated embodiment, the panels 120 and 121 generally define a plane. Other embodiments of the invention may have the panels 120 and 121 at a different orientation relative to one another or to the ground.
The panels 120 and 121 preferably have raised edges 123 . A base edge 124 of the lower panel 120 is located distal to a top edge 127 of the upper panel 121 . A top edge 126 of the lower panel is located proximate to a base edge 125 of the upper panel 121 . A support member 102 extends between the lower panel top edge 126 and the upper panel base edge 125 . The support member 102 may be unitary with the two panels 120 and 121 or may be separably attached to the panels. Other embodiments of the invention may have different arrangements for the support member, including a plurality of support members or a support member that supports the two panels other than extending between the edges 125 and 126 . In a preferred embodiment the support member 102 is integrally molded (such as by injection molding) with the panels 120 , 121 .
A tab 116 extends downwardly from the base edge 124 of the lower panel 120 . The tab 116 has tab grooves 136 , tab side edges 134 , and a bottom edge 130 much like the tab grooves 36 , tab side edges 34 and a bottom edge 30 of the vertical panel system 10 . Additionally, tab 116 has shoulder portions 135 that laterally extend from the tab side edges 134 . The shoulder portions 135 result in the tab 116 expanding to a width 150 ( FIG. 5 ) as it approaches the lower panel. In a preferred embodiment of the invention, the width 150 is approximately the same as the width 152 of the base 114 .
Referring now to FIG. 5 as well, only a lower portion 117 of the tab 116 is inserted in a slot 146 of the base 114 when the system 100 is assembled. The tab lower portion 117 extends between the tab bottom edge 130 to the shoulders 135 . FIG. 5 more clearly shows that the width 150 of the tab 116 is approximately the same as the width 152 of the base 114 . This results in the shoulder 135 making contact with the base upper surface 140 across the width 152 of the base 114 . The contact provides a very stable assembled system 100 as previously described in connection with the base edge 24 making contact with the base 14 .
In an embodiment of the invention, panel surfaces are sized and positioned to conform to Type I or Type II barricade requirements. More specifically, the reflective sheeting requirements of the Type I or Type II barricades are mounted to appropriately sized and positioned panel surfaces in a vertical panel system that embodies the invention.
Referring now to FIG. 6 , the size and positioning of a reflective portion 200 of a Type I barricade is shown relative to the ground 202 . The reflective portion 200 has white stripes 204 that alternate with orange strips 206 . The stripes 204 and 206 are oriented at a right-facing 45 degree angle and have a width 208 of six inches. Other reflective portions of Type I barricades may have the stripes 204 and 206 oriented in a left-facing manner. The portion 200 preferably has a height 210 of 8 to 12 inches and a length 212 of at least 2 feet. The top 214 of the portion 200 is at least 3 feet above the ground 202 .
Referring now to FIG. 7 , the size and positioning of an upper reflective portion 220 and a lower reflective portion 221 of a Type II barricade is shown relative to the ground 202 . The stripes 204 and 206 , the stripe width 208 , the stripe orientation, the height 210 and the length 212 of each reflective portion 220 and 221 is the same as for the reflective portion 200 . The portion 221 is positioned below the portion 220 . The top edge 214 of the upper portion 220 is preferably greater than 3 feet from the ground 202 .
In illustrated embodiments of the invention, the vertical panel has a contact surface that makes contact with the upper surface of the base. In the embodiment of the invention 10 shown in FIG. 1 , the contact surface is the portion of the base edge 24 that extends beyond the tab 16 . In the embodiment of the invention 100 shown in FIG. 4 , the contact surfaces are the shoulders 135 of the tab 116 . In preferred embodiments of the invention, the contact surface has an overall length that is approximately equal to the width of the base at the point of contact. The matching of the vertical panel contact surface length and the base width results in a laterally stable vertical panel system without having a vertical panel with excess material and the resulting higher manufacturing costs. Other, less preferred embodiments of the invention may have a vertical panel contact surface that does not extend across the width of the base. Additionally, other, less preferred embodiments of the invention may have portions of the contact surface extend beyond the width of the base.
Now with reference to FIGS. 9-11 , a modified and preferably preferred embodiment of the invention is illustrated. In this embodiment, a vertical panel system 310 comprises a vertical panel 312 which is securable to a base 314 and includes a panel portion 322 . As in prior embodiments, the vertical panel 312 is preferably blow molded of plastic, though any known fabrication techniques may be employed. As in the prior embodiments, as well, the panel portion 322 (preferably, opposing panel portions) is recessed relative to the raised edges of the vertical panel, to protect from incidental damage any reflective sheeting 360 (see FIG. 11 ) which may be disposed on the panel portion surface 322 .
As shown in the FIGS. 9-11 embodiment, the top end 326 of the vertical panel 312 comprises a flange 362 having a pair of handle apertures 364 , for easy carrying of the vertical panel 312 , and a center mounting hole 366 for ready attachment of accessories. Such accessories may include a barricade light 368 , as shown in FIG. 8 , which is secured to the vertical panel 312 by means of mechanical fasteners attached to the mounting hole 366 , and to a similar hole (not shown) in the light. The attachment mechanism is well known in the traffic safety product art for securing barricade lights to a variety of traffic safety products, typically barricades and traffic delineators. Other accessories might include a panel sign 370 , as shown in FIG. 12 , which may be attached to the vertical panel 312 by means of mechanical fasteners 372 and 374 , wherein fastener 372 is secured to the mounting hole 366 and fastener 374 is secured to a second mounting hole extending through the vertical panel surface 322 . The sign 370 may have any desired message displayed thereon, and may preferably be comprised of a corrugated semi-rigid material, or any other suitable rigid or semi-rigid material. In one preferred embodiment, the sign 370 is 36 inches square, although other dimensions may be suitable as well.
Another significant improvement in the FIG. 9 embodiment is the employment of a foot aperture 376 , molded or cut into a bottom portion of the vertical panel surface 322 , adjacent to the bottom edge 324 of the vertical panel 312 . This foot aperture has been found by the inventors to be a significant advantage when inserting the tab portion 316 into the slot 346 in the base 314 to assembly the vertical panel system 10 , in that it permits a user to merely place his or her foot conveniently into the aperture 376 and use downward force generated by the act of stepping down with the inserted foot to press the vertical panel 312 into the slot 346 . Without using the aperture 376 , which in preferred embodiments is approximately 3 inches high by 5 inches wide, the panel 312 must be pressed into the slot by pushing downwardly on the top edge of the panel 312 using the arms. As the insertion forces necessary to complete the assembly are quite high, this can be a tiring procedure.
In a particularly preferred embodiment, gussets 378 are molded in the vertical panel surface 322 adjacent to each side edge of the aperture 376 . These gussets comprise raised portions or ridges, relative to the remaining vertical panel surface 322 , which provide strength at the bend point.
Still another preferred feature is the employment of a plurality of stacking lugs 380 on each edge of the vertical panel 312 , for assisting in stacking a plurality of vertical panels 312 together. Protruding stacking lugs on one side of each of the vertical panels engage complementary recesses on opposing sides of adjacent stacked vertical panels to thereby engage the vertical panels to one another, thus decreasing slippage of the stacked vertical panels relative to one another.
With respect to FIG. 9 , in particular, the base 314 is an improved version of the bases shown in previous embodiments, in that carrying handles 382 have been molded or cut into opposing edges thereof. The base 314 is preferably molded of recycled rubber, such as crumb rubber, in order to reduce costs and to be environmentally responsible. However, Applicants have found that the use of crumb rubber in the vicinity of the slot 346 is not ideal, because it is much more prone to wear and tear (erosion) over time, shortening greatly the useful life of the base because the erosion will ultimately be too great to permit a proper friction/compression fit between the base and tab 316 . Accordingly, Applicants have developed an innovative solution whereby a zone 384 of virgin vulcanized rubber is insert-molded into the crumb rubber base during the fabrication process. The slot 346 is then formed in the vulcanized rubber zone, providing reinforcement from wear and tear due to repeated panel separation. In presently preferred embodiments, the base 314 is fabricated in two weights—28 pounds and 43 pounds.
Still another innovative feature is the employment of four raised anti-rotational foot pads 386 ( FIG. 8 ) on the lower surface of the base 314 , to minimize movement from wind, or turbulence from passing vehicles. This is particularly important in the case of vertical panels, where it is important to maintain a zero degree orientation relative to passing traffic. Preferably, these feet 386 are molded into the extreme corners of the base, and may comprise in one preferred embodiment a size of three inches in diameter and ¼ inch in height.
The vertical panels illustrated in the drawings are merely representative of the various shapes, sizes, and configurations which fall within the scope of the claimed invention. For example, vertical panel systems may be offered in various sizes, such as 36 inch×8 inch, 24 inch×12 inch, 24 inch×8 inch, or 29½ inch×12 inch, and may be utilized in combination with different sized bases (such as the 28 and 43 pound bases which are presently preferred). Additionally, the reflective sheeting on the panel face may cover some or all of the available surface, depending upon application. As an alternative to the illustrated striped pattern, a vertical panel may accommodate a display sign, with a message for passing motorists.
Although presently preferred embodiments of the present invention have been described in detail hereinabove, it should be clearly understood that many variations and/or modifications of the basic inventive concepts herein taught, which may appear to those skilled in the pertinent art, will still fall within the spirit and scope of the present invention, as defined in the appended claims. | A vertical panel system comprises a vertical panel having a panel with opposing first and second panel surfaces and a base edge. The system further comprises a base having a slot for engaging the base edge of the panel. An aperture is disposed in the panel in proximity to the base edge, which is of sufficient size to receive a foot of a user, for assisting in the engagement of the panel and the base. The base for the vertical panel system comprises a center zone fabricated of vulcanized rubber, and an outer zone fabricated of recycled rubber. The slot is disposed in the center zone. Thus, the combination solves a need to be environmentally responsible and cost effective by recycling rubber which would otherwise fill our landfills, yet provides increased durability by using virgin vulcanized rubber in the zone of the base which includes the engagement slot. | 4 |
CROSS-REFERENCE TO RELATED APPLICATION
This application claims the benefit of U.S. Provisional Patent Application No. 61/814,674, filed on Apr. 22, 2013, entitled “DRIVE ASSISTED ROLLER ASSEMBLY FOR ROLLING DOOR”, which is hereby incorporated by reference in its entirety.
FIELD OF THE INVENTION
The disclosed embodiments relate to the field of drive systems for opening and closing rolling doors.
BACKGROUND OF THE INVENTION
Existing drive systems for rolling curtains/doors employ rollers on the door edges which engage surfaces of a track in a door guide positioned on a pair of opposite sides of a door opening. The door (curtain) may be a vertical door, which is deployed from top to bottom across a door opening; a side-coiling curtain, which is deployed sideways from left-to-right (or right-to-left) across the door opening; or a horizontal curtain, which is deployed across a horizontal opening such as, for example, a floor opening containing an escalator.
In such doors, the rollers provide a rolling engagement along the guide tracks. The door (curtain) itself is typically comprised of interlocking, loosely-fitted slats, which are locked together at their ends to maintain the slats in alignment with each other.
A problem can arise with any door traversing a significant space in that, in a high wind or other load condition, such as during a storm, a wind force against the door can create a bowed condition at an unsupported portion of the door slats, which bowing has the effect of creating an unwanted locking condition between the rollers and a surface of the tracks. Such condition can have the effect of prohibiting or restricting rolling movement of the door, depending on the wind load.
Even during regular load conditions, some movement or “play” exists between the rollers and the guide track such that the front faces of the rollers will contact the edges of the guide tracks and cause friction there-between. This condition limits the closing and opening speeds of the door.
Typically, for horizontal and side-coiling curtains, (and in instances where vertical curtains require constant operating speed), a pusher, in particular, a cog, is used to move the curtain between the opened and closed positions. In conventional systems, this is typically accomplished by positioning the cog for engagement with surfaces of the door slats to deploy and retract the curtain with respect to a coil that holds the undeployed portion of the curtain. In systems that use direct engagement of the pusher cog with the slats, wear on the slat surfaces is created and unwanted noise generated due to the striking of the cog with the slats as the curtain is moved between its opened and closed positions. To account for the wear to the slats, the metal gauge used to manufacture the slats need to be of a sufficient thickness. This adds to the cost and weight of the curtain.
SUMMARY OF THE INVENTION
It is an object of the invention to provide an improved roller assembly that overcomes the deficiencies of the prior art and that, even under heavy load conditions on the door/curtain, provides for rolling contact of the rollers in the guide track.
In accordance with one aspect of the present invention, a door assembly for covering an opening defined by at least one structural element of a building, the door assembly includes: a shutter roller rotatable about an axis of rotation; a drive mechanism configured to rotate the shutter roller about the axis of rotation; a flexible door/curtain windable on and off the shutter roller such that the flexible door/curtain is movable into retracted and extended positions by operation of the drive mechanism, the flexible door having a plurality of connected slats, each having two ends; at least one guide rail assembly positioned on at least one side of the opening and coupled to the at least one side of the opening, the at least one guide rail assembly having: (a) an outer track, coupled to the at least structural element of the building and having at least a first portion extending parallel to the flexible door/curtain, (b) an inner track, coupled to the at least structural element of the building and having at least a first portion extending parallel to the outer track and parallel to the flexible door/curtain, (c) a roller support guide, arranged fixedly between the outer track and the inner track, and (d) first and second roller guides disposed opposite one another between the inner track and the outer track, with a space maintained between the first and second roller guides; and a plurality of coupling mechanisms, each of the plurality of coupling mechanisms being affixed to ends of one or more of the plurality of slats of the door/curtain, each of the plurality of coupling mechanisms comprising: (a) at least two door/curtain mounting brackets, each door/curtain mounting bracket having: (i) a mounting surface configured to connect to a slat of the door/curtain, and (ii) an extending surface oriented at approximately 90 degrees with respect to the substantially rectangular portion, the extending surface having at least one endlock configured to maintain alignment of the slats of the door/curtain; (b) a roller mounting bracket having: (i) a first roller arranged at an upper portion of the roller mounting bracket, the first roller being rotatable around an axis perpendicular to the lengthwise direction of the slats, and (ii) an extending portion, oriented at approximately 90 degrees with respect to the upper portion of the roller mounting bracket and connected to the at least one endlock; and (c) at least one second roller, each at least one second roller being rotatable around an axis perpendicular to the axis of rotation of the first roller and connected to the at least one endlock. The first roller and the at least one second roller are arranged so as to cooperate with the outer track, inner track, roller support guide and first and second roller guides to ensure that the door/curtain moves rollingly within the guide rail assembly even when the door/curtain is subjected to a deflecting force.
In another aspect, the at least one guide rail assembly further has a mounting support configured to secure the at least one guide rail assembly to the at least one structural element of the building, at least a first end of the mounting support being configured to be affixed to the at least one structural element of the building.
In another aspect, the coupling mechanisms are linked to one another by a link coupled to posts of adjacent coupling mechanisms.
In another aspect in an assembled state of the door assembly, the at least one second roller of each of the plurality of coupling mechanisms is maintained between the first and second roller guides even when the door/curtain is subjected to a deflecting force.
In another aspect, in an assembled state of the door assembly, the door assembly is configured such that each first roller is maintained in the at least one guide rail assembly between the roller support guide and at least one of the inner track and outer track, to ensure rolling contact between the first roller and the guide rail assembly even when the door/curtain is subjected to a deflecting force.
In another aspect, the coupling mechanisms each further include a spacing mechanism arranged between the at least one second roller and one or both of the extending surface of door/curtain mounting bracket and the extending portion of the roller mounting bracket.
In another aspect, the at least one second roller includes two second rollers.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller via an intermediate pusher cog.
In another aspect, the pusher cog has a plurality of cog teeth, and the pusher cog assists in moving the door/shutter between a closed position and an open position by engagement of the cog teeth with spaces formed in the plurality of coupling mechanisms between the second rollers.
In another aspect, the drive mechanism is contained within a drive housing.
In another aspect, the door assembly is a side coiling door assembly in which: the at least one guide rail assembly is coupled to a top side of the opening; the slats and shutter roller are arranged perpendicular to the ground; and the coupling mechanisms are arranged at top ends of the slats, proximal to the top side of the opening.
In another aspect, the drive mechanism is contained within a drive housing.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller via an intermediate pusher cog.
In another aspect, the pusher cog has a plurality of cog teeth, and the pusher cog assists in moving the door/shutter between a closed position and an open position by engagement of the cog teeth with spaces formed in the plurality of coupling mechanisms between the second rollers.
In another aspect, the door assembly is a horizontal coiling door assembly in which: the opening comprises a hole formed in a floor of the building; the at least one guide rail assembly comprises two guide rail assemblies, one coupled to the floor at one side of the hole formed in the floor, and the other coupled to the floor at the other side of the hole formed in the floor; the slats and shutter roller are arranged parallel to the ground and perpendicular to the direction of closing and opening the door/curtain; and the coupling mechanisms are arranged at both ends of the slats, respectively proximal to the one side of the hole in the floor and to the other side of the hole in the floor.
In another aspect, the drive mechanism is contained within a drive housing.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller via an intermediate pusher cog.
In another aspect, the pusher cog has a plurality of cog teeth, and the pusher cog assists in moving the door/shutter between a closed position and an open position by engagement of the cog teeth with spaces formed in the plurality of coupling mechanisms between the second rollers.
In another aspect, the door assembly is a vertical coiling door assembly in which: the opening is a hole formed in a wall of the building; the at least one guide rail assembly comprises two guide rail assemblies, one coupled to one side of the hole formed in the wall, and the other coupled to the other side of the hole formed in the wall; the slats and shutter roller are arranged perpendicular to the ground and perpendicular to the direction of closing and opening the door/curtain; and the coupling mechanisms are arranged at both ends of the slats, respectively proximal to the one side of the hole in the wall and to the other side of the hole in the wall.
In another aspect, the drive mechanism is contained within a drive housing.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller.
In another aspect, the drive mechanism includes a motor coupled to the shutter roller via an intermediate pusher cog.
In another aspect, the pusher cog has a plurality of cog teeth, and the pusher cog assists in moving the door/shutter between a closed position and an open position by engagement of the cog teeth with spaces formed in the plurality of coupling mechanisms between the second rollers.
In another aspect, the motor is coupled directly to the shutter roller by a belt or chain drive configuration.
In accordance with a second aspect of the present invention, a coupling is provided for a door assembly for covering an opening defined by at least one structural element of a building, the door assembly having: a shutter roller rotatable about an axis of rotation; a drive mechanism configured to rotate the shutter roller about the axis of rotation; a flexible door/curtain windable on and off the shutter roller such that the flexible door/curtain is movable into retracted and extended positions by operation of the drive mechanism, the flexible door having a plurality of connected slats, each having two ends; at least one guide rail assembly positioned on at least one side of the opening and coupled to the at least one side of the opening, the at least one guide rail assembly having: (a) an outer track, coupled to the at least structural element of the building and having at least a first portion extending parallel to the flexible door/curtain, (b) an inner track, coupled to the at least structural element of the building and having at least a first portion extending parallel to the outer track and parallel to the flexible door/curtain, (c) a roller support guide, arranged fixedly between the outer track and the inner track, and (d) first and second roller guides disposed opposite one another between the inner track and the outer track, with a space maintained between the first and second roller guides. The coupling includes: a plurality of coupling mechanisms, each of the plurality of coupling mechanisms being affixed to ends of one or more of the plurality of slats of the door/curtain. Each of the plurality of coupling mechanisms includes: (a) at least two door/curtain mounting brackets, each door/curtain mounting bracket having: (i) a mounting surface configured to connect to a slat of the door/curtain, and (ii) an extending surface oriented at approximately 90 degrees with respect to the substantially rectangular portion, the extending surface having at least one endlock configured to maintain alignment of the slats of the door/curtain; (b) a roller mounting bracket having: (i) a first roller arranged at an upper portion of the roller mounting bracket, the first roller being rotatable around an axis perpendicular to the lengthwise direction of the slats, and (ii) an extending portion, oriented at approximately 90 degrees with respect to the upper portion of the roller mounting bracket and connected to the at least one endlock; and (c) at least one second roller, each at least one second roller being rotatable around an axis perpendicular to the axis of rotation of the first roller and connected to the at least one endlock. The first roller and the at least one second roller are arranged so as to cooperate with the outer track, inner track, roller support guide and first and second roller guides to ensure that the door/curtain moves rollingly within the guide rail assembly even when the door/curtain is subjected to a deflecting force.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and/or other aspects and advantages will become more apparent and more readily appreciated from the following detailed description of the disclosed embodiments taken in conjunction with the accompanying drawings in which:
FIGS. 1A and 1B are front elevational and side views, respectively, illustrating a coupling attached to a section of a door/curtain, in accordance with an embodiment of the present invention;
FIG. 1C is a perspective view of the coupling separate from the door/curtain to which it is shown attached in FIGS. 1A and 1B ;
FIGS. 2A and 2B are front elevational and side views, respectively, illustrating a plurality of couplings attached to an extended section of a door/curtain, in accordance with an embodiment of the present invention;
FIG. 3 is a diagram showing the couplings and door/curtain shown in FIGS. 1A to 2B in a guide track, in accordance with an embodiment of the present invention;
FIG. 4 is a side view illustrating the coupling and door/curtain being driven by a pusher cog, in accordance with an embodiment of the present invention;
FIG. 5 is a perspective view illustrating the coupling and door/curtain being driven by a pusher cog, in accordance with an exemplary embodiment of the present invention as used in a horizontal coiling door;
FIGS. 6A to 6D are diagrams illustrating the use of the coupling and door/curtain shown in FIGS. 1A to 2B in the context of a side coiling door;
FIGS. 7A to 7C are diagrams illustrating the use of the coupling and door/curtain shown in FIGS. 1A to 2B in the context of a vertical coiling door;
FIGS. 7D and 7E are diagrams illustrating the use of the coupling and door/curtain shown in FIGS. 1A to 2B in the context of a vertical coiling door using a pusher cog; and
FIGS. 8A to 8D are diagrams illustrating the use of the coupling and door/curtain shown in FIGS. 1A to 2B in the context of a horizontal coiling door.
DETAILED DESCRIPTION
The disclosed exemplary embodiments relate to rolling steel door/curtains provided with an inventive roller coupling configured to movably secure the door/curtain to a guide track. The door/curtain according to a preferred embodiment is made of a plurality of interlocking slats which are pivotally connected to each other to provide for a rolling of the curtain about a take-up roll. Exemplary configurations of rolling steel door/curtains employing the inventive modified roller coupling will be described below in detail with regard to FIGS. 1A to 8D .
According to an exemplary embodiment, discussed herein in connection with FIGS. 1A-2B , a steel door/curtain 10 , having slats 100 , is affixed at at least one side to a coupling mechanism comprising a plurality of couplings 200 .
FIGS. 1A and 1B depict front and side views of a single instance of the modified coupling 200 , connected to two slats 100 . FIG. 1C is a perspective view of a single instance of the coupling 200 , not shown as being attached to slats 100 of the door/curtain 10 . FIGS. 2A and 2B depict front and side views of a plurality of such couplings 200 connected to plural slats 100 making up a door/curtain 10 .
As can be seen in FIGS. 1A-2B , the slats 100 are connected to the couplings 200 at at least one end of the slat 100 , by a portion of the coupling 200 that will be referred to as a curtain mounting bracket 201 , having a rectangular member 202 . The connection is effected preferably via a plurality of rivets or screws 204 . In the views of FIGS. 1A and 2A , the curtain mounting brackets 201 are shown in phantom, to indicate that they are behind the door slats 100 in those views.
One end of the mounting bracket 201 has an extending surface 206 oriented at approximately 90° with respect to the rectangular member 202 . This extending surface forms an endlock 208 to maintain alignment of adjacent slats of the curtain. Formed at each endlock 208 is a post 210 about which a traveling roller 212 is disposed and sandwiched between two spacers. In the illustrated embodiment, the spacer 213 , for example an annular brass spacer, is used to maintain the spacing between the top of each travelling roller 212 and transversely extending portion of the locking roller mounting bracket 216 .
The spacing between the bottom of the travelling roller 212 and the endlock 208 is preferably maintained by an annular ridge, formed in the inner wall of the travelling roller 212 , abutting a ledge formed on the post 210 , neither of which is visible in the figures. However, the bottom spacing is not limited to this configuration and can also be achieved, for example, by providing another annular spacer 213 in the gap between the endlock 208 and the travelling roller 212 .
The locking roller mounting bracket 216 has a transversely extending portion 217 that has a hole at each end. In the assembled combination of the door/curtain 10 and the coupling 200 , the posts 210 each extend through the inner opening of the travelling roller 212 , the spacer 213 , a hole in the transversely extending portion of the locking roller mounting bracket 216 , and a receiving hole formed in a connecting link 214 , as shown in FIGS. 1A and 1B , and are secured to those respective components by fasteners such as nuts 218 , preferably using a washer 219 between the nut 218 and the connecting link 214 .
When coupled with the door slats 100 , the connecting links 214 and locking roller mounting brackets 216 are alternated such that, except for an endmost curtain locking roller mounting bracket 216 , each post 210 will be fastened to adjacent connecting links 214 and locking roller mounting brackets 216 , as shown, for example, in FIGS. 2A and 2B . An endmost curtain mounting bracket would not include a connecting link on the side of the locking roller mounting bracket 216 towards the end of the door/curtain 10 .
The posts 210 provide a location for the traveling rollers 212 but also a spacing between the endlock 208 of each curtain mounting bracket 201 and either an end of a locking roller mounting bracket 216 or a connecting link 214 .
As shown in the side view of FIG. 1B , the locking roller mounting bracket 216 has a longitudinal L-shaped cross section with one end corresponding to the transversely extending portion 217 , in this cross sectional view, fastened to the post 210 , and another end supporting a locking roller 220 , which is rotatably mounted on the locking roller mounting bracket 216 . As can be seen in FIG. 1A , each instance of the locking roller mounting bracket 216 is associated with one locking roller 220 and two traveling rollers 212 . For each locking roller mounting bracket 216 , the locking roller 220 and two travelling rollers 212 are oriented at 90° with respect to each other such that they engage different surfaces of a door mounting guide track 300 , to be described next.
With reference to FIG. 3 , the guide track 300 for one side of a door/curtain 10 is shown. In certain known door configurations, such as a side coiling door, the guide track 300 would only be used at one side of the door, namely the top side. In other configurations, such as a horizontal coiling door and a vertical coiling door, each side of the door/curtain 10 cooperates with a guide track 300 . In cases in which a second instance of the guide track 300 and second set of couplings 200 are utilized at the other side of the door/curtain 10 , the structure on the other side would be a mirror image of the structure shown in FIG. 3 .
In the illustrated embodiment of FIG. 3 , the guide track 300 includes a mounting/support angle 302 , an outer track angle 304 , an inner track angle 306 , and a locking roller retaining guide 308 . A pair of traveling roller guides 310 are positioned in opposing relation to each other on the outer track angle 304 and inner track angle 306 on either side of the traveling rollers 212 to provide a guide surface along which the traveling rollers 212 may roll during deployment and retraction of the door/curtain 10 .
In a preferred embodiment, the travelling roller guides 310 are preferably of different heights. For example, as in the exemplary embodiment illustrated in FIG. 3 , the height of the roller guide 310 on the outer track angle 304 can be made larger than the height of the roller guide 310 on the inner track angle 306 . Such a configuration advantageously provides clearance for a smoke seal 312 , which, in the exemplary embodiment, is also attached to the inner track angle 306 and extends toward the door/curtain 10 . The smoke seal 312 functions to prevent the escape of smoke from one side of the door/curtain 10 to the other side of the door/curtain 10 , which would otherwise occur through the track 300 in the absence of the smoke seal.
In the mounting configuration illustrated in FIG. 3 , the locking roller 220 is positioned between the outer track angle 304 and the locking roller retaining guide 308 . The locking roller 220 maintains positioning of the edges of the door/curtain 10 in the track 300 and also facilitates opening and closing of the door/curtain 10 , especially during a wind load condition, which can cause a deformation of the door/curtain 10 , such as a bowing of the door/curtain 10 .
In such a bowed condition, for example, the locking roller 220 will contact either the locking roller retaining guide 308 or the outer track angle 304 . In either event, rotational movement of the locking roller 220 , and therefore the door/curtain 10 to which it is attached, along either surface is accommodated, thereby allowing the door/curtain 10 to be opened or closed, even in a high wind load condition.
In the exemplary illustrated embodiment, the mounting/support angle 302 has a L-shaped configuration and is affixed at one end to the outer track angle 304 and the inner track angle 306 by a nut and bolt combination 314 b . The other end is preferably affixed to, e.g., a masonry wall 500 , by a nut and bolt combination 314 a.
FIGS. 4 and 5 illustrate how the door/curtain 10 , coupling 200 and guide track 300 cooperate to allow for movement, by operation of a pusher cog 400 , of the door in either a deployment direction or a retracting direction. As can be seen in FIGS. 4 and 5 , the positioning of the connection links 214 provides a space, between the travelling rollers 212 , into which teeth 402 of the pusher cog 400 can be received to facilitate deployment and retraction of the roller curtain without requiring contact between the cog and the slats of the curtain. While not shown in FIGS. 4 and 5 , the pusher cog 400 can be driven, for example, in any known manner, e.g., either directly or indirectly, by an electronic or manual door operator via, for example, a sash chain, timing belt, or the like.
The arrangement illustrated in FIGS. 4 and 5 advantageously allows the pusher cog 400 to be positioned proximate the tracks, to engage the travelling rollers 212 in the space to drive the door/curtain 10 between the opened and closed positions. Also, as described above, the locking rollers 220 are oriented with respect to the locking roller retaining guide 308 and the outer track angle 304 so that, even during high wind conditions, which can deform the door/curtain 10 into, for example, a bowed condition, no sliding motion will occur between the door/curtain 10 and surfaces in the guide track 300 . Instead, due to the advantageous configuration of the rollers, coupling, door/curtain and guide track illustrated in FIGS. 1A to 5 , all engagement between the door/curtain 10 and guide track 300 are with rollers. This arrangement provides for rolling curtains to no longer be restricted in movement during a load condition.
Unlike some conventional horizontal and side-coiling curtain systems, the configuration described above with respect to FIGS. 1A to 5 does not require the pusher cog to directly engage the door slats themselves. Thus, no wear or damage is caused to the door slats. This reduces operational noise and also allows for a smaller gauge metal to be used for the door slats, thereby reducing weight. The reduced weight, in turn, allows for less stored spring energy to be used to open and close the door.
Moreover, because no pusher surface is needed on the door slats, an insulated, two-sided curtain can be used because the driving cog engages the openings but not the slats. In other words, because a slat surface is not needed to provide for engagement with the teeth of the pusher cog, a two-sided curtain having a flat surface on either curtain side can be used, with insulation sandwiched between the two sides. In addition, because there is no direct contact between the pusher cog and the slats, the door opening cycle is increased. Further, a lighter gauge metal stock can be used for the curtain slats because a less rugged curtain can now be employed as a result of the elimination of direct contact between the pusher cog and the curtain slats.
For vertical coiling curtains, an increased operational speed with a higher cycle can be achieved. Moreover, the curtain will be capable of regular opening and closing operation in high load conditions because of reduced friction between the door rollers and the track. A pusher cog can also be added to increase or regulate the opening and closing speed of the curtain.
FIGS. 6A to 6D illustrate an exemplary utilization of the inventive coupling mechanism comprising couplings 200 in the context of a side coiling door. When referring to components already described above, the same reference numeral is used as in the prior description.
As is known to those skilled in the art, side coiling doors extend and retract horizontally, with the door/curtain 10 remaining perpendicular to the ground. In such a configuration, the bottom end of the door/curtain 10 typically runs in a track formed in the floor (not shown in the drawings), using, e.g., rollers or a sliding configuration.
In the side coiling door configuration illustrated in FIGS. 6A to 6D , the top of the door/curtain 10 is fitted with couplings 200 which ride in guide track 300 in a manner substantially as shown in FIGS. 3-5 . Also, while the engagement of the pusher cog 400 and the couplings 200 are shown schematically in FIGS. 6A and 6C , the engagement between the pusher cog 400 and the couplings is effected in the same manner as shown in detail in FIGS. 4 and 5 .
As shown in FIGS. 6A to 6D , in the side coiling door configuration, the door/curtain 10 is opened and closed by operation of a drive unit 403 , preferably enclosed in a drive unit housing 406 , which, in the illustrated embodiment, extends from the floor to the top of the side coiling door. The drive unit 403 includes the pusher cog 400 , having cog teeth 402 , which cooperate with and engage the couplings 200 attached to the top of the door/curtain 10 , to move the door/curtain 10 in the manner discussed above with respect to FIGS. 4 and 5 . The pusher cog 400 is configured to rotate in one direction to un-coil the door/curtain 10 from a coil pipe 408 , when closing the door/curtain 10 , and in the opposite direction when retracting the door/curtain 10 to an open position. The coil pipe 408 extends in the housing 406 the entire height of the door/curtain 10 . In the closed (i.e., retracted) position, the door/curtain 10 is substantially completely wrapped around the coil pipe 408 for secure storage.
The drive unit 403 also includes a motor 410 configured to set the pusher cog 400 in motion in either a clockwise or counter-clockwise direction. The motor 410 can be any standard motor that can be controlled, e.g., by a switch or other control, to drive a pusher cog 400 in the required directions, e.g., the clockwise and counter-clockwise directions.
FIG. 6A is a front elevational view of the side coiling door configuration that utilizes the inventive couplings 200 , and FIG. 6B is a view taken along section 6 B- 6 B′. In the side coiling door configuration, the guide track 300 is disposed along the top of the door/curtain 10 and is affixed, in the manner shown in FIG. 6B , to a structural support 700 . The structural support 700 is, for example, a laterally extending portion of the structure of the building in which the side coiling door is installed, for example a steel cross beam or a concrete member.
As can be seen in FIG. 6B , in the exemplary embodiment of the side coiling door, the rails of the guide track 300 are affixed to the door/curtain 10 and coupling 200 in substantially the same manner as shown in FIGS. 1-3 . In the illustrated embodiment, the rails of the guide track 300 are affixed to the structural support 700 by a transverse structural support member 704 , coupled to, and suspended from, the structural support 700 using, e.g., nut and bolt combinations 702 . In particular, each of the outer track angle 304 and the inner track angle 306 are affixed by nuts and bolts to the transverse structural support member 704 .
The door/curtain 10 is attached, along its top edge, to the couplings 200 , in the manner discussed above in relation to FIGS. 1-3 , that is, by the curtain mounting brackets 201 , preferably via rivets or screws 204 . As can been in FIG. 6B , the locking roller 220 rollingly contacts the locking roller retaining guide 308 , which, in the case of a side coiling door, supports at least a portion of the weight of the door/curtain 10 , since gravity tends to urge contact between the locking roller 220 and the locking roller retaining guide 308 .
The travelling roller guides 310 are disposed at each side of the travelling rollers 212 and function to maintain the door/curtain 10 moving along the guide track 300 , even in the case of a force being applied to the door/curtain 10 . In a typical configuration, a finish ceiling 706 can be provided at the top of the coiling door, at a position that hides guide track 300 and the portion of the door/curtain 10 at which the door/curtain 10 attaches to the couplings 200 , although the finish ceiling does not form any part of the present invention. Although not shown in FIG. 6B , the door also preferably includes a smoke seal 312 , in the same manner as shown in FIG. 3 , situated between the door/curtain and one rail.
FIGS. 6C and 6D are a plan view and magnified partial view, respectively, of the side coiling door configuration. In FIG. 6C , the door/curtain 10 itself, and the rails of the guide track 300 , are illustrated schematically to show the workings of the coil pipe 408 , the pusher pipe 404 and the pusher cog 400 in the drive unit housing 406 , which has already been described above.
At the right side of FIG. 6C , the furthest extending portion of the door/curtain 10 in the closed position is shown in relation to a side wall reception unit 750 that receives the leading edge of the door/curtain. A detailed view of this portion of FIG. 6C is shown in the magnified view of FIG. 6D .
In particular, in a preferred embodiment, in order to provide a secure connection of the leading edge of the door/curtain 10 with the wall, the door/curtain 10 has, at its leading edge, a leading edge unit 250 configured to lockingly engage in the side wall reception unit 750 . The side wall reception unit 750 has side members 752 at right angles to a wall 754 . A receiving channel 756 provides a break in the wall 754 into which the leading edge unit 250 can engage. As seen in FIG. 6D , the leading edge unit 250 is configured to lockingly engage with a support 758 that is surrounded by side wall reception unit 750 .
Next, operation of a vertical coiling door will be described utilizing the inventive couplings 200 . As before, elements having the same configuration as those described previously will be denoted with the same reference numerals as in the previous figures. Two variations of the vertical coiling door are described below. In the first variation, the coil of the vertical coiling door is directly driven by a motor, without the use of a pusher cog. This variation is described with reference to FIGS. 7A to 7C .
In a second variation, which is described with reference to FIGS. 7D and 7E , the motor drives a pusher cog, which cooperates with the couplings 200 to wind and unwind the door/curtain 10 onto and off of the coil pipe.
With regard to the first variation, as shown in FIGS. 7A to 7C , a vertical coiling door configuration comprises a door/curtain 10 that is wrapped around a horizontally oriented coil pipe 408 located along the top of the vertical coiling door. Guide tracks 300 extend vertically along each edge of the door/curtain 10 to form channels that permit the door/curtain 10 , attached at each edge to couplings 200 , to move easily up and down, from a closed to an open position, or vice versa. When the door is in the open position, the door/curtain 10 may be maintained, rolled up on the coil pipe 408 , entirely within the housing 606 that surrounds the coil pipe 408 . To close the door/curtain 10 , rotational force is applied from the motor 410 to the coil pipe 408 , for example by belt/chain 409 , to unspool the wound door/curtain 10 from the coil pipe 408 .
As shown in FIGS. 7A to 7C , in the vertical coiling door configuration, the door/curtain 10 is opened and closed by operation of a drive unit 604 , preferably enclosed in a drive unit housing 606 , which, in the illustrated embodiment, extends across the top portion of the vertical coiling door. The drive unit 604 includes a motor 410 configured to set the coil pipe 408 in motion in either a clockwise or counter-clockwise direction. The motor drives the coil pipe using a belt or chain 409 . The motor 410 can be any standard motor that can be controlled, e.g., by a switch or other control, to drive the coil pipe in the required directions, e.g., the clockwise and counter-clockwise directions. The coil pipe 404 is configured to rotate in one direction to un-coil the door/curtain 10 , when closing the door/curtain 10 , and in the opposite direction when retracting the door/curtain 10 to an open position. The coil pipe 408 extends the entire width, from one lateral side of the door/curtain 10 to the other lateral side, along the top of the vertical coiling door. In the closed (i.e., retracted) position, the door/curtain 10 is substantially completely wrapped around the coil pipe 408 for secure storage.
FIG. 7A is a plan view of the vertical coiling door configuration that utilizes the inventive couplings 200 , and FIG. 7B is a view taken along section 7 B- 7 B′. In the vertical coiling door configuration, two guide tracks 300 are provided, one proximal to each lateral edge of door/curtain 10 . Each guide track 300 is affixed, in the manner shown in FIG. 7C , to a structural support 900 . The structural support 900 is, for example, a portion of the wall structure of the building in which the vertical coiling door is installed, for example a masonry wall.
The plan sectional view of FIG. 7C , shows the one side of the door/curtain 10 attached to the roller assembly of the couplings 200 in the guide track 300 . A mirror image identical structure is employed at the other side of the door/curtain 10 . As discussed above with respect to FIG. 3 , the door/shutter 10 is attached to the couplings 200 by curtain mounting brackets 201 . As in FIG. 3 , the guide track 300 includes a mounting/support angle 302 , an outer track angle 304 , an inner track angle 306 , and a locking roller retaining guide 308 . A pair of traveling roller guides 310 are positioned in opposing relation to each other on the outer track angle 304 and inner track angle 306 on either side of the traveling rollers 212 to provide a guide surface along which the traveling rollers 212 may roll during deployment and retraction of the door/curtain 10 . The locking roller 220 is positioned between the outer track angle 304 and the locking roller retaining guide 308 . The locking roller 220 maintains positioning of the edges of the door/curtain 10 in the track 300 and also facilitates opening and closing of the door/curtain 10 , especially during a wind load condition, which can cause a deformation of the door/curtain 10 , such as a bowing of the door/curtain 10 .
The second variation is exactly the same as the first variation except that door/curtain 10 is moved from the closed to the open position, and vice versa, using pusher cogs 400 at either end of the housing, which engage the couplings 200 in the same manner shown in FIGS. 4 and 5 . As can be seen from FIG. 7D , the housing 606 extends across the top of the vertical coiling door, but in the second variation, the housing has within it both a pusher pipe 404 and a coil pipe 408 , upon which the door/curtain 10 is stored in the retracted, i.e., open door position.
In this variation, the drive unit 604 includes two pusher cogs 400 , each having cog teeth 402 , which cogs 400 cooperate with and engage the couplings 200 attached to both lateral sides of the door/curtain 10 , to move the door/curtain 10 , at each side, in the manner discussed above with respect to FIGS. 4 and 5 . Preferably, in the second variation of the vertical coiling door configuration, one pusher cog 400 is disposed at each end of a pusher pipe 404 . The pusher cogs 400 , and the pusher pipe 404 , are configured to rotate in one direction to un-coil the door/curtain 10 from a coil pipe 408 , when closing the door/curtain 10 , and in the opposite direction when retracting the door/curtain 10 to an open position. In all other ways, the structure of the second variation of the vertical coiling door is identical to that of the first variation and those identical elements will not be described again here.
FIGS. 8A to 8D illustrate an exemplary utilization the inventive coupling mechanism comprising couplings 200 in the context of a horizontal coiling door. When referring to components already described above, the same reference numeral is used as in the prior description.
A horizontal coiling door configuration is used, for example, for covering a gap in a floor, for example, one formed by an escalator. In such configuration the door/curtain 10 is oriented horizontally in a plane substantially parallel with the plane of the floor. The door/curtain 10 can, in this configuration, be opened by winding the door/curtain onto a coil pipe.
As is known to those skilled in the art, horizontal coiling doors extend and retract substantially horizontally, with all or the majority of the door/curtain 10 remaining parallel to the ground, i.e., the floor.
In the horizontal coiling door configuration illustrated in FIGS. 8A to 8D , both lateral sides of door/curtain 10 are fitted with couplings 200 that ride in respective guide tracks 300 arranged, at each lateral side of the horizontal coiling door, in a manner substantially as shown in FIGS. 3-5 . Also, while the engagement of the pusher cog 400 and the couplings 200 are shown schematically in FIGS. 8A and 8C , for one side of the horizontal coiling door, the actual engagement between the pusher cog 400 and the couplings 200 is effected in the horizontal coiling door, in the same manner as shown in detail in FIGS. 4 and 5 .
As shown in FIGS. 8A to 8D , in the horizontal coiling door configuration, the door/curtain 10 is opened and closed by operation of a drive unit 503 , preferably enclosed in a drive unit housing 506 , which, in the illustrated embodiment, extends across the floor from one side to the other side of the horizontal coiling door. The drive unit 503 includes two pusher cogs 400 , each having cog teeth 402 , which cogs 400 cooperate with and engage the couplings 200 attached to both lateral sides of the door/curtain 10 , to move the door/curtain 10 , at each side, in the manner discussed above with respect to FIGS. 4 and 5 . Preferably, in the horizontal coiling door configuration, one pusher cog 400 is disposed at each end of a pusher pipe 404 . The pusher cogs 400 , and the pusher pipe 404 , are configured to rotate in one direction to un-coil the door/curtain 10 from a coil pipe 408 , when closing the door/curtain 10 , and in the opposite direction when retracting the door/curtain 10 to an open position. The coil pipe 408 extends the entire width, from one lateral side of the door/curtain 10 to the other lateral side. In the closed (i.e., retracted) position, the door/curtain 10 is substantially completely wrapped around the coil pipe 408 for secure storage.
The drive unit 503 also includes a motor 410 configured to set the two pusher cogs 400 in motion in either a clockwise or counter-clockwise direction. The motor 410 can be any standard motor that can be controlled, e.g., by a switch or other control, to drive the pusher cogs 400 in the required directions, e.g., the clockwise and counter-clockwise directions.
FIG. 8A is a plan view of the horizontal coiling door configuration that utilizes the inventive couplings 200 , and FIG. 8B is a view taken along section 8 B- 8 B′. In the horizontal coiling door configuration, two guide tracks 300 are provided, one proximal to each lateral edge of door/curtain 10 . Each guide track 300 is affixed, in the manner shown in FIG. 8B , to a structural support 800 . The structural support 800 is, for example, a downwardly extending portion of the floor structure of the building in which the horizontal coiling door is installed, for example a steel cross beam or a concrete member.
As can be seen in FIG. 8B , in the exemplary embodiment of the horizontal coiling door, the rails of the guide track 300 are affixed to the door/curtain 10 in substantially the same manner as shown in FIGS. 1-3 . In the illustrated embodiment, the rails of the guide track 300 are affixed to the structural support 800 by the mounting/support angle 302 , coupled to the structural support 800 using, e.g., nut and bolt combinations 314 a . As in FIG. 3 , each of the outer track angle 304 and the inner track angle 306 are affixed by nut and bolt combination 314 b to the mounting/support angle 302 . This configuration is repeated, in a mirror image, at the other lateral edge of the door/curtain 10 .
The door/curtain 10 is attached, along each lateral edge, to the couplings 200 , in the manner discussed above in relation to FIGS. 1-3 , that is, by the curtain mounting brackets 201 , preferably via rivets or screws 204 . As can been in FIG. 8B the locking roller 220 is maintained between the locking roller retaining guide 308 and the outer track angle 304 .
The travelling roller guides 310 are disposed at each side of the travelling rollers 212 and function to maintain the door/curtain 10 moving along the guide track 300 , even in the case of a force being applied to the door/curtain 10 . It is noted that in the case of a horizontal coiling door, the travelling rollers 212 will rollingly contact the lower one of the roller guides 310 under normal conditions, since the travelling rollers 212 are being urged to contact the lower roller guide by the force of gravity. Although not shown in FIG. 8B , the door also preferably includes a smoke seal 312 , in the same manner as shown in FIG. 3 , situated between the door/curtain and one rail.
FIGS. 8C and 8D are a sectional view and magnified partial view, respectively, of the horizontal coiling door configuration. In FIG. 8C , the door/curtain 10 itself, and the rails of the guide track 300 , are illustrated schematically to show the workings of the coil pipe 408 , the pusher pipe 404 and the pusher cog 400 in the drive unit housing 506 , which has already been described above.
At the right side of FIG. 8C , the furthest extending portion of the door/curtain 10 is shown in relation to a side wall reception unit 850 that receives the leading edge of the door/curtain 10 . A detailed view of this portion of FIG. 8C is shown in the magnified view of FIG. 8D .
In particular, in a preferred embodiment, in order to provide a secure connection of the leading edge of the door/curtain 10 with the wall, the door/curtain 10 has, at its leading edge, a leading edge unit 260 configured to allow the end of the door/curtain 10 to lockingly engage in the reception unit 850 . The reception unit 850 , in the illustrated example, has a J-shaped member 802 that is coupled to the rails of the guide track 300 and to a support 804 , which is affixed to the floor of the building. The J-shaped member 802 forms a receiving channel 806 into which the leading edge unit 260 can lockingly engage with the reception unit 850 by dropping into the receiving channel 804 when the door/curtain 10 is at a point of full extraction.
Although example embodiments have been shown and described in this specification and figures, it would be appreciated by those skilled in the art that changes may be made to the illustrated and/or described example embodiments without departing from their principles and spirit. | A coupling for a door/curtain includes a plurality of coupling mechanisms affixed to ends of slats of the door/curtain. Each coupling mechanism includes a roller mounting bracket having a first roller arranged at an upper portion of the roller mounting bracket, and an extending portion, oriented at approximately 90 degrees with respect to the upper portion of the roller mounting bracket; and at least one second roller. Each second roller is rotatable around an axis perpendicular to the axis of rotation of the first roller. The first roller and the at least one second roller are arranged so as to cooperate with an outer track, inner track, roller support guide and first and second roller guides of a guide rail assembly to ensure that the door/curtain moves rollingly within the guide rail assembly even when the door/curtain is subjected to a deflecting force. | 4 |
BACKGROUND
1. Field of the Invention
The present invention is directed towards an optical assembly and, in particular, an optical assembly capable of high speed data transmission.
2. Discussion of Related Art
As data rates increase, the need for components that can accommodate those data rates also increase. Further, there is great interest in providing low-cost transceiver components that support high data rates in small form-factor packages.
Coaxially arranged optical assemblies, such as the TO-56 packages for example, are common standard form-factors for housing optical network components. The TO-56 package allows for coupling, with an optical coupler, to an optical fiber communication line. This coaxial style packaging for optical coupling with optical fiber provides a cost effective solution for many transceiver applications. However, as data rates increase (especially beyond the 2.5 Gbps range), a new solution is needed to achieve high performance. As the higher performance is attained, however, the cost of producing high-performance optoelectronic packages can increase dramatically.
Several problems arise when high performance optoelectronic devices are assembled in small form-factor packages. For example, the thermal properties of the device become more problematic as high performance devices may generate more heat than is comfortably dissipated by a small package. Further, due to impedance mismatches and other electronic effects, high speed data signals may be degraded between, for example, a laser driver and a laser. Optical alignments also become more critical at higher data rates because loss of the small tolerances associated with high bandwidth optical transmission can become more of a problem. All of these issues can make it difficult to manufacture high performance optoelectronic devices at low cost.
Therefore, there is a need for transceiver components in small coaxial style package that both perform well at high data rates (for example above about 2.5 Gbps) and that are manufacturable at low cost.
SUMMARY
In accordance with the present invention, a high performance coaxial style packaged transceiver assembly with low manufacturing cost is presented. In some embodiments the transceiver assembly includes a laser driver and a laser submount, wherein the laser driver IC is mounted on an interface board and then mounted on the same heatsink material as is the laser submount. In some embodiments, the assembly provides for a high performance transmission system in a coaxial style packaging. An optical assembly according to the present invention can include a feed-through assembly, the feed-through assembly including an access for a laser driver and a heat sink, and a laser assembly mounted on the heat sink, wherein the access for the laser driver and the laser assembly are both thermally coupled to the heat sink.
In some embodiments of the invention, the output impedance of the laser driver is matched to the combined impedance of the laser and matching assembly to lower power consumption of the transceiver package. Further, in some embodiments the integrated resistor and laser submount are directly mounted on a heatsink, thereby improving high temperature performance by thermally conducting heat through the heat sink rather than through the electrical leads. In some embodiments, the thermal paths of the laser driver and the laser are sufficiently isolated to allow for efficient thermal dissipation without interference from the laser driver. In other words, in some embodiments, the thermal paths and proximity of the laser driver and the laser are balanced. In some embodiments, this balance can be achieved by sacrificing lowest-possible laser driver temperatures in order to achieve the lowest laser temperatures while maintaining acceptable electrical performance.
In some embodiments, the transceiver assembly includes a thin film spiral inductor placed with the laser die on the submount to minimize the stub length seen by the high speed signal at the laser input, achieving high signal performance.
In some embodiments, final optical alignment is obtained by typing the optical assembly according to the assembled location of the laser emission with respect to a nominal laser emitter location within the optical assembly. A lens cap, which includes a ball lens, can then be positioned with respect to the laser assembly in response to the type of optical assembly. This process results in a higher yield of high performance devices.
Since a laser driver can be positioned very close to the laser, and since impedance matching to the combination of resistor and laser can be accomplished with an inductor positioned close to the laser, signal distortion between the laser driver and the laser can be much reduced. Further, in some embodiments, electrical traces instead of individual pins carry signals throughout the optical assembly. The electrical characteristics of electrical traces can be better controlled than pins and contributes to the high performance of optical assemblies according to the present invention. The reduction in signal distortion allows for high performance optical assemblies to be constructed in a small standard package.
A method of producing an optical assembly according to the present invention can include forming a feed-through assembly, the feed-through assembly including an access for a laser driver wherein the laser driver will be thermally coupled to a heat sink; forming a laser assembly; and mounting the laser assembly on the feed-through assembly such that the laser assembly is thermally coupled to the heat sink.
These and other embodiments are further described below with respect to the following figures.
DESCRIPTION OF THE FIGURES
FIG. 1A shows an embodiment of an optical assembly according to the present invention.
FIG. 1B shows an optical and electrical block diagram of the optical assembly shown in FIG. 1A .
FIG. 1C shows an optical and electrical diagram for the circuits of the optical assembly illustrated in FIGS. 1A and 1B .
FIGS. 2A through 2D show mounting of laser diode and photodiode assemblies of an embodiment of an optical assembly according to the present invention.
FIG. 3A shows an embodiment of a feed-through assembly of an optical assembly according to the present invention.
FIGS. 3B through 3R illustrate an embodiment of the feed-through shown in FIG. 3A .
FIGS. 4A through 4I illustrate layout and assembly of an embodiment of optical assembly 100 according to the present invention.
FIGS. 5A through 5E illustrate assembly of a particular embodiment of a photodiode assembly compatible with the particular embodiment of feed-through assemblies shown in FIGS. 3B through 3O .
FIGS. 6A through 6F illustrate assembly of a particular embodiment of a laser assembly compatible with the particular embodiment of feed-through assembly shown in FIGS. 3B through 3O .
FIGS. 7A through 7I illustrate an embodiment of an assembly method for production of an optical assembly according to the present invention.
Elements having the same designation in the figures have the same or similar functions.
DETAILED DESCRIPTION
FIG. 1A illustrates an optical assembly 100 according to the present invention. Optical assembly 100 includes a feed-through assembly 101 and a lens cap 102 . Lens cap 102 can, in some embodiments, be attached with feed-through assembly 101 to form a hermetic seal. In some embodiments, a photo diode assembly 105 and laser assembly 104 are mounted to feed-through assembly 101 and enclosed with lens cap 102 . Lens cap 102 further includes a lens 110 , which in some embodiments is a ball lens, in order to couple light from laser assembly 104 into an optical fiber. In some embodiments, further components can be included within and without the area sealed by feed-through assembly 101 and lens cap 102 . For example, an impedance matching inductor 103 can be mounted to feed-through assembly 101 within the area sealed by feed-through assembly 101 and lens cap 102 . Further, feed-through assembly 101 can include a mounting access 129 for a laser driver 106 . Laser driver 106 , in some embodiments, can receive digital data signals and drive a laser of laser assembly 104 to produce a corresponding optical signal.
In some embodiments, laser assembly 104 can be mounted directly on a heat sink 125 . Heat sink 125 is part of feed-through assembly 101 . In some embodiments, laser assembly 104 is mounted on ceramic layers of feed-through assembly 101 , as shown in FIG. 1A , and thermally coupled to heat sink 125 .
During assembly, optical assembly 100 can be “typed” according to the offset of the laser emission laser assembly 104 after laser assembly 104 is attached to feed-through 101 . Cap 102 can then be positioned and attached to feed-through 101 in accordance with the type of optical assembly 100 .
In some embodiments, brackets 107 and 108 can be provided to mechanically attach feed-through 101 to a ceramic layer (not shown). Further, brackets 107 and 108 can be electrically coupled to conducting traces formed on feed-through 101 to electrically couple optical assembly 100 to a ceramic layer (not shown).
FIG. 1B shows an example transceiver system 130 that can utilize one or more devices such as optical assembly 100 illustrated in FIG. 1A . Transceiver system 130 includes transceivers 131 and 132 optically coupled through optical fiber 137 - 1 through 137 -(N+M). Each of optical fibers 137 - 1 through 137 -(N+M) include connectors that are optically coupled to transceivers 131 and 132 . Transceiver 131 includes transmitters 133 - 1 through 133 -N, each of which is optically coupled to a corresponding one of receivers 135 - 1 through 135 -N of transceiver 132 . Further, transceiver 131 includes receivers 134 - 1 through 134 -M, each of which is optically coupled to a corresponding one of transmitters 136 - 1 through 136 -M of transceiver 132 . Transceiver 131 can include any number of transmitters N and any number of receivers M. Typically, for many commercial systems, the number of transmitters N and the number of receivers M are both 1. One or more of transmitters 133 - 1 through 133 -N and 136 - 1 through 136 -M include an optical assembly 100 according to the present invention. The receiver portions of transceiver system 130 , i.e. receivers 134 - 1 through 134 -N and 136 - 1 through 136 -M, includes a photodetector system and electrical filter/driver for receiving optical signals from an optical fiber.
FIG. 1C shows an optical and electrical diagram for the circuits of optical assembly 100 . As shown in FIG. 1C , a laser driver 106 is coupled to laser assembly 104 . Laser assembly 104 includes a laser which provides optical output. The optical output from laser assembly 104 is captured by a ball lens 110 on end cap 102 (see FIG. 1A ) to couple light into an optical fiber (see FIG. 1B ). Photo diode assembly 105 captures light from laser assembly 104 and provides electrical feedback to laser driver 106 . Photodiode assembly 105 and laser assembly 104 are coupled to photodiode power and laser pump power through conductors provided on feed-through assembly 101 shown in FIG. 1A . Control, data, and power are also provided to laser driver 106 through conductors provided on feed-through assembly 101 .
Laser assembly 104 can be any source of light that can be modulated in response to a signal from laser driver 106 . In some embodiments, laser assembly 104 can be a Mitsubishi Electric and Electronics model ML792H28 laser. In some embodiments, optical laser assembly 104 can be an uncooled InGaAsP 1310 nm DFB laser. The wavelength of light output by laser assembly 104 , in some embodiments, is nominally 1310 nm (e.g. about 1290 to about 1330 nm); however, laser assembly 104 may produce any other central wavelength.
Laser driver 106 can be any circuit that converts a received digital signal to a signal appropriate for modulating the laser of laser assembly 104 . In some embodiments, laser driver 106 can be a Maxim Max3932E/D driver (Maxim Corporate Headquarters, 120 San Gabriel Drive, Sunnyvale, Calif. 94086).
In some embodiments, laser driver 106 and laser assembly 104 are mounted on the same interface board of feed-through assembly 101 . In some embodiments, laser driver 106 is mounted on a ceramic substrate of assembly 101 , which is mounted on heat sink 125 , while laser assembly 104 is mounted directly on heat sink 125 (see FIG. 1A ). Reducing the distance between laser driver 106 and laser assembly 104 by mounting the two components on the feed-through assembly 101 allows for higher data rates by shortening the transmission distance between laser driver 106 and laser 104 .
As shown in FIG. 1C , impedance matching between the output impedance of laser driver 106 and the input impedance of laser assembly 104 is accomplished by resistor 109 and inductor 103 . In some embodiments, resistor 109 and laser assembly 104 are mounted directly on heat sink 125 , which can result in an improved high temperature performance. Thermal conduction through heat sink 125 instead of through conducting leads or traces reduces the amount of electrical interference caused by thermal effects in the leads. Further, matching the output impedance of laser driver 106 to the combined impedance of the laser of laser assembly 104 and matching resistor 109 results in lower power consumption of resistor 109 . For example, matching a 20 Ohm output impedance of laser driver 106 to resistor 109 and the input impedance of laser assembly 104 results in lower power consumption by resistor 109 than does matching the 50 Ohm output impedance of the combination of laser driver 106 and resistor 109 with the input impedance of laser assembly 104 .
Inductor 103 may be a microwave spiral inductor such as that produced by US Microwave L10 62nH-20Q case 30×30 (US Microwaves, 2964–2966 Scott Blvd., Santa Clara, Calif. 95054), for example. Mounting inductor 103 adjacent to laser assembly 104 on feed-through assembly 101 and, in some embodiments directly onto laser assembly 104 , can minimize the stub length, and hence the additional impedance due to the length of the conductor coupling laser driver 106 with the input terminal of laser assembly 104 . The reduced stub length can aid in high data rate performance. Further, utilizing a thin film spiral inductor, inductor 103 can be placed within a small package such as the TO-56 standard package. In some embodiments, inductor 103 can be mounted on laser assembly 104 .
FIGS. 2A through 2D illustrate the physical, optical, and electrical configuration of an embodiment of optical assembly 100 with photodiode assembly 105 and laser assembly 104 on feed-through assembly 101 . As shown, laser assembly 104 , with laser 119 , is mounted such as to provide optical coupling. Laser 119 emits in both the forward and rear directions, providing optical input to photodetector assembly 105 .
Throughout this disclosure, directional references to forward and rear refer to the direction of transmission of light with the forward direction being toward an optical fiber (i.e., ball lens 110 is at the front because it couples light into the optical fiber). Further, references to top and bottom (or up and down) are relative to laser 119 and heat sink 125 , with heat sink 125 being on the bottom and laser 119 being on the top of optical assembly 100 .
Electrical connections are made between photodetector assembly 105 and laser assembly 104 and the conductors mounted on feed-through assembly 101 . FIG. 2D illustrates some clearance dimensions, in millimeters, for an embodiment of feed-through assembly 101 according to the present invention. In particular, clearances for a wire bond tool 118 with respect to parts of feed-through 101 are illustrated for a particular embodiment of the invention. In some embodiments, electrical connections between photodiode assembly 105 , laser assembly 104 and the conductors of feed-through assembly 101 can be by gold wire-bond technologies, which are familiar to those skilled in the art.
FIG. 3A illustrates some embodiments of feed-through assembly 101 according to the present invention. In the embodiment of feed-through assembly 101 shown in FIG. 3A , insulating ceramic layers 121 , 122 , 123 , and 124 are bonded with a spacer 120 and heat sink 125 . The combination is mounted within supports 127 and 126 and mounted to sealant ring 128 . Insulating ceramic layers 121 , 122 , 123 , and 124 provide electrical connections throughout feed-through assembly 101 . Further, access 129 is provided in ceramic layer 121 to electrically and mechanically mount laser driver 106 to ceramic layer 122 .
In some embodiments, ceramic layers 121 , 122 , 123 , and 124 can be formed from a ceramic material with standard metallization utilized to form electrical conductors. In some embodiments, the characteristics of the metallization layers can be tailored to possess particular properties by controlling widths and material composition of the conducting traces. Resistor 109 can be formed directly on one of ceramic layers 121 , 122 , 123 , or 124 or, alternatively, may be formed directly on laser assembly 104 .
FIG. 3I shows an embodiment of ceramic layer 121 with metallization 150 . In the embodiment shown in FIG. 3I , for example, each of the traces of metallization 150 can be 100 Ohm traces. In particular, traces to the left of the line marked A can be formed by a first layer of tin-lead solder, for example about 0.013 millimeters thick, with a second layer of copper about 0.025 millimeters thick deposited over the first layer. A third layer of a substrate film is formed over the second layer. In some embodiments, the substrate film is a polymide film, for example about an 0.025 millimeter thick layer of Kapton produced by Dow Chemical, is formed.
Finally, a fourth layer of copper plating is added. This layering provides electrical connections to feed-through 101 directly. Between the lines marked A and B, however, a different layering of 100 Ohm traces can be utilized. Between lines A and B, a first layer of tin-lead solder having a thickness of about 0.013 millimeter can be added and a second layer of copper trace of about 0.025 mm thickness can be added over the first layer. Finally, a top layer of substrate film, for example about 0.025 mm of Kapton, can be added. To the right of the line marked B, a layer of substrate material, for example a 0.025 mm layer of Kapton, can be utilized in the formation of traces of metallization 150 .
As is apparent, the metallization utilized on feed-through 101 must withstand the rigors of attachment to supports 126 and 127 , and sealing ring 128 . In some embodiments, supports 126 and 127 are hermetically sealed to spacer 120 , insulating plates 121 through 124 , and heat sink 125 by, for example, a gold-copper braze. In some embodiments, the hermetic seal provides a He leak rate of less than about 1×10 −8 atm-cc/sec. In formation of a hermetic seal between supports 126 and 127 and spacer 120 , insulating plates 121 through 124 , and heat sink 125 , solder material, braze material, or glass may be used.
FIG. 3B shows a cross-sectional view of the embodiment of feed-through 101 shown in FIG. 3A after assembly. The dimensions and tolerances shown in FIGS. 3B through 3R are in millimeters and apply to one particular example embodiment of the invention and are not generally limiting. FIGS. 3C through 3H show various views of an assembled embodiment of feed-through 101 shown in FIG. 3B . FIG. 3I illustrates the dimensions and metallization of a particular embodiment of insulating layer 121 shown in FIG. 3B . FIG. 3J shows the dimensions of a particular embodiment of insulating layer 122 shown in FIG. 3B . FIG. 3K shows a particular embodiment of insulating layer 123 of the embodiment of feed-through 101 shown in FIG. 3B . FIG. 3L shows the dimensions of a particular embodiment of insulating layer 124 of the embodiment of feed-through 101 shown in FIG. 3B . FIG. 3M shows the dimensions of the bottom side of insulating layer 124 of the embodiment of feed-through 101 shown in FIG. 3B , and in particular shows metallization to provide external electrical connections for the embodiment of feed-through 101 shown in FIG. 3M . FIG. 3N shows the dimensions of a particular embodiment of support 126 of the embodiment of feed-through 101 shown in FIG. 3B . FIG. 3O shows the dimensions of support 127 for the particular embodiment of feed-through 101 shown in FIG. 3B . FIG. 3P shows dimensions for spacer 120 for the particular embodiment of feed-through 101 shown in FIG. 3B . FIG. 3Q shows dimensions for sealing ring 128 for the particular embodiment of feed-through 101 shown in FIG. 3B . FIG. 3R shows the dimensions for heat sink 125 for the particular embodiment of feed-through 101 shown in FIG. 3B .
FIG. 4A illustrates assembly of an embodiment of optical assembly 100 according to the present invention. Photodiode assembly 105 and laser assembly 104 are constructed and mounted on feed-through assembly 101 . Cap 102 , with ball lens 110 , are then mounted to sealant ring 128 . As shown in the embodiment of optical assembly 100 shown in FIG. 4A , lens assembly 104 can be mounted directly onto heat sink 125 of feed-through assembly 101 . Photodiode assembly 105 can be mounted on insulating board 121 of feed-through assembly 101 .
Photodiode assembly 105 includes photodiode submount 401 and photodiode 402 mounted on photodiode submount 401 . Submount 401 provides structure for photodiode 402 and electrical contacts to electrically couple photodiode 402 with conducting traces on feed-through assembly 101 . Photodiode 402 can be any device that produces an electrical signal in response to an optical signal. FIGS. 5A through 5E illustrate a particular embodiment of submount 401 . Submount 401 is an “L-shaped” mount that is formed from an insulating material appropriate for holding photodiode 402 . Submount 401 , for example, can be formed of alumina, alumina nitrate, or other suitable material. Metallization of conducting leads 501 can be formed on submount 401 in order to electrically couple photodiode 402 , when mounted on submount 401 , to conducting traces in feed-through assembly 101 . Conducting leads 501 should be capable of withstanding the conditions of mounting photodiode assembly 105 onto feed-through assembly 101 . In some embodiments, conducting leads 501 can be formed from electroless Ni and electroless Au about 1.5 micron thick.
FIG. 5A shows a planar view of a particular embodiment of a first surface of submount 401 with conducting leads 501 . FIG. 5B shows a planar view of a particular embodiment of a second surface oriented perpendicularly to the first surface of submount 401 . FIG. 5C shows a planar view of a third surface oriented opposite the first surface of submount 401 . FIG. 5E shows a view of submount 401 along the directions indicated by the notation 5 E— 5 E in FIG. 5C . FIG. 5D shows a view of submount 401 rotated 12.5° clockwise from the view indicated by the designation 5 D— 5 D in FIG. 5E .
Photodiode 402 , as shown in FIG. 4A , can be mounted to a conducting surface such as surface 502 as shown in FIG. 5D . A second electrical connection can be made to conducting surface 503 of FIG. 5D by wire bonding. Electrical contact, then, can be made between photodiode 402 and electrical traces on submount 401 .
As shown in FIG. 4A , laser assembly 104 includes laser subassembly 404 . Laser 119 is mounted onto laser subassembly 404 . In the embodiment shown in FIG. 4A , inductor 103 is also mounted on laser assembly 104 . In some embodiments, laser 119 can be an InGaAsP 1310 nm DFB laser, which can be purchased as model ML792H28 from Mitsubishi Electric. Inductor 103 can be purchased from US Microwave as an L10 62nH-20Q case 30×30 inductor.
FIGS. 6A through 6F illustrate formation of an embodiment of laser submount assembly 404 according to the present invention. Although a particular embodiment is described in FIGS. 6A through 6F , one skilled in the art will recognize that the present invention is not limited to this embodiment.
FIG. 6A shows an embodiment of laser assembly submount 404 . Submount 404 includes a top portion 601 and a bottom portion 602 . Both top portion 601 and bottom portion 602 can be formed from aluminum nitride, for example material AN271 purchased from Kyocera. Other manufacturers, including Dupont, Alfa, and Tokuyama, produce similar materials. Conducting traces can be deposited onto top portion 601 and bottom portion 602 to provide both electrical connections and thermal transport paths.
FIG. 6B shows a top surface of top portion 601 , with metallization. Top portion 601 also includes vias 606 which, when filled with a conducting material, provide electrical and thermal connections through top portion 601 . Further, a thin film resistor can be deposited in resistor region 605 . Resistor 109 of FIG. 1C , then, can be deposited in region 605 . In some embodiments, thin film resistor 109 deposited in region 605 can be rated for about 12 Ohm+/−2% at about 250 mW of power and can be formed from aluminum. Thatched areas 607 can be plated with a conductor which can act as a thermal conductor. Thatched areas 607 , then, are electrically isolated from region 605 and 604 . The plating in area 607 can, for example, be formed by about 0.1 micron of titanium, about 0.2 micron of lead, and about 1.5 micron of gold. The plating can be tested and should not be damaged (e.g., no peeling or discoloration) after, for example, a timed bake (e.g., about 3 minutes at about 400° C.).
Region 603 provides a mount for laser 119 . Region 603 may be electrically coupled to the plating in region 607 , which would provide an electrical ground for laser 119 . Region 603 includes further metallization in order to mount and provide electrical and thermal contact with laser 119 . In some embodiments, the plating as shown in region 607 is further covered with about 0.5 micron of platinum and about 4.0 micron of gold-tin solder. In some embodiments, the gold-tin solder should be about 76%+/−2% gold by weight.
Region 604 provides an area on which to mount spiral inductor 103 . Spiral inductor 103 can be mounted, for example, with a non-conductive epoxy material.
FIG. 6C shows top portion 601 mounted to bottom portion 602 for a particular embodiment of laser submount assembly 402 according to the present invention. FIG. 6D shows dimensions of metallization features for a particular embodiment of top portion 601 of laser submount assembly 402 . In the particular embodiment of top portion 601 shown in FIG. 6D , the thickness of top portion 601 shown is prior to metallization. Further, the dimensions of resistor area 605 is a maximum area for the printed resistor.
FIGS. 6E and 6F illustrate an embodiment of bottom portion 602 of laser submount assembly 402 . As shown in FIG. 6E , a portion of the top surface of bottom portion 602 is partially plated in region 610 with conducting material. In some embodiments, for example, about 0.1 microns of titanium is deposited on the top surface of bottom portion 602 , about 0.2 microns of lead is deposited over the titanium, and about 1.5 microns of gold is deposited over the lead. Other metallizations can, of course, be utilized as well. In some embodiments, other conductors such as copper, silver, or aluminum may be utilized to form the metallizations. As before, the metallization should withstand further processing and may be tested, for example, by a timed bake (e.g., about 3 minutes at about 400° C. to check for peeling, blistering or discoloration). As shown in FIG. 6F , the entire bottom surface of bottom portion 602 can also be metallized to allow coupling of laser submount 404 with heat sink 125 of feed-through assembly 101 . The bottom surface 611 of bottom portion 602 may, for example, be coated with a gold-tin solder. In some embodiments, the gold-tin solder can be about 76%+/−2% gold by weight.
When top portion 601 is coupled with bottom portion 602 , vias 606 provide electrical and thermal connections between region 607 of top portion 601 and region 610 of bottom portion 602 . Therefore, heat from laser 603 is conducted through region 610 and bottom portion 602 to heat sink 125 . Further, heat from resistor region 605 can be conducted through the material of top portion 601 to conducting portion 610 and finally to heat sink 125 .
Although particular dimensions are illustrated in FIGS. 6A through 6F , those dimensions are included to describe a particular example embodiment of laser submount assembly 402 . The present invention is not limited to these dimensions. The particular dimensions shown in FIGS. 6A through 6F are, unless otherwise stated, in units of millimeters.
FIG. 4B shows a planar view of an embodiment of the assembled optical assembly 100 shown in FIG. 4A . FIG. 4C shows a view of the assembled optical assembly 100 shown in FIG. 4A along the line designated as 4 E— 4 E as shown in FIG. 4B . FIG. 4D illustrates the view along the line desianated 4 G— 4 G of the embodiment of the assembled optical assembly 100 shown in FIGS. 4B and 4C .
FIG. 4E is a schematic diagram along the line designated as 4 E— 4 E shown in FIG. 4B of an embodiment of optical assembly 100 shown in FIG. 4A . Fully assembled, optical assembly 100 includes feed-through assembly 101 , photodiode assembly 105 mounted on feed-through assembly 101 , laser assembly 104 mounted on heat sink 125 of feed-through assembly 101 , and cap 102 with ball lens 110 mounted on feed-through assembly 101 . Feed-through assembly 101 , in some embodiments, includes printed insulating ceramic layers 121 , 122 , 123 , and 124 coupled together. One skilled in the art will recognize a number of metallization geometries which allow electrical connections to photodiode assembly 105 and laser assembly 104 along with a laser driver 106 (see FIG. 1A ), which can be mounted in access 129 of printed ceramic layer 121 . Feed-through assembly 101 also includes heat sink 125 . In the embodiment shown in FIG. 2E , laser assembly 104 is mounted directly on heat sink 125 . In other embodiments, other arrangements may be made to thermally couple laser assembly 109 with heat sink 125 . Further, laser driver 129 can be mounted on ceramic layer 122 and, through ceramic layers 122 , 123 , and 124 , is also thermally coupled to heat sink 125 . Better thermal stabilization of optical assembly 101 , then, can be achieved by this arrangement. Feed-through assembly 101 also includes spacer 120 and supports 126 and 127 , which are mechanically coupled to form a hermetic seal around ceramic layers 121 , 122 , 123 , and 124 and heat sink 125 . An embodiment of photodiode assembly 105 is illustrated in FIGS. 5A through 5E and discussed above. An embodiment of laser assembly 104 is illustrated in FIGS. 6A through 6F and discussed above.
As illustrated in FIG. 4E , laser 119 , which is part of laser assembly 104 , provides an output optical beam directed in the forward direction through ball lens 110 . The optical beam from laser assembly 104 can then be coupled to an optical fiber as illustrated in FIG. 1B . Laser 119 also generates optical radiation directed in the backward direction towards photodiode 402 of photodiode assembly 105 . Photodiode 402 can provide feedback to laser driver 106 mounted in access 129 in order to monitor the output power of laser 119 .
FIGS. 4F and 4I illustrate layout and alignment of laser assembly 104 and photo diode assembly 105 on feed-through assembly 101 . FIG. 4F shows a top-down view of optical assembly 100 with photodiode assembly 105 and laser assembly 104 mounted on feed-through assembly 101 . Laser 119 of laser assembly 104 is optically aligned with ball lens 110 for coupling into an optical fiber. Further, photodiode 402 is optically aligned with laser 119 to provide feedback for laser driver 106 which can be mounted in access 129 . FIG. 4I is a blow-up of the area in the area designated as area 4 I shown in FIG. 4F .
As shown in FIG. 4I , photodiode 402 is mounted on photodiode subassembly 401 . Photodiode 402 can be, for example, an KPDE030C-15-13T InGaAs photodiode produced by Kyosemi (Kyosemi USA, 368 S. Abbott Ave, Milpitas, Calif. 95035). Typically, photodiode 402 includes two electrical connectors that provide power to photodiode 402 and from which a signal indicating the incident optical power on photodiode 402 can be determined. Photodiode 402 , therefore, is mounted on conducting area 502 (see FIG. 5D ) to provide one electrical contact. A wire bond to conducting area 503 is provided to form the other electrical connection for photodiode 402 . Electrical connections to traces on insulating ceramic layers 121 , 122 , 123 , and 124 are provided by the metallization 501 of photodiode subassembly 401 , which is mounted on ceramic layer 121 such that the conducting traces on photodiode assembly 105 are in contact with electrical traces on ceramic layer 121 .
Inductor 103 is connected by wire bonding through wire 411 to resistor area 605 and by wire 410 to traces on insulating ceramic layer 121 . Ground straps 413 provide electrical and thermal connections between area 607 and areas of insulating ceramic layer 121 . Laser 119 is electrically and thermally coupled through its base to area 607 . Further, laser 119 is electrically coupled through wire 412 to resistor area 605 .
Photodiode 402 can be aligned by an outside reticle or other externally controlled marks which can be “dialed in” to external features of the header. Markings formed on laser submount 404 can also be utilized to position laser 119 .
FIG. 4H shows a magnified view of laser 119 with ball bonded wire coupling to resistor area 605 . The area shown in FIG. 4H is that area designated as the area designated as area 4 H in FIG. 4F . Laser fiducials 415 , which can be utilized for optically aligning laser 119 , are also shown in FIG. 4H .
FIG. 4G shows a view along direction designated as direction 4 G— 4 G as illustrated in FIG. 4C . As shown in FIGS. 4F , 4 G and 4 I, the laser emission line and the optical axis of lens 110 need not be completely aligned. In accordance with an aspect of the present invention, cap 102 may be offset slightly so that the optical axis of ball lens 110 does not coincide completely with the laser emission. Offsetting cap 102 can allow better coupling of light out of optical assembly 101 and also allows for correction of misalignment of laser 119 during production.
In some embodiments of the invention, the facet location of laser 119 can be located by machine vision and cap 102 can be offset such that ball lens 110 is placed within a small tolerance zone of the laser emission axis. Cap offsetting in response to the position of the facets of laser 119 , once mounted, can allow for much higher OSA yields than does the practice of simply bonding cap 102 to feed-through 101 .
In some embodiments, offsetting of cap 102 does not need to be an active capping process, which usually involves a large amount of alignment time. Since typical tolerances of the optical design of optical assembly 100 allows for a small deviation of laser 119 relative to ball lens 110 , individual optical assemblies 100 can be classified as one of several “types” on production. These individual types represent various zones of the location of the facets of laser 119 with respect to ball lens 110 after final assembly. For example, a “type 1” header might have a laser facet which is offset by 0.050 mm, for example, in a certain direction, “type 2 ” might indicate 0.100 mm in the same or other direction. These different types represent the most typical placement areas observed for the laser facets and a composite picture of the overlapping areas of “coverage” each “type” allows would cover nearly the entire range of laser and ball lens placements which would occur from industry-standard TO56 header assembly processes. In this way, the offset capping can be reduced to 5 or 6 “types” or “settings” such that matching their (laser facet) offset with a corresponding, pre-determined cap offset becomes practical. The offset of the cap can be accomplished via cap mandrels which have offset pockets and which are indexed to the rotational orientation of the header. The measurement of the laser facet will be made via magnified machine vision and will be taken relative to features which are later also used to locate the position of the cap prior to attachment.
Therefore, when cap 102 is attached to sealing ring 128 , first the facet of laser 119 is located and optical device 100 is typed. Cap 102 is positioned and attached in accordance to the typing of optical device 100 . The facet of laser 119 can be located automatically in a machine vision position tool.
FIG. 7A shows an assembly process 700 for producing optical assembly 100 according to the present invention. In step 710 , feed-through assembly 101 is assembled. Feed-through assembly 101 can be produced, for example, by Kyocera (Kyocera International, Inc., 8611 Balboa Ave, San Diego, Calif. 92123-1580), NTK (NTK Technologies, 3255-2 Scott Boulevard, Suite 101 , Santa Clara, Calif. 95054), or Sumitomo (Sumitomo Corporation of America, 600 Third Ave., New York, N.Y. 10016-2001). In step 720 , photodiode assembly 105 is produced. In step 730 , laser assembly 104 is produced. In step 743 , photodiode assembly 105 is attached to feed-through assembly 101 . In step 750 , laser assembly 104 is attached to feed-through assembly 101 . In step 760 , electrical connections between traces on feed-through assembly 101 , laser assembly 104 , and photodiode assembly 105 are made. In step 770 , the partially assembled optical assembly 100 is typed based on the emission axis of laser 119 of laser assembly 104 . In step 780 , cap 102 with ball lens 110 is attached to feed-through assembly 101 based on the type determined in step 770 . In step 790 , optical assembly 100 can be tested. In some embodiments, certain of these steps may be rearranged. For example, steps 720 and 730 may occur in a different order. Similarly with steps 730 and 740 , for example. One skilled in the art will recognize several variations of the flow chart shown in FIG. 7A .
FIG. 7B illustrates an example method for performing step 710 to assemble feed-through assembly 101 . In step 711 , each of ceramic layers 121 , 122 , 123 , and 124 are produced. Ceramic layers 121 , 122 , 123 , and 124 can be formed to the appropriate shapes from a ceramic material, for example AN271 alumina tape. Further, access areas and vias can be formed in ceramic layers 121 , 122 , 123 , and 124 to accommodate electrical and thermal conductivity throughout feed-through 101 . Metallization for creating electrical traces on ceramic layers 121 , 122 , 123 , and 124 can be formed by first depositing, for example, a layer of Kapton in certain portions (i.e., to the right of line B in FIG. 3I , for example). In the embodiment shown in FIG. 3I , between the lines labeled A and B of ceramic layer 121 , a first layer of SnPb solder about 0.013 mm thick and about 0.160 mm wide is deposited on the ceramic material. A second layer of copper trace about 0.025 mm thick and about 0.160 mm wide is deposited over the first layer of SnPb solder. Finally, a top layer of, for example, Kapton about 0.025 mm thick can be deposited over the copper trace. To the left of the line marked A on FIG. 3I , a top layer of copper plating about 0.025 mm thick is placed. Metallization is formed both to conduct heat and provide electrical connectivity through feed-through 101 . One skilled in the art will readily determine a number of ways to metallize ceramic layers 121 , 122 , 123 , and 124 to achieve this purpose. Ceramic layers 121 , 122 , 123 , and 124 can be attached, both electrically and mechanically, to one another during cofiring. In other words, in some embodiments traces are printed on green ceramic layers 121 , 122 , 123 and 124 by a thick film process and then the layers are cofired together to form a cohesive, rigid, multilayered unit.
In step 712 , heat sink 125 is attached to the bottom of ceramic layer 124 . Heat sink 125 is attached to provide a position for the later mounting of laser assembly 104 and to provide a heat sink for a laser drive 106 , which can be placed in access 129 in ceramic layer 121 , in contact with ceramic layer 122 . An example of the placement of heat sink 125 is shown in FIG. 3E . Heat sink 125 can be formed from any thermally conducting material, for example a copper-tungsten material (10CU90W) that can be obtained from Kyocera.
In step 713 , ceramic spacer 120 can be attached by epoxy to the top of ceramic layer 121 , as shown in FIG. 3B . FIG. 3B also shows the placement of ceramic spacer 120 for a particular embodiment of optical assembly 100 .
In step 714 , supports 127 and 126 are positioned onto spacer 120 and heat sink 125 around ceramic layers 121 , 122 , 123 , and 124 , and attached so that a hermetic seal is produced around ceramic layers 121 , 122 , 123 , and 124 . In some embodiments, supports 126 and 127 can be formed from an iron-nickel alloy, Fe—Ni50 Kovar, which can be obtained from a number of suppliers. In some embodiments, supports 126 and 127 are sealed to ceramic spacer 120 , heat sink 125 , and ceramic layers 121 , 122 , 123 , and 124 by a silver copper brazing technique. In some embodiments, the He leak rate through feed-through 101 is less than about 1×10 −8 atm cc/sec. The metallization performed on ceramic layers 121 , 122 , 123 , and 124 should not be damaged by the bonding techniques used.
In step 715 , sealant ring 128 is positioned and attached to supports 126 and 127 . In some embodiments, sealant ring 128 is formed of the same material as is supports 126 and 127 and is bonded to supports 126 and 127 concurrently with the bonding of supports 126 and 127 to spacer 120 , ceramic layers 121 , 122 , 123 , and 124 , and heat sink 125 .
In step 716 , feed-through assembly 101 is inspected. Inspection of feed-through assembly 101 can include a visual inspection through a microscope to check for blistering or discoloration of the metallization. Inspection step 716 may also include electrical tests to check the electrical connectivity of various metallization traces through feed-through 101 .
FIG. 7C illustrates assembly of photodiode assembly 104 . In step 721 , photodiode 402 can be inspected. Photodiode 402 can, for example, be an InGaAs PIN diode or any other device which provides an electrical signal in response to light incident on a surface of photodiode 402 . Inspection of photodiode 402 can include a visual inspection, for example with a 10-100× microscope.
In step 722 , photodiode submount 401 can be inspected. Submount 401 , as illustrated in the embodiment shown in FIGS. 5A through 5E , can be formed from alumina or other insulating material, such as AlN or BeO, for example. Submount 401 is metalized to provide electrical connections to photodiode 402 . Inspection step 722 can include a visual inspection, for example, with a 10-100× microscope, of the metallization as well as the material of submount 401 . Submount 401 , with metallization as described here, can be obtained from Stellar Industries (Stellar Industries Corp., 225 Viscoloid Ave., Leominster, Mass. 01453-4388), ATP (Advanced Thermal Products, Inc., P.O. Box 249, 328 Ridgeway Rd., St. Marys, Pa. 15857), NTK, or Kyocera.
In step 723 , photodiode 402 is positioned on photodiode submount 401 and fixed to photodiode submount 401 . As shown in FIGS. 4I and 5D , photodiode 401 is also electrically coupled to region 502 of metallization on photodiode submount 401 . In some embodiments, photodiode 402 is attached to region 502 of submount assembly 401 with a silver epoxy or glass+paste. After visual inspection, for example with a 10-100× microscope, the silver paste epoxy, for example Epotek H20E (Epoxy Technology, 14 Fortune Dr., Billerica, Mass. 01821), can be cured. Epotek H20E, for example, is cured by heating for about 30 minutes at a temperature less than about 150° C. In some embodiments, photodiode 402 can be attached to submount 401 attached with Ag-filled glass preforms or paste. Such paste is also manufactured by Ablestik (Ablestik Laboratories, 20021 Susana Rd., Rancho Dominquez, Calif. 90221) (e.g., 2105S) and DieMat (Diemat, Inc., 19 Central St., Byfield, Mass. 01922) (e.g., DM2700PF).
In step 724 , photodiode 402 is further electrically connected to metallization deposited on submount 401 . In some embodiments, a gold ball bonding technique can be utilized to attach a wire between a connection on the front of photodiode 402 to metallization region 503 on submount 401 . Once photodiode 402 is mounted and electrically connected to the metallization traces formed on photodiode subassembly 401 , photodiode assembly 105 is formed.
In step 725 , electrical testing of photodiode assembly 105 can be performed. In some embodiments, a burn-in with a voltage of about 2V at a temperature of about 100° C. for about 96 hours can be performed. Other embodiments of the invention may utilize different procedures for testing photodiode assembly 105 electrically.
FIG. 7D illustrates step 730 of process 700 , forming laser assembly 104 . In step 731 , upper portion 601 is formed and metallization is added. In embodiments as shown in FIGS. 6A through 6F , a resistor region 605 is formed with a thin film resistor material deposited in resistor region 605 to form resistor 109 as shown in FIG. 1B . Further, vias 606 are formed to provide electrical and thermal contact to bottom portion 602 . In some embodiments, upper portion 601 can be formed from aluminum nitride (AN271) and metallization can be formed from a first layer of Ti about 0.1 micron thick covered by a layer of lead about 0.2 micron thick and further covered by a layer of gold about 1.5 micron thick. Other metallizations can also be utilized. Further, in some embodiments region 603 can also include a layer of platinum 0.5 micron thick deposited over the gold layer and a layer of gold-tin solder about 4.0 micron thick.
In step 732 , bottom region 602 can be formed. Bottom region 602 can be formed of an insulating material which is metallized on the top surface to provide electrical and thermal contact through vias 606 of top portion 601 . Further, the bottom surface of bottom region 602 can be metallized to provide thermal and electrical contact when mounted on heat sink 125 . In some embodiments, bottom region 602 can be formed of aluminum nitride (AN271) metallized with the same materials as were used for upper region 601 .
In step 733 , laser subassembly is formed by positioning upper portion 601 on bottom portion 602 and bonding them together. Upper portion 601 can then be cofired with bottom region 602 to form laser subassembly 404 . Cofiring is the process by which “unfired” or “green” ceramic layers are sandwiched together and are brought to elevated temperature under pressure. This procedure fuses the ceramic layers together to form an integral, multi-layered part. The conductive traces which were applied to the ceramic prior to the cofiring process maintain their conductivity and function as a printed wire board.
In step 734 , laser 119 is attached to region 603 of upper portion 601 . Laser 119 can be attached, for example, by bonding to the gold-tin solder deposited in region 603 . Bonding can be achieved by heating the assembly for a period of time, for example to about 300° C. for 30 minutes.
In step 735 , inductor 103 is epoxied to region 604 of upper portion 601 . Finally, in step 736 electrical connections between laser 119 and the thin film resistor deposited in resistor region 605 and connections between inductor 103 and the thin film resistor deposited in resistor region 605 can be accomplished by a gold ball bonding method.
FIG. 7E illustrates an example of step 740 shown in FIG. 7A . In step 741 , photodiode assembly 105 is positioned on ceramic layer 121 . In step 742 , photodiode assembly 105 can be attached to and electrically coupled to traces on ceramic layer 121 of feed-through 101 with a Ag paste epoxy (e.g., Epotek H20E). Curing of the epoxy may be accomplished, for example, by heating for about 30 minutes at low temperature (e.g., less than about 150° C.). In step 743 , photodiode assembly 105 is tested on feed-through assembly 101 . For example, a visual inspection through a 10-100× microscope can be performed. Additionally, a dark current check can be performed. In some embodiments, the dark current from photodiode 402 should be less than about 100 nA.
FIG. 7F shows an example of step 750 shown in FIG. 7A . In step 750 , laser assembly 104 is attached to heat sink 125 of feed-through assembly 101 . In some embodiments, laser assembly 104 is attached through a Ag epoxy or with a Au—Sn solder. In step 752 , a plasma cleaning process can also be performed in preparation for performing ball-bonding.
FIG. 7G illustrates step 760 shown in FIG. 7A . In step 761 , ribbon bands 413 , wires 410 , and possibly wires 411 and 412 are attached, for example by ball bonding. As shown in FIG. 7F , a plasma cleaning process may be performed prior to the ball bonding step. In step 762 , a wire pull test may be performed. In a wire pull test, each of ribbon bands 413 and wires 410 , 411 , 412 and others are pulled slightly to ensure that they are firmly bonded.
FIG. 7H shows an example of step 770 of FIG. 7A . In step 771 , laser facet location and orientation of laser 119 on laser assembly 104 is determined. Facet location and orientation can be determined, for example, by reflecting an optical beam from the laser surface and measuring the reflected beam. Other machine vision techniques for determining the facet location and orientation of laser 119 can also be used. In some embodiments, laser fiducial marks (see marks 415 shown in FIG. 4H ) can be utilized to determine facet location and orientation. In step 772 , the laser emission axis offset is determined from the location and orientation of the laser facet. Once the laser emission axis is determined, in step 773 optical assembly 101 can be classified as belonging to a particular type. For example, “type 1” may indicate that the laser facet is offset by a certain distance in a first direction while “type 2” may indicate that the laser facet is offset by a certain distance in the opposite direction. There may be any number of types, and there should be a sufficient number of different types in the classification to allow cap 102 to be positioned within the allowable tolerances required of optical assembly 101 .
FIG. 7I illustrates an example of step 780 of FIG. 7A . In step 780 , cap 102 is positioned according to type in step 781 and attached to sealant ring 128 in step 782 . In step 781 , cap 102 is positioned in order to focus the light emission from laser 119 to couple with an optical fiber. From the type of optical assembly 100 , the position of cap 102 can be determined. Therefore, based on type, cap 102 is positioned relative to laser 119 . In step 782 , cap 102 is attached, for example by brazing, to sealant ring 128 .
In step 790 shown in FIG. 7A , optical assembly 100 is tested. For example, a leakage test to ensure that the area between cap 102 and sealant ring 128 is sealed can be performed. In some embodiments, a He leak of less than about 5×10 −8 atm cc/sec should be attained. Further, electronic testing can be performed. Further, a burn-in step can be performed. For example, a current of 50 mA to laser 119 at a temperature of about 100° C. for about 96 hours can be performed. A second set of electronic tests, for example LIV testing, can be performed. LIV testing is a standard DC test of laser performance involving testing the light output (L) of the laser at various currents (I) and voltages (V) and is typically performed over a range of temperatures. Finally, a high speed data test can be performed by modulating laser 119 at a particular rate and monitoring the emissions through lens 110 .
One skilled in the art will recognize numerous variants based on the embodiments of the invention disclosed here. These variants are considered within the scope and spirit of this disclosure. Further, several of the figures include numerical dimensions that are intended to illustrate a particular embodiment of the invention and are not intended to be generally limiting. As such, the invention is limited only by the following claims. | An optical assembly that can be utilized as a transmitter in a high data rate optical transceiver system is presented. The optical assembly allows a laser driver to be mounted near the laser and allows the laser driver and the laser to utilize a common heat sink. Further, assembly can be performed reliably and quickly to reduce the cost of production of the optical assembly. | 7 |
This application is a continuation-in-part of application Ser. No. 07/634,439 filed on Dec. 27, 1990, now U.S. Pat. No. 5,108,029, which is a continuation-in-part of application Ser. No. 07/465,848, filed on Jan. 16, 1990, (now abandoned).
FIELD OF THE INVENTION
The present invention pertains to a pour spout and more particularly, to a container having a reclosable pour spout attached thereto.
BACKGROUND OF THE INVENTION
There are various types of devices that have been proposed for attachment to containers to facilitate the emptying of the contents from the container. For example, U.S. Pat. No. 4,813,578 discloses a pour spout provided with a flange portion for attaching the pour spout to the exterior surface of a container. The flange portion of the pour spout is attached to the exterior surface by heat sealing the plastic material from which the pour spout is fabricated to the plastic outer coating on the container. Such an arrangement is susceptible to certain improvements because it has been found that the securement of the pour spout to the container may deteriorate somewhat over time. In particular, once the pour spout is attached to a container, it is believed that the plastic layer on the container has a tendency to undergo additional curing or other changes. As a result, the adhesion at the interface between the flange portion of the pour spout and the outer surface of the container may be affected and diminished slightly, e.g., the plastic coating on the container may shrink slightly relative to the flange portion of the pour spout.
While this consideration is of concern in most all types of pour spouts that are secured to a container, it may be of particular concern in the case of pour spouts which have a flip top type of reclosable cap for closing the pour spout. In the case of pour spouts employing a flip top type of reclosable cap, an upwardly directed force is required to open the cap. If the integrity of the attachment of the pour spout to the outer surface of the container has been diminished in the foregoing manner, the force required to open the cap will contribute to further diminishing the secure attachment of the pour spout to the container.
U.S. Pat. No. 4,909,434 discloses a method of securing a pouring spout in liquid-tight relation to the innermost and outermost surfaces of a carton. The pouring spout is provided with a preformed flange and a liquid passageway oriented substantially perpendicular to the flange. The pouring spout is mounted on the carton by inserting the liquid passageway of the pouring spout through a hole that is cut in the carton. The flange is brought into contacting relation with the outer surface of the carton wall while the liquid passageway is deformed to form a second flange on the interior of the carton. Sufficient heat and pressure is then applied to the two flanges to continuously fuse the flanges to the innermost and outermost layers of the carton wall around the entire periphery of the hole in the carton. This pouring spout is also susceptible of various improvements.
SUMMARY OF THE INVENTION
To address the foregoing concerns and others, the present invention provides a pour spout that is attached to the container in a manner that is well suited for helping to ensure that the pour spout remains reliably and securely attached to the container and is not easily pulled from the container. In accordance with one aspect of the present invention, the container includes an exterior surface, an interior surface, an interior for holding contents and an opening extending through a wall thereof for permitting emptying of the contents from the container. The reclosable pour spout that is secured to the container includes a flange member having oppositely positioned first and second sides. An aperture extends through the flange member and the second side of the flange member is secured to the outer periphery of the wall of the container. An extension is connected to and extends axially away from the flange member and the extension has an aperture extending therethrough that communicates with the aperture in the flange member. A stem is connected to and extends axially away from the second side of the flange member and the stem has an aperture extending therethrough that communicates with the aperture in the flange member. The pour spout is positioned on the container such that the stem 15 extends through the opening in the wall of the container and into the interior of the container. A portion of the stem is turned outwardly and toward the interior surface of the wall to which the flange member is secured to produce a mechanical engagement between the turned stem and the container which tends to resist any tendency of the pour spout to be pulled from the container.
In accordance with another aspect of the present invention, a method of providing a container with a pour spout includes the steps of providing a pour spout having a hollow cylindrical portion and an annular flange member connected to and extending radially outwardly from a outer peripheral surface of
n the cylindrical portion, wherein the flange member is positioned intermediate opposite ends of the cylindrical portion and wherein the cylindrical portion has a part positioned between the flange member and one end of the cylindrical portion that defines a stem. The method also includes providing a container, mounting the pour spout on the container by inserting the stem into an opening in the container wall, and turning a portion of the stem outwardly to form an outwardly turned portion of the stem and turning the stem toward the inner surface of said container wall to form an upwardly turned portion of the stem.
BRIEF DESCRIPTION OF THE DRAWINGS FIGURES
FIG. 1 is a cross-sectional side view of one embodiment of the reclosable pour spout according to the present invention attached to a container;
FIG. 2 is a cross-sectional side view of another embodiment of the reclosable pour spout according to the present invention attached to a container;
FIG. 3 is a cross-sectional side view of another embodiment of the reclosable pour spout according to the present invention attached to a container; and
FIG. 4 is a bottom perspective view of the embodiment of the pour spout illustrated in FIG. I.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring initially to FIG. 1, only those features of the reclosable pour spout necessary for a proper understanding of the present invention will be described herein. For a more detailed description of the various features of the reclosable spout, reference is made to the aforementioned parent applications, application Ser. No. 634,439 filed on Dec. 27, 1990 and application Ser. No. 465,848 filed on Jan. 16, 1990, the entire disclosure of both of which is incorporated herein by reference.
As seen in FIG. 2, the reclosable pour spout 10 according to the present invention includes a base member 12 and a cap 14. The cap 14 may be integrally connected to and formed in one piece with the base member 12. The cap 14 can be connected to the cap 14 by way of a strip of connecting material 18.
The base member 12 as illustrated in FIG. 4 is defined by a substantially planar flange member 20, an upwardly extending substantially cylindrical extension 24 and a downwardly extending substantially cylindrical stem 26. Preferably, the cylindrical extension 24, the cylindrical stem 26 and the flange member 20 are all formed integrally and in one piece from a suitable plastic material. In the embodiment illustrated in FIGS. 1 and 4, the stem 26 can have a substantially constant thickness along its length. The extension 24 and the stem 26 together define a hollow cylindrical portion and the flange member 20 surrounds that cylindrical portion at a point intermediate the ends of the cylindrical portion.
To provide the pour spout 10 with an extremely effective airtight and liquid-tight seal, it is desirable that the inner surface of the cap 14 and the outer peripheral surface of the cylindrical extension 24 interact with one another in the manner illustrated in the FIG. 2. Generally speaking, the extension 24 is provided with an annular ridge 32 and an annular recess 34 while the inner surface of the cap 14 is provided with an outwardly tapering part 36 that cooperates with the annular ridge 32 and the annular recess 34. Further details pertaining to the construction of the cylindrical extension 24 and the inner surface of the cap 14 are described more fully in the aforementioned application Ser. No. 634,439 and reference is made to that application for a more detailed description of those features.
One possible way of securing the pour spout 10 to the container 100 is by way of a suitable adhesive. The adhesive can be applied to the bottom surface 28 of the flange member 20 and the facing outer surface of the container 100. To help prevent the adhesive from flowing into the package and contaminating the contents, an annular barrier strip 38 is provided on the exterior surface of the cylindrical stem 26. The annular strip 38 functions as a barrier for inhibiting the adhesive from flowing beyond the barrier 38. The annular barrier strip 38 can be seen in the perspective view of FIG. 4.
As seen more clearly in FIG. 4, the cylindrical stem 26 is provided with oppositely positioned and generally V-shaped cutout portions 40. Preferably, the portion of the stem 26 below the barrier strip 38 and extending away from the flange member has a reduced thickness accomplished by maintaining the interior dimension identical with the remainder of the stem 26. The generally V-shaped cutout portions 40 help facilitate the process of forming the stem 26 from the initial configuration shown in FIG. 4 to the final configuration depicted in FIG. 2 in which the pour spout 10 is mounted on the container 100. It is to be understood that the description of the pour spout being mounted or secured to a container or a container body is meant to include the pour spout being attached to a container, to a container blank prior to formation into the container, and to a container blank in any intermediate stage of the container formation process.
Initially the pour spout 10 is placed on the container 100 by inserting the cylindrical stem 26 into the hole formed in the container 100. Thereafter, a suitably shaped plate is brought into contact with the free end 42 of the cylindrical stem 26 to cause a portion of the stem 26 to turn outwardly and form an outwardly turned portion 25, to turn slightly upwardly toward the wall of the container 100 to form an upwardly turned portion 27, and to turn outwardly again to form another outwardly turned portion 29. As can be seen from FIG. 2, the outwardly turned portion 29 preferably extends somewhat parallel to the wall of the container 100. Additionally, the outwardly turned portion 29 of the stem 26 is preferably in contact with the inner surface of the wall of the container 100. As an alternative to the specific construction shown in FIG. 2, the free end 42 of the stem 26 could be turned upwardly slightly such that the free end 42 of the stem 26 is in contact with the inner surface of the wall of the container 100.
By forming the stem 26 of the pour spout 10 relative to the container 100 in the manner illustrated in FIG. 2, the pour spout 10 is mechanically secured in place on the container 100. When an upwardly directed force is applied to the pour spout 10, such as might occur upon opening of the cap 14 or if the container is picked up by the pour spout, the outwardly turned portion 2 of the stem 26 rests against the inner surface of the container 100 and tends to distribute the upwardly directed force across the surface of the container. Thus, even if the interface between the flange member 20 and the outer surface of the container 100 is altered slightly as a result of further curing of the plastic layer on the container, the ability of the pour spout to be pulled away from the container will be substantially inhibited.
The embodiment of the pour spout shown in FIG. 1 is similar to that illustrated in FIG. 1 except that an annular ledge 30' is included that extends around the entire periphery of the cylindrical stem 26'. The annular ledge 30' is spaced from the bottom surface 28, of the flange member 20' by a distance that generally corresponds to the thickness of the container 100'. During fabrication of the container 100', a hole is formed in the container to receive the stem 26' of the pour spout 10'. It can be readily appreciated that due to the nature of the material from which the container 100' is fabricated, the periphery of the hole in the container 100' can be displaced slightly in the plane of the material when the cylindrical stem 26' is inserted into the hole. The portion of the container wall surrounding the stem 26' becomes, positioned between the ledge 30' and the bottom surface 28' of the flange member 20' in the manner illustrated in FIG. 1. As a result, the pour spout 10' is held in place relative to the container 100' in the axial direction so that the pour spout 10' can be securely attached to the container by suitable means. Thus, the ledge 30' helps to maintain the position of the pour spout 10' on the container 100' to help ensure that the pour spout 10' is securely attached to the container 100'.
It should be readily understood that the annular ledge 30' which extends completely around the outer periphery of the cylindrical stem 26' could be replaced with a plurality of spaced apart ledges which extend around a portion of the cylindrical stem, such as is disclosed in application Ser. No. 634,439.
It can be readily seen from a review of FIGS. 1-3 that the outwardly turned portion 29, 29' of the stem 26, 26' is not sealed to the inner surface of the container 100. However, in certain applications, it may be desirable to secure the outwardly turned portion 29, 29' of the stem 26 to the inner surface of the container, such as for example by use of an adhesive.
To attach the pour spout 10, 10' to the container 100, 100', an adhesive is applied between the bottom surface 28, 28, of the flange member 20, 20' and the facing outer surface of the container 100, 100'. To help ensure that the adhesive does not flow outwardly beyond the outer edges of the flange 20, 20' and does not flow inwardly between the outer periphery of the stem 26, 26' and the inner periphery of the hole in the container, two annular ridges 46, 46', 48, 48' (shown in exaggerated scale) are provided on the bottom surface 28, 28' of the flange member 20, 20'. However, it may be desirable to eliminate the annular ridge 48, 48' so that adhesive can flow partially down the stem 26 to the annular barrier strip 38, 38' to aid sealing the hole in the container. Alternatively, additional adhesive/sealant can be applied to the stem 26 between the flange members 20, 20' and the annular barrier strip 38, 38' to accomplish essentially the same result while still preventing substantial adhesive in the interior of the carton. The annular ridges 46, 48 are also useful in helping to concentrate the adhesive in a confined annular area to thereby aid in proper securement of the pour spout 10, 10' to the container 100, 100'. The use of such annular ridges 46, 48 is described in the aforementioned application Ser. No. 634,439, and reference is made to that application for a more detailed description of that feature.
Turning to FIG. 3, another embodiment of the reclosable pour spout of the present invention is illustrated. To simplify the illustration and description, the integrally formed cap is not illustrated. However, it is to understood that the cap could be configured in the manner illustrated with respect to the embodiment shown in FIGS. 1 and 2.
As seen in FIG. 3, the reclosable pour spout 50 includes a flange member 52, an axially upwardly extending and integrally formed cylindrical extension 54 and an integrally formed and axially downwardly extending cylindrical stem 56. Although the cylindrical extension 54 is shown as having a slightly different configuration then that illustrated with respect to the embodiments shown in FIGS. 1 and 2, it is to be understood that the extension 54 could be configured in the same manner illustrated with respect to the embodiments shown in FIGS. 1 and 2.
In the embodiments shown in FIG. 3, the thickness of the cylindrical extension 56 can decrease from the flange member 52 to the free end 58 of the extension 56. The stem 56 is reduced in thickness to help facilitate the forming of the stem 56 in the manner necessary to result in the configuration shown in FIG. 3. Preferably, in the FIG. 3 embodiment, the V-shaped notches are not provided in the stem 56. Thus, the stem 56 is unbroken such that from the bottom surface of the flange member 52 to the free end 58 of the stem 56, the sem forms a complete cylindrical member.
The securement of the embodiment of the reclosable attachment shown in FIG. 1 to the container is effected by inserting the cylindrical stem 56 into the hole in the container 200. An adhesive can be applied between the bottom surface of the flange member 52 and the outer surface of the container 200 to secure the pour spout 50 to the container.
A tool can then be employed to form the cylindrical stem 56 into the configuration shown in FIG. 3. The tool is such that it causes the stem 56 to flair outwardly at a point 60 just below the flange member 52. This outward flaring of the stem 56 also causes the portion 62 of the container surrounding the hole periphery to flair downwardly toward the interior of the container and slightly outwardly, thereby defining a generally U-shaped crotch 61. In addition to causing a portion of the stem 56 to be turned outwardly to define an outwardly turned portion 55, the tool also causes a portion of the stem 56 to turn upwardly to define an upwardly turned portion 57. Additionally, the upwardly turned portion 57 is turned in towards the stem 56 so that the free end 58 of the stem 56 fits into the generally U-shaped crotch 61 formed by the turning of the portion 62 of the container. In a slightly altered construction, the upwardly turned portion 57 of the stem could be turned slightly less than that illustrated in FIG. 3 so that the free end 58 of the stem 56 faces and is substantially in contact with the inner surface of the container wall. In this latter alternative, the upwardly turned portion 57 of the stem could be somewhat perpendicularly arranged with respect to the container wall. Generally speaking, in the embodiment of the pour spout shown in FIG. 3, the portion of the stem 56 of the pour spout 50 that has been turned is substantially C-shaped in cross-section.
As a result of the formation of the stem 56 into the configuration shown in FIG. 3, the portion 62 of the container material surrounding the hole periphery is positioned within a substantially closed region 64 defined by the outwardly and upwardly turned portion of the stem 56. Such an arrangement can be advantageous in that any adhesive that may flow radially inwardly between the outer periphery of the stem 5 and the inner periphery of the hole in the container 200 will be prevented from flowing into the interior of the container and contaminating the contents in the container since it will be trapped within the enclosed region 64.
The formation of the stem 56 of the pour spout 50 relative to the container 100 in the manner shown in FIG. 3 produces a pour spout 50 that, like the embodiments illustrated in FIGS. 1 and 2, is mechanically secured in place on the container 200. Consequently, when an upwardly directed force is applied to the pour spout 50, such as might occur upon opening of the cap (not shown) or if the container 200 is picked up by the pour spout 50, the upwardly turned portion 57 of the stem 56 presses against the inner surface of the container 200, thereby resisting an tendency of the pour spout to be pulled out of the container 200. Thus, even if the integrity of the adhesion at the interface between the flange member 52 a the outer surface of the container 200 is diminished slightly as a result of further curing of the plastic layer on the container as noted above, the contact between the turned stem 56 and the inner surface of the container 200 will tend to prevent the pour spout 50 from being pulled out of the container 200.
While the embodiment of the pour spout illustrated in FIG. 3 is not illustrated as being provided with annular ridges on the bottom surface of the flange member 52 for purposes of confining the adhesive, it is to be understood that annular ridges similar to the annular ridges 46, 48 shown in FIG. 2 could be provided, if desired.
Although the embodiment of the pour spout 10 illustrated in FIGS. 1, 2 and 4 is described being mounted on the container through use of the described method of forming the upturned portion of the stem 26, it is to be understood that the method described for forming the upturned portion of the stem 56 illustrated in FIG. 3 and for mounting the pour spout 50 on the container could be used as an alternative, thereby resulting in downwardly and outwardly flared portions of the container. Similarly, the method described for mounting the pour spout 10 illustrated in FIGS. 1, 2 and 4 on the container could be employed in connection with the mounting of the pour spout 50 shown in FIG. 3.
It is also to be recognized that all of the embodiments of the pour spouts disclosed herein and described above could be provided with a tamper evident and accidental opening preventive feature for indicating if the pour spout has been tampered with and for helping to inhibit accidental opening of the pour spout. Various embodiments of such a tamper evident and accidental opening preventive feature are disclosed in the aforementioned application Ser. No. 634,439 and are incorporated herein by reference.
The principles, preferred embodiments and modes of operation of the present invention have been described in the foregoing specification. The invention that is intended to be protected herein should not, however, be construed as limited to the particular forms disclosed, as these are to be regarded as illustrative rather than restrictive. Variations and changes may be made by others and equivalents employed without departing from the spirit of the present invention. Accordingly, the foregoing detailed description should be considered exemplary in nature and it is expressly intended that all such variations, changes and equivalents which fall within the spirit and scope of the present invention as set forth in the attached claims, be embraced thereby. | A container for holding pourable contents includes an exterior surface, an interior surface, an interior for holding contents and a reclosable pour spout mounted on the container. The pour spout includes a flange member having oppositely positioned first and second sides. An aperture extends through the flange member and the second side of the flange member is secured to the outer periphery of the wall of the container. An extension is connected to and extends axially away from the outer surface of the container and the extension has an aperture extending therethrough that communicates with the aperture in the flange member. A stem is connected to and extends axially away from the second side of the flange member. The stem has an aperture extending therethrough that communicates with the aperture in the flange member and the pour spout is positioned on the container such that the stem extends through the opening in the wall of the container and into the interior of the container. At least a portion of the stem is turned outwardly and toward the interior surface of the wall to which the flange member is secured to produce a mechanical engagement between the turned stem and the container which tends to resist any tendency of the pour spout to be pulled from the container. | 1 |
BACKGROUND OF THE INVENTION
The present invention relates to a transmission arrangement of the kind for converting the rotary movement of a motor into a linear curved movement of a driven body.
Transmission arrangements of that kind are used in particular as window lifting assemblies in motor vehicles, in which the doors, as viewed in the direction of travel, are curved convexly outwardly so that the windows must be moved along a curved path which follows the curvature of the door when they are opened or closed.
For that purpose it is known to arrange in the door a fixed electric motor driving a gear wheel or the like which engages into a cylindrical wire spiral or coil member and, upon being rotated, displaces it in the longitudinal direction. The wire spiral or coil member which has only a low degree of inherent stiffness transversely with respect to its longitudinal direction is so enclosed by a sheet metal tube which is slit in the longitudinal direction, that the wire spiral or coil member can only move back and forth in the tube. The one end of the wire spiral or coil member is rigidly connected to the window to be moved, while the element which connects those two parts together extends through the slit in the sheet metal tube. The part of the sheet metal tube in which the end of the wire spiral or coil member, which is connected to the window, moves back and forth, extends parallel to the path of movement of the window.
As only pulling or pushing forces can be applied by such an arrangement in the longitudinal direction of the sheet metal tube and the wire spiral or coil member which is guided therein, it is necessary to provide additional guide devices which carry frictional moments and lateral tilting moments of the member to be moved. That is difficult in particular when the window is to be guided only at one side, for design reasons.
So that the window stops in the respective position attained after the drive motor is switched off and cannot be pressed downwardly, generally the sheet metal tube which encloses the wire spiral or coil member is additionally wound to form at least one loop so that the cable friction as between the wire spiral or coil member and the sheet metal tube produces a self-locking effect which is independent of the motor or the engagement of the motor gear wheel into the wire spiral or coil member. However that cable friction has to be overcome in any deliberate lifting or lowering operation and therefore results in the consumption of an additional amount of power.
Another disadvantage of the known arrangement is that the sheet metal tube must be at least twice the length of the full lifting motion of the window so that the wire spiral or coil member continues to be guided in the sheet metal tube when the window is in the fully lowered position. That results in a comparatively large amount of space being required.
SUMMARY OF THE INVENTION
In comparison therewith the invention is based on the object of providing a transmission arrangement of the kind set forth in the opening part of this specification, which is of minimum structural size and which makes it possible for the member to be moved to be guided precisely along the curved path without involving additional guide means and to carry corresponding counteracting moments.
The invention therefore no longer uses a motor which is stationary in relation to the article to be moved and which drives a displaceable element (the wire spiral or coil member) which is also displaced with that article and which is of such a flexible configuration that it can admittedly adapt to the curved path but cannot perform any guide function. Instead, the arrangement provides a stationary spindle which is curved in accordance with the curved path of movement and along which the motor moves in the longitudinal direction by virtue of the rotary movement between the rotor and the stator. In that respect, in the present context, the reference to a curved spindle means an elongated curved bar or rod which is of substantially circular configuration in each of its cross-sections perpendicular to the longitudinal axis, and provided on the peripheral surface of which is at least one helical thread or flight which extends at least over the length of the path to be covered by the article to be moved. The thread pitch, pitch angle, pitch depth and cross-sectional shape of the thread flight can vary within wide limits. At any event the thread counterpart portion and therewith the motor assembly and the article to be moved are afforded such a good guidance effect, by virtue of the curved spindle, that it is substantially possible to eliminate additional guide elements. As the spindle only has to be immaterially longer than the path of movement to be covered by the article to be moved, that arrangement gives a minimum installation size. Even under compact spatial conditions, that makes it possible in many cases for the article to be guided to be supported on the spindle beneath its center of gravity or in the vicinity of that optimum support point, so that the tilting moments which occur are substantially less in comparison with an eccentric support arrangement which is very frequently required in the state of the art.
Another advantage of the transmission arrangement according to the invention arises in relation to the use thereof as a window lifting apparatus in the door of a motor vehicle: more specifically, in this case the spindle can be of such a massive construction and can be so strongly connected to the frame components of the door that it serves as an additional collision protection for the occupants of the vehicle.
An option which has been found to be particularly advantageous is one which involves the complete transmission's being mounted directly to the pane so that that transmission can be used for any kind of motor vehicle, because it is only the spindle that has to be adapted to the respective curvature.
If higher tilting moments are to be carried because it is not possible to provide for support precisely beneath the center of gravity of the article to be moved, in accordance with the invention two thread counterpart portions are screwed on to one and the same curved spindle in such a way that, in the longitudinal direction of the spindle, they are at a spacing from each other which affords a sufficiently long lever arm. The two thread counterpart portions are then either directly or indirectly connected together in such a way that they move in the longitudinal direction of the curved spindle in the same sense and at the same speed.
The direct connection of the two thread counterpart portions is effected by means of a sleeve which embraces the spindle and which also rotates with the thread counterpart portions and which preferably forms an integral component of the rotor of the electric motor. The sleeve is in the shape of a straight circular cylinder, the axis of which intersects in the form of a chord the arc formed by the center line of the curved spindle. The centers of rotation of the two thread counterpart portions are disposed at the two points of intersection.
As an alternative thereto each of the two thread counterpart portions may be a component of its own motor rotor. In that case two motors are in practice arranged on one and the same curved spindle, the stators of the motors being connected together and to the article to be moved. That connection can also be made by means of a sleeve which embraces the spindle and which in this case also may be of a configuration which departs from the straight circular-cylindrical shape.
The invention is described hereinafter by means of embodiments with reference to the drawings in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a transmission arrangement according to the invention which is integrated into the window lifting apparatus of a motor vehicle, the transmission arrangement having two thread counterpart portions which are in the form of nuts and which are connected together by a sleeve,
FIG. 2 is a plan view in the direction indicated by the arrows II--II of the apparatus shown in FIG. 1, with the spindle being omitted for the sake of clarity,
FIG. 3 shows an embodiment in which two transmission arrangements according to the invention which are driven by two synchronized motors are connected together by a sleeve,
FIG. 4 shows an embodiment in which the thread counterpart portions are formed by two flat discs which are connected together by a sleeve which at the same time forms the rotor of the motor assembly,
FIG. 5 is a plan view of part of the embodiment shown in FIG. 4 along line V--V, with the spindle being omitted for the sake of clarity, and
FIG. 6 shows the engagement of the screwthread pitch of the spindle in FIG. 4 into the slot in a thread counterpart portion in two different angular positions.
DESCRIPTION OF PREFERRED EMBODIMENTS
The transmission arrangement 1 shown in FIGS. 1 and 2 essentially comprises the spindle 2, the curvature of which is shown in greatly exaggerated form for the sake of clarity, and the two thread counterpart portions which are each in the form of a hexagonal nut 4 and which are screwed at a spacing from each other on to the spindle 2 and which are connected together by a long sleeve 5.
For the purposes of making that connection, the sleeve 5 which is in the form of a straight circular cylinder is provided at its inside wall with two radially inwardly projecting shoulders 7, each of which is so arranged in the vicinity of one of the two axial ends of the sleeve 5 that its surface which faces toward that axial end is at a spacing from the end of the sleeve 5 which is approximately equal to 1.5 times the thickness of the nuts 4. From each of the axial ends, pushed into the sleeve 5 is a connecting portion 8, the outside of which is in the form of a straight circular cylinder which bears with its outer peripheral surface against the inner peripheral surface of the sleeve 5. Each of the connecting portions 8 sits with its inner axial end face against the associated shoulder 7 of the sleeve 5 and is non-rotatably connected to the sleeve by way of a pin 10 which can be seen in FIG. 2. An opening 11 which is of hexagonal cross-section extends centrally through each of the connecting portions 8, passing therethrough in the axial direction. The dimensions of the through opening 11 are matched to the outside dimensions of the hexagonal nut 4 so that the nut is non-rotatably connected to the sleeve 5 by the connecting portion 8. As can be very clearly seen from FIG. 1, because of the curvature of the spindle 2, each of the hexagonal nuts 4 must be so arranged in the through opening 11 in the associated connecting portion 8 that it is tilted relative to the longitudinal axis or the axis of symmetry of the sleeve 5. That means that, upon a rotary movement of the sleeve 5, each of the hexagonal nuts 4 performs a wobble or swash-plate-like movement relative to the sleeve 5. So that that movement can occur without serious frictional losses, the outside surfaces of the hexagonal nuts 4, which extend in the longitudinal direction, are of a spherical configuration and the cross-section of the through opening 11 is of sufficiently large size. The shoulders 7 project inwardly to such an extent that, on the one hand the sleeve 5 can rotate freely about the spindle 2, while on the other hand the nuts 4 can transmit in the axial direction to the shoulders 7 and therewith the sleeve 5, the forces which are required to displace the arrangement. The assembly may also have two such shoulders per nut so that those pressure forces can be exerted in both directions of movement.
The sleeve 5 is supported against the inside peripheral surface of a motor housing 14 which is disposed coaxially therearound, by way of two ball bearing assemblies 12 which are arranged in the region of the axial ends of the sleeve. The motor housing 14 is also substantially in the form of a straight circular cylinder and is entrained upon displacement of the nuts 4 and the sleeve 5, along the spindle 2. The motor housing 14 includes stator windings (not shown) which can be supplied with current by way of connections (also not shown). The rotary magnetic fields produced by the current flowing through the stator windings act in known manner on permanent magnets 15 mounted on the outside of the sleeve 15 in such a way that it rotates. In conjunction with the permanent magnets 15 therefore the sleeve 5 forms the rotor of an electric motor. Fitted on to the motor housing 14 at its end which is the upper end in FIG. 1 is a disc carrier 16 which is non-rotatably connected to the motor housing 14 and which is also substantially in the form of a straight circular cylinder. A straight circular-cylindrical opening 17 passes through the disc carrier 16 in the axial direction, the opening 17 permitting the spindle 2 to pass unimpededly therethrough. In the radial direction, a guide projection 19 which is integrally connected to the disc carrier 16 projects into the circular-cylindrical opening 17 to such an extent that its radially inward end engages into a guide groove 20 which is provided in the spindle 2 and which extends over almost the entire length of the spindle 2. In that way the disc carrier 16 and therewith also the motor housing 14 is non-rotatably guided on the spindle 12 slidably in the longitudinal direction thereof. In order to improve that guidance effect, the arrangement may also have a plurality of such guide projections, each of which engages into an associated guide groove. That guide arrangement only serves to prevent a rotary movement of the motor housing 14 about the spindle 2. The guidance effect for the body to be moved along the curved path is produced by the association of the entire motor assembly with the spindle 2.
Fixed to the disc carrier 16 is a window pane 21 of a motor vehicle, of which only part is shown in FIGS. 1 and 2 and which here forms the member to be moved. The square portions 22 provided at the ends of the spindle 2 serve to clamp the spindle 2 fixedly in position in the interior of a motor vehicle door. In that situation the curvature of the spindle 2 is so adapted to the curvature of the respective motor vehicle door that the window pane 21 is displaced vertically, following that curved configuration, when the motor is supplied with current and the sleeve 5 and therewith the connecting portions 8 and the hexagonal nuts 4 rotate about the central axis of symmetry of the sleeve 5.
The external screwthread of the spindle 2 and the internal screwthread of the hexagonal nuts 4 which include only a few thread pitches are so matched to each other that the different pitches of the thread portion or flight on the side which is towards the center point of the curvature on the one hand and on the side which is away from the center point of the curvature on the other hand can be accommodated by a suitably large clearance. That clearance in the screwthread configuration may of course be very small since, as already mentioned above, the curvature of the screwthreaded spindle 2 is in actual fact considerably smaller than that shown in the drawings. The spacing between the two hexagonal nuts 4 and thus the length of the sleeve 5 are so selected that the tilting moments which occur upon displacement of the window 21 can be satisfactorily accommodated and the window does not suffer from tilting and twisting.
The embodiment shown in FIG. 3 comprises two transmission arrangements 1 according to the invention, which are formed by virtue of the fact that two nuts 4 are screwed on to one and the same spindle 2, each nut 4 having a few screwthread portions and being in the form of a straight circular cylinder on its outside. Each of the two nuts 4 carries permanent magnets 15 on its outside and is supported by way of a ball bearing assembly 12 in a motor housing 14 which is also substantially in the form of a straight circular cylinder and the windings of which are once again not specifically shown. Accordingly each of the nuts 4, together with the permanent magnets 15 disposed thereon, forms the rotor of an electric motor which rotates relative to the motor housing 14 serving as a stator when the field windings thereof are supplied with current. The two transmission arrangements 1 are at a spacing in the longitudinal direction of the curved spindle 2 and are connected together by a sleeve 5 which however is not rotatable in the present case but connects together the two stators or motor housings 14. In the regions in which the motor housings 14 are fitted into the sleeve 5, the peripheral surfaces of the motor housings are of a spherical configuration in order to permit adaptation to differently curved spindles 2. In order to permit synchronous movement of the two drive arrangements and their associated motors, it can be provided that one and the same current flows through the two motors. The overall assembly can again be non-rotatably guided on the fixed spindle 2, as was described in relation to the embodiment shown in FIG. 1. Instead of the straight sleeve 5, in this case also it is possible to use a sleeve which is curved to correspond to the spindle 2, or a suitable connecting linkage or the like.
If the tilting moments to be carried are not substantial, because for example the member to be displaced can be supported precisely beneath its centre of gravity, then only one of the two transmission arrangements shown in FIG. 3 may be directly connected to the member to be guided and the sleeve 5 and the other transmission arrangement may be omitted. It will be appreciated that in that case two force-transmitting shoulders are required.
In the embodiment shown in FIGS. 4 through 6, the curved spindle 2 has a screwthread flight 24 of very great pitch. That makes it possible for the two thread counterpart portions of which only the upper can be seen in FIG. 4 to be in the form of flat discs which here at the same time form the terminal or axial end discs of a long sleeve 5, which is in the form of a straight circular cylinder. Each of the two flat discs 25 has a central circular opening 26 which extends therethrough and the inside diameter of which is somewhat larger than the outside diameter of the core of the screwthread on the spindle 2. Extending radially outwardly from the opening 26 is a slot 28 which, extending inclinedly, as viewed from the side, connects the underside of the flat disc 25 to the top side thereof. The dimensions of the slot 28 and in particular its radial depth are so selected that the thread flight 24 can engage into same and can extend through same from one side of the flat disc 25 to the other. As can be seen in particular from FIG. 5, the slot 28 which is shown at the top in FIG. 5, of the flat disc 25 which is at the bottom in FIG. 4, is displaced through 180° relative to the slot 28 of the flat disc 25 which is at the top in FIG. 4. That provides that, in the event of a rotary movement of the sleeve 5 in the course of which the two slots, moving along the screwthread 24, move around the spindle 2, the spacing between the two discs 25 can always remain the same. The dash-dotted line 30 in FIG. 5 shows the location of the section in FIG. 4.
In this embodiment it can be particularly clearly seen that the pitch on the side of the curved spindle 2, which is towards the center point of the curvature, is smaller than on the side which is away from the center point of the curvature. The result of that is that the screwthread 24 extends substantially more steeply on the side which is towards the center point of the curvature than on the opposite side, as is shown in greatly exaggerated view in FIG. 6. FIG. 6 shows the configuration of the screwthread 24 on the side towards the center point of the curvature, in solid lines, while it is shown by dash-dotted lines on the side which is remote from the center point of the curvature. It will be seen that the slot 28 in the flat disc 25 is so provided with rounded-off walls 31, 32 that in both limit positions the screwthread 24 can pass through the slot 28 and has adequate guidance in that situation against the walls 31, 32 of the slot. The rounded walls 31, 32 are of a spherical configuration in the second dimension so that the different inclinations of the screwthread on the inside and outside of the spindle still do not have any influence.
Moreover in this embodiment also the sleeve 5 is supported by way of two ball bearing assemblies 12 on a motor housing 14 which is in the form of a straight circular cylinder and which has stator windings (not shown) which, when current flows therethrough, apply to the permanent magnets 15 which are non-rotatably connected to the sleeve 5, a force for causing the sleeve 5 to rotate. In this case also a head corresponding to the disc carrier 16 is mounted at the top side of the motor housing 14; the article to be moved can be connected to said head. The assembly also includes a guide means (not shown) which prevents rotary movement of the motor housing 14 and the head 16 about the curved spindle 2 while, however, permitting longitudinal displacement of those components. | A structure which is of the utmost simplicity, rigidity and reliability has a transmission arrangement (1) for converting the rotary movement of a motor into a linear movement of a driven body (21) along a curved path. It is of a configuration that includes a stationarily arranged spindle (2) which is curved to correspond to the shape of the curved path, and at least one thread counterpart portion (4) which is engaged with the thread of the curved spindle and which is rotatable about the spindle, and by virtue of that rotary movement, displaceable in the longitudinal direction of the spindle. The stator (14) of the motor is connected to the driven body and is mounted non-rotatably and longitudinally displaceably with respect to the curved spindle, and the rotor (5, 15) of the motor is non-rotatably connected to the thread counterpart portion. | 4 |
BACKGROUND OF THE INVENTION
[0001] The orexins (hypocretins) comprise two neuropeptides produced in the hypothalamus: the orexin A (OX-A) (a 33 amino acid peptide) and the orexin B (OX-B) (a 28 amino acid peptide) (Sakurai T. et al., Cell, 1998, 92, 573-585). Orexins are found to stimulate food consumption in rats suggesting a physiological role for these peptides as mediators in the central feedback mechanism that regulates feeding behaviour (Sakurai T. et al., Cell, 1998, 92, 573-585). Orexins regulate states of sleep and wakefulness opening potentially novel therapeutic approaches for narcoleptic or insomniac patients (Chemelli R. M. et al., Cell, 1999, 98, 437-451). Orexins have also been indicated as playing a role in arousal, reward, learning and memory (Harris, et al., Trends Neurosci., 2006, 29 (10), 571-577). Two orexin receptors have been cloned and characterized in mammals. They belong to the super family of G-protein coupled receptors (Sakurai T. et al., Cell, 1998, 92, 573-585): the orexin-1 receptor (OX or OX1R) is selective for OX-A and the orexin-2 receptor (OX2 or OX2R) is capable to bind OX-A as well as OX-B. The physiological actions in which orexins are presumed to participate are thought to be expressed via one or both of OX 1 receptor and OX 2 receptor as the two subtypes of orexin receptors.
[0002] Orexin receptors are found in the mammalian brain and may have numerous implications in pathologies such as depression; anxiety; addictions; obsessive compulsive disorder; affective neurosis; depressive neurosis; anxiety neurosis; dysthymic disorder; behaviour disorder; mood disorder; sexual dysfunction; psychosexual dysfunction; sex disorder; schizophrenia; manic depression; delirium; dementia; severe mental retardation and dyskinesias such as Huntington's disease and Tourette syndrome; eating disorders such as anorexia, bulimia, cachexia, and obesity; addictive feeding behaviors; binge/purge feeding behaviors; cardiovascular diseases; diabetes; appetite/taste disorders; emesis, vomiting, nausea; asthma; cancer; Parkinson's disease; Cushing's syndrome/disease; basophile adenoma; prolactinoma; hyperprolactinemia; hypophysis tumour/adenoma; hypothalamic diseases; inflammatory bowel disease; gastric diskinesia; gastric ulcers; Froehlich's syndrome; adrenohypophysis disease; hypophysis disease; adrenohypophysis hypofunction; adrenohypophysis hyperfunction; hypothalamic hypogonadism; Kallman's syndrome (anosmia, hyposmia); functional or psychogenic amenorrhea; hypopituitarism; hypothalamic hypothyroidism; hypothalamic-adrenal dysfunction; idiopathic hyperprolactinemia; hypothalamic disorders of growth hormone deficiency; idiopathic growth deficiency; dwarfism; gigantism; acromegaly; disturbed biological and circadian rhythms; sleep disturbances associated with diseases such as neurological disorders, neuropathic pain and restless leg syndrome; heart and lung diseases, acute and congestive heart failure; hypotension; hypertension; urinary retention; osteoporosis; angina pectoris; myocardinal infarction; ischemic or haemorrhagic stroke; subarachnoid haemorrhage; ulcers; allergies; benign prostatic hypertrophy; chronic renal failure; renal disease; impaired glucose tolerance; migraine; hyperalgesia; pain; enhanced or exaggerated sensitivity to pain such as hyperalgesia, causalgia, and allodynia; acute pain; burn pain; atypical facial pain; neuropathic pain; back pain; complex regional pain syndrome I and II; arthritic pain; sports injury pain; pain related to infection e.g. HIV, post-chemotherapy pain; post-stroke pain; post-operative pain; neuralgia; emesis, nausea, vomiting; conditions associated with visceral pain such as irritable bowel syndrome, and angina; migraine; urinary bladder incontinence e.g. urge incontinence; tolerance to narcotics or withdrawal from narcotics; sleep disorders; sleep apnea; narcolepsy; insomnia; parasomnia; jet lag syndrome; and neurodegenerative disorders including nosological entities such as disinhibition-dementia-parkinsonism-amyotrophy complex; pallido-ponto-nigral degeneration; epilepsy; seizure disorders and other diseases related to general orexin system dysfunction.
SUMMARY OF THE INVENTION
[0003] The present invention is directed to processes for preparing a pyridyl piperidine compound which is an antagonist of orexin receptors, and which is useful in the treatment or prevention of neurological and psychiatric disorders and diseases in which orexin receptors are involved.
DETAILED DESCRIPTION OF THE INVENTION
[0004] The present invention is directed to a process for preparing a compound of the formula I:
[0000]
[0005] or a pharmaceutically acceptable salt thereof,
[0000] which comprises:
contacting a compound of the formula II:
[0000]
[0000] with a compound of the formula III:
[0000]
[0000] in the presence of a coupling agent,
to give the compound of the formula I.
[0006] In a specific embodiment, the present invention is directed to a process for preparing a compound of the formula I:
[0000]
[0007] or a pharmaceutically acceptable salt thereof,
[0000] which comprises:
contacting a compound of the formula H:
[0000]
[0000] with a compound of the formula III:
[0000]
[0000] in the presence of 1-propyl phosphonic anhydride and a weak organic base to give the compound of the formula I.
[0008] The present invention is further directed to a process for preparing a compound of the formula I:
[0000]
[0009] or a pharmaceutically acceptable salt thereof,
[0000] which comprises:
contacting a compound of the formula V:
[0000]
[0000] with 5-fluoro-2-hydroxypyridine of the formula VI:
[0000]
[0000] in the presence of cesium carbonate to give the compound of the formula IV:
[0000]
[0000] followed by removal of the protecting group in the compound of the formula IV to give the compound of the formula II:
[0000]
[0000] followed by contacting the compound of the formula II with a compound of the formula III:
[0000]
[0000] in the presence of a coupling agent,
to give the compound of the formula I.
[0010] In an embodiment of the present invention, the step of contacting a compound of formula V with a compound of formula VI to give a compound of formula IV is conducted in an amide solvent. An amide solvent is an organic solvent containing an amide functionality.
[0011] In an embodiment of the present invention, the amide solvent is selected from the group consisting of: formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetate, N,N-dimethylacetamide, N,N,N′,N′-tetramethylurea, 2-pyrrolidone, and N-methylpyrrolidone.
[0012] In an embodiment of the present invention, the amide solvent is N,N-dimethylformamide or N-methylpyrrolidone.
[0013] In an alternate embodiment, the present invention is directed to a process for preparing a compound of the formula I:
[0000]
[0014] or a pharmaceutically acceptable salt thereof,
[0000] which comprises:
contacting a camphorsulfonate salt of the formula VII:
[0000]
[0000] with 2,5-difluoropyridine of the formula Via:
[0000]
[0000] in the presence of a strong organic base to give the compound of the formula II:
[0000]
[0000] followed by contacting the compound of the formula II with a compound of the formula III:
[0000]
[0000] in the presence of a coupling agent,
to give the compound of the formula I.
[0015] In an embodiment of the present invention, the step of contacting camphorsulfonate salt of the formula VII with 2,5-difluoropyridine of the formula VIa, the strong organic base is selected from the group consisting of: sodium t-butoxide and sodium ethoxide. In an embodiment of the present invention, the strong organic base is sodium t-butoxide.
[0016] In an alternate embodiment, the present invention is directed to a process for preparing a compound of the formula V:
[0000]
[0000] which comprises:
contacting methyl vinyl ketone of the formula XIII:
[0000]
[0000] with dimethyl malonate of the formula XII:
[0000]
[0000] in the presence of a weak inorganic base to give a compound of the formula XI:
[0000]
[0000] followed by biocatalytic transamination to give a compound of the formula X:
[0000]
[0000] followed by reduction with a first hydride reducing agent of the compound of the formula X to give a compound of the formula IX:
[0000]
[0000] followed by reduction with a second hydride reducing agent of the compound of the formula IX to give a compound of the formula VIII:
[0000]
[0000] followed by formation of the camphorsulfonate salt of the compound of the formula VIII and isolation to give a camphorsulfonate salt of the formula VII:
[0000]
[0000] followed by protecting the free amine in the compound of the formula VII with an amino protecting group to give a compound of the formula VI:
[0000]
[0000] followed by contacting the compound of formula VI with tosyl chloride in the presence of a weak organic base to give the compound of the formula V.
[0017] In an alternate embodiment, the compound of the formula X:
[0000]
[0000] may be reduced directly with a second hydride reducing agent to give the compound of the formula VIII:
[0000]
[0018] In an embodiment of the present invention, the step of contacting methyl vinyl ketone of the formula XIII with dimethyl malonate of the formula XII, the weak inorganic base is selected from the group consisting of: potassium carbonate, sodium carbonate and sodium bicarbonate. In an embodiment of the present invention, the weak inorganic base is potassium carbonate.
[0019] In an embodiment of the present invention, the biocatalytic transamination to give a compound of the formula X is conducted with a transaminase enzyme. In one embodiment, the transaminase enzyme is ATA-117 (commercially available from Codexis). In another embodiment, the transaminase enzyme Vibrio (commercially available from Codexis) may be used to provide the other enantiomer of the compounds of the formula X. In an embodiment of the present invention, the biocatalytic transamination with a transaminase enzyme is optionally conducted under conditions that remove the byproduct from the reaction of the transaminase enzyme. In an embodiment of the present invention, the biocatalytic transamination with a transaminase enzyme is optionally conducted in the presence of lactate dehydrogenase and glucose dehydrogenase to remove the byproduct from the reaction of the transaminase enzyme.
[0020] In an embodiment of the present invention, the reduction with a first hydride reducing agent of the compound of the formula X to give a compound of the formula IX is conducted with a borohydride reducing agent, such as calcium borohydride or sodium borohydride. In an embodiment of the present invention, the reduction of the compound of the formula X to give the compound of the formula IX is conducted with sodium borohydride in the presence of calcium chloride in ethanol solvent.
[0021] In an embodiment of the present invention, the reduction with a second hydride reducing agent of the compound of the formula IX to give a compound of the formula VIII is conducted with a metal hydride reducing agent, such as lithium aluminum hydride or lithium borohydride.
[0022] In an embodiment of the present invention, the protecting the free amine in the compound of the formula VII with an amino protecting group to give a compound of the formula VI, the amino protecting group is a BOC protecting group or a CBZ protecting group.
[0023] In an embodiment of the present invention, in the step of contacting a compound of the formula VI with tosyl chloride to give a compound of the formula V, the weak organic base is pyridine, triethylamine, or N,N-diisopropylethylamine.
[0024] In an embodiment of the present invention, in the step of contacting a compound of the formula II with a compound of the formula III to give the compound of the formula I, the coupling agent is 1-propyl phosphonic anhydride, oxalyl chloride or thionyl chloride.
[0025] In an embodiment of the present invention, in the step of contacting a compound of the formula II with a compound of the formula III to give the compound of the formula I, the weak organic base is di-isopropylethylamine, triethylamine, N-methylmorpholine, or di-aza-[2.2.2]bicyclo-octane.
[0026] In an embodiment of the present invention, in the step of contacting a compound of the formula II with a compound of the formula III to give the compound of the formula I, the reaction is conducted in dichloromethane, dichloroethene, acetonitrile, isopropanol, toluene, N,N-dimethylacetamide, dimethylformamide, or tetrahydrofuran solvent.
[0027] In another embodiment, the invention is directed to a process for preparing a compound of the formula I which comprises contacting a compound of the formula II with a compound of the formula XIV in the presence of a reagent that forms a metal amide of the compound of the formula II.
[0028] In an embodiment of the present invention, the reagent used to form the metal amide of a compound of the formula II is isopropylmagnesium chloride, butyllithium, or trimethylaluminum.
[0029] In an alternate embodiment, the present invention is directed to a process for preparing a compound of the formula III:
[0000]
[0000] which comprises:
contacting 2-iodo-5-methylbenzoic acid of the formula XVII
[0000]
[0000] with methanol in the presence of a strong acid to give methyl 2-iodo-5-methyl benzoate of the formula XVI:
[0000]
[0000] followed by contacting the methyl 2-iodo-5-methyl benzoate of the formula XVI with pinacol borane or pinacolato di-borane in the presence of palladium acetate, tri-O-tolylphosphine and a weak organic base to give a boronate compound of the formula XV:
[0000]
[0000] followed by contacting the compound of the boronate formula XV with 2-chloropyrimidine in the presence of PdCl 2 (dppf)-CH 2 Cl 2 and a weak inorganic base to give the compound of the formula XIV:
[0000]
[0000] followed by hydrolysis of the methyl ester with an inorganic base to give the compound of the formula III.
[0030] In an embodiment of the present invention, the step of contacting the step of contacting a compound of the formula XVI with pinacol borane in the presence of palladium acetate, tri-O-tolylphosphine and a weak organic base to give a boronate compound of the formula XV is conducted by adding the palladium reagent to the reaction mixture after the other reagents have been combined.
[0031] In an embodiment of the present invention, the step of contacting the boronate of formula XV with 2-chloropyrimidine to give the compound of formula XIV is conducted with PdCl 2 (dppf)-CH 2 Cl 2 , PdCl 2 (PPh 3 ) 2 , or PdCl 2 dppb in the presence of Na 2 CO 3 , K 2 CO 3 , or NaHCO 3 .
[0032] A specific embodiment of an alternate aspect of the present invention is directed to a process for preparing a compound of the formula I:
[0000]
[0000] or a pharmaceutically acceptable salt thereof,
which comprises:
[0000]
[0033] The subject compound is disclosed as an antagonist of orexin receptors in PCT Patent Publication WO 2008/147518.
[0034] The compounds of the present invention may contain one or more asymmetric centers and can thus occur as “stereoisomers” including racemates and racemic mixtures, enantiomeric mixtures, single enantiomers, diastereomeric mixtures and individual diastereomers. Additional asymmetric centers may be present depending upon the nature of the various substituents on the molecule. Each such asymmetric center will independently produce two optical isomers and it is intended that all of the possible optical isomers and diastereomers in mixtures and as pure or partially purified compounds are included within the scope of this invention. The present invention is meant to comprehend all such isomeric forms of these compounds. When bonds to the chiral carbon are depicted as straight lines in the Formulas of the invention, it is understood that both the (R) and (S) configurations of the chiral carbon, and hence both enantiomers and mixtures thereof, are embraced within the Formula. For example, Formula I shows the structure of the compound with the designation of specific stereochemistry. When the compounds of the present invention contain one chiral center, the term “stereoisomer” includes both enantiomers and mixtures of enantiomers, such as the specific 50:50 mixture referred to as a racemic mixtures.
[0035] The independent syntheses of these diastereomers or their chromatographic separations may be achieved as known in the art by appropriate modification of the methodology disclosed herein. Their absolute stereochemistry may be determined by the x-ray crystallography of crystalline products or crystalline intermediates which are derivatized, if necessary, with a reagent containing an asymmetric center of known absolute configuration. If desired, racemic mixtures of the compounds may be separated so that the individual enantiomers are isolated. The separation can be carried out by methods well known in the art, such as the coupling of a racemic mixture of compounds to an enantiomerically pure compound to form a diastereomeric mixture, followed by separation of the individual diastereomers by standard methods, such as fractional crystallization or chromatography. The coupling reaction is often the formation of salts using an enantiomerically pure acid or base. The diasteromeric derivatives may then be converted to the pure enantiomers by cleavage of the added chiral residue. The racemic mixture of the compounds can also be separated directly by chromatographic methods utilizing chiral stationary phases, which methods are well known in the art. Alternatively, any enantiomer of a compound may be obtained by stereoselective synthesis using optically pure starting materials or reagents of known configuration by methods well known in the art.
[0036] As appreciated by those of skill in the art, halogen or halo as used herein are intended to include fluoro, chloro, bromo and iodo. Similarly, C 1-6 , as in C 1-6 alkyl is defined to identify the group as having 1, 2, 3, 4, 5 or 6 carbons in a linear or branched arrangement, such that C 1-8 alkyl specifically includes methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tett-butyl, pentyl, and hexyl. A group which is designated as being independently substituted with substituents may be independently substituted with multiple numbers of such substituents.
[0037] The term “pharmaceutically acceptable salts” refers to salts prepared from pharmaceutically acceptable non-toxic bases or acids including inorganic or organic bases and inorganic or organic acids. Salts derived from inorganic bases include aluminum, ammonium, calcium, copper, ferric, ferrous, lithium, magnesium, manganic salts, manganous, potassium, sodium, zinc, and the like. Particular embodiments include the ammonium, calcium, magnesium, potassium, and sodium salts. Salts in the solid form may exist in more than one crystal structure, and may also be in the form of hydrates, Salts derived from pharmaceutically acceptable organic non-toxic bases include salts of primary, secondary, and tertiary amines, substituted amines including naturally occurring substituted amines, cyclic amines, and basic ion exchange resins, such as arginine, betaine, caffeine, choline, N,N′-dibenzylethylene-diamine, diethylamine, 2-diethylaminoethanol, 2-dimethylaminoethanol, ethanolamine, ethylenediamine, N-ethyl-morpholine, N-ethylpiperidine, glucamine, glucosamine, histidine, hydrabamine, isopropylamine, lysine, methylglucamine, morpholine, piperazine, piperidine, polyamine resins, procaine, purines, theobromine, triethylamine, trimethylamine, tripropylamine, tromethamine, and the like.
[0038] When the compound of the present invention is basic, salts may be prepared from pharmaceutically acceptable non-toxic acids, including inorganic and organic acids. Such acids include acetic, benzenesulfonic, benzoic, camphorsulfonic, citric, ethanesulfonic, fumaric, gluconic, glutamic, hydrobromic, hydrochloric, isethionic, lactic, maleic, malic, mandelic, methanesulfonic, mucic, nitric, pamoic, pantothenic, phosphoric, succinic, sulfuric, tartaric, p-toluenesulfonic acid, and the like. Particular embodiments include the citric, hydrobromic, hydrochloric, maleic, phosphoric, sulfuric, fumaric, and tartaric acids. It will be understood that, as used herein, references to the compounds of Formula I are meant to also include the pharmaceutically acceptable salts.
[0039] Several methods for preparing the compounds of this invention are illustrated in the following Schemes and Examples. Starting materials are made according to procedures known in the art or as illustrated herein. The following abbreviations are used herein: 2-MeTHF: 2-methyltetrahydrofuran; Ac: acetyl; Ar: aryl; AY: assay yield; Bn: benzyl; Boc: tert-butyloxy carbonyl; Boc 2 O: di-tert-butyldicarbonate; BSA: bovine serum albumin; Cbz: carbobenzyloxy; CDI: carbonyl diimidazole; CSA: camphor sulfonic acid; DEAD: diethylazodicarboxylate; DCE: dichloroethane; DCM: dichloromethane; DIPEA: N,N-diisopropylethylamine; DMF: N,N-dimethylformamide; DMSO: dimethylsulfoxide; EDC: N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide; Et: ethyl; EtOH: ethanol; Et 3 N: triethylamine; GC-FID: gas chromatography-flame ionization detector; HOBT: hydroxybenzotriazole hydrate; HPLC: high performance liquid chromatography; LC-MS: liquid chromatography-mass spectrometry; LRMS: low resolution mass spectrometry; Me: methyl; MTBE: methyl tert-butyl ether; NAD: nicotinamide adenine dinucleotide; NMP: N-methylpyrrolidone; PdCl 2 (dPPf)-CH 2 Cl 2 : [1,1′-Bis(diphenylphosphino)ferrocene]dichloropalladiuna(II) dichloromethane; Ph: phenyl; PhMe: toluene; PLP: pyridoxal-5′ phosphate; rt: room temperature; SOCl 2 : thionyl chloride; T3P: 1-propylphosphonic anhydride; t-Bu: Cert-butyl; TsCI: tosyl chloride; TFA: trifluoracetic acid; THF: tetrahychofuran. The compounds of the present invention can be prepared in a variety of fashions.
[0040] In some cases the final product may be further modified, for example, by manipulation of substituents. These manipulations may include, but are not limited to, reduction, oxidation, alkylation, acylation, and hydrolysis reactions which are commonly known to those skilled in the art. In some cases the order of carrying out the foregoing reaction schemes and examples may be varied to facilitate the reaction or to avoid unwanted reaction products. The following examples are provided so that the invention might be more fully understood. These examples are illustrative only and should not be construed as limiting the invention in any way.
Example A
[0041]
Dimethyl (3-oxobutyl)malonate (A-1)
[0042] To a visually clean and dry 100 L round bottom flask equipped with an addition funnel, a nitrogen inlet and a thermocouple were added acetonitrile and potassium carbonate. Dimethyl malonate was added and the resulting mixture was cooled to 17° C. (ice/water bath). The methyl vinyl ketone was added over 3 h with the internal temperature not rising above 26° C. After 18 h, HPLC showed full conversion. The mixture was transferred to a 100 L extractor charged with 60 L MTBE and 20 L water. The layers were separated and the aqueous layer was back extracted with 20 L MTBE. The combined organic layers were washed with 20 L water, allowing 5 h for the emulsion to settle. The organic layer was then filtered through activated carbon and batch concentrated, flushing with 20 L MTBE to afford 15.1 kg of A-1 (80 wt % by 1 H NMR, 80% yield). Data for A-1: 1 H NMR (400 MHz, CDCl 3 ) δ 3.69 (s, 6H), 3.40 (t, J=7.3 Hz, 1H), 2.50 (t, J=7.2 Hz, 2H), 2.15-2.06 (m, 5H).
Dimethyl(3-oxobutyl)malonate (A-1)
[0043] Potassium carbonate (5.62 kg), dimethyl malonate (54.8 kg) and acetonitirile (90 kg) were charged to the reaction vessel and stirred together at 15° C. Methyl vinyl ketone (28.5 kg) was pumped into the vessel over 2 hours at below 25° C. The slurry was stirred at 18-20° C. for 2 hours. MTBE (132 kg) was charged to the vessel to dilute the reaction mixture followed by water (114 kg). The mixture was stirred for five minutes then the layers were allowed to separate and the aqueous layer run off. More water (57 kg) was charged to the vessel, the reaction mixture stirred for another 5 minutes, the layers allowed to separate, and again the aqueous layer run off. The organic layer was concentrated under reduced pressure until most of the solvent had been removed (volume approx 80 L) affording 76 kg of A-1 as an oil.
Methyl (6R)-6-methyl-2-oxopiperidine-3-carboxylate (A-2)
[0044] To a visually clean 20 L round bottom flask was charged 7.15 kg of 64 wt % A-1 and rotary evaporated to remove residual acetonitrile and MTBE. The resulting solution was 83 wt %. To a visually clean 100 L Buchi jacketed reactor with overhead stirring was added 45 L water. Heating to 30° C. was initiated, followed by addition of 852 g Na 2 HPO 4 , 7.2 kg D-alanine, 6.48 kg Glucose, 22.5 g NAD, and 45 g PLP. The pH was adjusted to 7.4 with NaOH and then 450 g ATA-117 transaminase, 9 g Lactate Dehydrogenase, and 45 g glucose dehydrogenase were added and rinsed into the vessel with 2.5 L water. After all enzymes were in solution, the rotavaped solution of A-1 was added, followed by a final 2.5 L water. pH control utilizing 5 N NaOH was initiated. The reaction was allowed to stir for 42 hours; the reaction was complete at 31 hours. To the reaction vessel were added 19.4 kg NaCl and 6.0 L 5N HCl to adjust the pH to 3.5. 20 L of acetonitrile was added and allowed to stir for 10 min. The agitator was turned off and the reaction mixture allowed to settle for 1 h. The acetonitrile layer was drummed off; the aqueous layer was re-extracted with acetonitrile, and these acetonitrile layers were combined. The resulting acetonitrile solution was filtered through Solka-Floc and combined with a second batch of similar size and batch concentrated to remove both acetonitrile and water. The resulting oil contained high levels of heterogeneous NaCl. The oil was then dissolved in 50 L EtOAc and transferred to a visually clean 20 L round bottom flask and rotavaped to provide A-2 as an oil (5.5 kg, 94 wt %, 74% yield, 99% ee determined by HPLC on Chiralpak). Data for A-2: LRMS (MSH)=172.
Methyl (6R)-6-methyl-2-oxopiperidine-3-carboxylate (A-2)
[0045] Water (516 kg) was charged to a 1000 L vessel followed by disodium hydrogen orthophosphate (36.3 kg), D-alanine (41.8 kg) and D-glucose (37.6 kg). The mixture was warmed to 30° C. to dissolve the solids. NAD (130.5 g) and PLP (261 g) were added and the pH checked (7.8). ATA-117 transaminase (2.61 kg), lactate dehydrogenase (52.2 g), and finally glucose dehydrogenase (130.5 g) were added and rinsed into the vessel with 2.5 L water. After all enzymes were in solution, A-2 (39.2 kg total, 29 kg assay) was added, followed by a final water rinse (5 kg). The reaction mixture was stirred at 30° C. with the pH being adjusted to pH 7.6 every 2-3 hours by the addition of 5N NaOH for the first 6 hours. The reaction was then left to stir overnight (16 hours) before the pH was again adjusted to pH 7.6. The reaction was allowed to stir for 44 hours. Sodium chloride (90 kg) was added to the reaction mixture and the pH adjusted to pH 3.6 by the addition of 5N HCl (66 L). Dichloromethane (200 kg) was charged to the vessel followed by solka-Flok (15 kg) and the mixture allowed to stir for 10 minutes. The batch was then filtered through more Solka-Flok (5 kg). The Solka-Flok was washed with more dichloromethane (65 kg). The filtrates were returned to the vessel, and the layers allowed to separate. The lower organic layer was run off and the aqueous layer re-extracted with dichloromethane (200 kg). The lower organic layer was run off and the aqueous layer discarded. The organic layers were recombined, returned to the vessel and washed with 8% sodium bicarbonate solution (54 L) for 20 minutes. The layers were allowed to separate and the organic layer run off. The aqueous layer was discarded and the organic layer returned to the vessel. The dichloromethane solution of A-2 (19.3 kg assay) was stored at room temperature until required.
(6R)-3-(Hydroxymethyl)-6-methylpiperidin-2-one (A-3)
[0046] A visually clean and dry 140 L extractor, equipped with glycol cooling coils, nitrogen inlet, large gas exit and thermocouple was charged with an 18.7 wt % solution of A-2 in EtOH [4.6 L/kg] and an additional 71.4 L EtOH [25.4 L/kg]. Calcium chloride (3.65 kg) was added in 3 portions over 15 min and stirred until complete dissolution with cooling from 26 to 22° C. Sodium borohydride (2.49 kg) was added in 3 portions over 20 min. After the last addition, the temperature increased to 25° C. Gas evolution subsided within 30 min. The reaction mixture was allowed to stir for 20 h with the cooling set to keep the temperature below 22° C. The mixture was cooled to 5° C. and was quenched by careful addition of 11.2 L 6 N HCl over 30 min, keeping the temperature below 9.5° C. It was warmed to room temperature and stirred for 2 h. Wet pH paper dipped in the mixture showed pH 2. It was filtered over Solka-Floc and rinsed with 2×12 L EtOH. Each bin was assayed for a total of 2.55 kg (108% AY). The filtrate was combined with a second batch of similar size for batch concentration. After most of the ethanol was evaporated, 8 L of water were added to coevaporate EtOH and partially solubilize precipitate. After transferring the 23 L aqueous layer to the extractor, the volume was adjusted with water to 31.6 L. It was extracted with 53 L then 2×26.5 L 1-butanol (HPLC assay shows 92 g, 1.9% losses in the aqueous layer). The combined organic layers were washed with 10.5 L brine (HPLC assay shows 419 g, 8.8% losses to the wash). The organic layer was assayed to 4.21 kg (92% recovery, 96% AY) and concentrated to a minimum volume. It was then azeotroped with 12 L water, then 120 L isopropanol. The KF was assayed to 0.5% water on a total volume of ˜40 L. The suspension was filtered over Solka-Floc and rinsed with 2×10 L isopropanol. The filtrate was stirred in the extractor to homogenize it and was assayed to 4.13 kg (94% AY, 1.7:1 dr). The solution was separated in two equal batches. Each batch was concentrated to a minimum volume and azeotroped with 140 L THF to yield A-3 as a beige suspension. (94% yield). 1 H NMR shows 0.6 eq isopropanol. Data for A-3: LRMS (MSH)=144.
[(6R)-6-methylpiperidin-3-yl]methanol (A-4)
[0047] A visually clean and dry 100 L 5-neck round-bottom flask equipped with a mechanical stirrer, a thermocouple, a nitrogen inlet and a cooling bath was charged with A-3 (2.07 kg, 1.0 eq) and THF (20 L, 10 mL/g). The mixture was cooled to −25° C. The LiAlH4 (2.6M soln, 22.2 L, 4.0 eq) was added over a period of 3.5 h, keeping the mixture between −25° C. and +12° C. An important gas evolution (H 2 ) was observed during the addition of the first 6 L of LiAlH 4 . Upon completion of the addition, the mixture was allowed to warm to 20° C., then heated using steam to 50° C. The mixture was aged at this temperature for a period of 12 h. GC-FID and LC-MS showed >99% conversion to the desired piperidine-alcohol. The mixture was cooled to −25° C., and the reaction was quenched using the Fieser work-up. Water (2.2 L) was added over 3 h to the mixture, creating an important gas evolution and exotherm (temperature was kept between −25° C. and +13° C.). 3.75M NaOH (2.2 L) was then added to the mixture over a period of 1.5 hrs. Finally, water (6.6 L) was added over a period of 1 hr. The mixture was cooled to 5° C. and aged 1.5 h. The suspension was filtered, and the cake was rinsed with THF (20 L). 1.54 kg (2.33% wt) were obtained, therefore the assay yield of A-4 was 82% (dr=1.7:1, favoring the trans isomer). Data for A-4: LRMS (M+H)=130.
[(3R,6R)-6-methylpiperidin-3-yl]methanol-CSA salt (A-5)
[0048] A visually clean and dry 140 L 5-neck extractor equipped with a mechanical stirrer, a thermocouple, a nitrogen inlet and a cooling coil was charged with A-4 (3.04 kg, 1.0 eq) and THF (60 L, 20 mL/g). To the mixture was added a THF solution (4 mL/g, 12 L) of (D)-(+)-CSA (4.37 kg, 0.8 eq) over a period of 1 h. The salt crystallized out without seeding. Upon completion of the addition, the mixture was aged 45 min at 20° C., then MTBE (10 mL/g, 30 L) was added over 45 min. The mixture was aged for 45 min, then cooled to 2° C. over 45 min. The mixture was aged at this temperature for a period of 30 min, then filtered. The salt was rinsed 2×6 mL/g (2×18 L) with THF/MTBE 1/1, then 1×6 mL/g (1×18 L) MTBE, and was dried on the fit under a nitrogen atmosphere for a period of 16 h to provide 4.46 kg (52% yield) of A-5 as a white solid. The diastereoselectivity of the salt (measured on a free base sample after salt break) was 40-50:1.
[(3R,6R)-6-methylpiperidin-3-yl]methanol-CSA salt (A-5)
[0049] Crude A-2 (40 g assay; 55.94 g total) was dissolved in THF (773 mL). Ethanol (43.1 g) was added to the solution and the solution cooled to 0° C. LiBH4 (228 ml; 4.1M in THF) was added over 30 minutes at below 5° C. and mixture was stirred at RT. Mixture was warmed to 20° C. and stirred overnight. The reaction mixture was cooled to 10° C. and added 6M HCL (240 mL) with care over 30 minutes. The white cloudy mixture was stirred at 20° C. for 2 hours. pH of mixture: pH=1. The pH of the reaction mixture was adjusted to pH 12-14 by the addition of 10 M NaOH (120 mL) and isopropyl acetate (120 mL) added. The layers were separated and the aqueous layer re-extracted with isopropyl acetate (2×240 mL). The organic layers were combined and evaporated to residue. The oily residue was flushed with isopropanol (3×200 mL) to give a water content of <200 μL/mL. The crude oil was then dissolved in THF (450 mL). Solvent analysis gave no IPAc present, <1% IPA present. A solution of D-(+)-camphorsulfonic acid (54.3 g) in THF (130 mL) was added over 30 minutes to the THF solution of the piperidinol. A white solid crystallized. The mixture was stirred at 20° C. overnight. The slurry was diluted with MTBE (300 mL) and the mixture was cooled to 0° C. for 2 hours before filtering. The solid was washed with 1:1 THF:MTBE (100 mL) and MTBE (100 mL). The solid was dried in vacuo at 45° C. overnight to give A-5 as a white solid (39.7 g) in 47% yield, diastereomer ratio: 20:1 trans:cis (NMR)
tert-butyl (2R,5R)-5-(hydroxymethyl)-2-methylpiperidine-1-carboxylate (A-6)
[0050] A visually clean and dry 140 L extractor, equipped with glycol cooling coils, nitrogen inlet, and thermocouple was charged with 40 L of dichloromethane followed by A5 (4.2 kg). To this suspension was added triethyamine in one portion (4.8 L, no exotherm observed) followed by Boc 2 O (2.66 kg added over 5 min, 4° C. exotherm observed). After 30 minutes, the reaction mixture became homogeneous. An LCMS assay (after 3 h) showed complete consumption of the starting material. The reaction mixture was diluted with ammonium chloride 2 M (40 L) and the layers were separated. The organic layer was washed with half saturated brine (20 L) and the layers were separated. An HPLC assay of the crude reaction mixture indicated a 105% AY (2.81 kg). This crude reaction mixture was dried over Na 2 SO 4 (200 wt %), filtered and transferred into a 100 L flask for the tosylation reaction.
tert-butyl (2R,5R)-2-methyl-5-({[(4-methylphenyl)sulfonyl]oxy}methyl)piperidine-1-carboxylate (A-7)
[0051] A Visually Clean and Dry 100 L Reactor Equipped with a Mechanical Stirrer, a nitrogen inlet and a thermocouple was charged with the crude dichloromethane solution of A-6 (final volume was adjusted to 10 L, approximatly 2.2 mL/g). To this cold solution (0° C.) was added pyridine (5.5 L, no exotherm observed) followed by TsCi (in 4 portions over 1 h, exotherm observed but easily controlled). The reaction mixture was warmed to room temperature and stirred for 18 h (HPLC showed complete consumption of the starting material). The reaction mixture was transferred into a 140 L extractor and diluted with MTBE (7 mL/g), NH 4 Cl sat. (20 L) and water (10 L). The layers were separated and the organic layer was washed with CuSO 4 .5H 2 O (20 L followed by 10 L), sat NaHCO 3 (10 L) and half saturated brine (10 L). The crude organic layer was filtered on a pad of silica gel (1.5 kg) and the pad was rinsed with MTBE (10 L). The assay yield of A-7 measured on the resulting solution was 93% (4.28 kg). Data for A-7: LRMS (M-Boc)=284.0.
tert-butyl (2R,5R)-5-{[(5-fluoropyridin-2-yl)oxy]methyl}-2-methylpiperidine-1-carboxylate (A-8)
[0052] A visually clean and dry 100 L 5-neck round-bottom flask equipped with a mechanical stirrer, a thermocouple, a nitrogen inlet and a cooling bath was charged with A-7 (3.23 Kg, 1.0 eq) and NMP (65 L, 20 mL/g). 5-Fluoro-2-hydroxypyridine (1.19 kg, 1.25 eq) was added, followed by the addition of the Cs 2 CO 3 (7.37 Kg, 2.7 eq). No exotherm was observed.
[0053] The mixture was warmed to 60° C. and aged at this temperature for a period of 26 h. HPLC showed >99.9% conversion to the desired product. The mixture was cooled to 15° C., the reaction was quenched by the addition of water (65 L), added over 1 h to control the exotherm (15° C. to 28° C.). The piperidine-O-pyridine was extracted using MTBE (20 mL/g, 65 L). The organic layer was washed 2×10 mL/g 10% LiCl (2×32 L), then 2×10 mL/g NaCl half saturated solution (2×32 L). The assay yield of A-8, measured on the MTBE layer, was 2.16 kg, 79% yield. Data for A-8: HRMS (M+H)=325.1922.
5-fluoro-2-{[(3R,6R)-6-methylpiperidin-3-yl]methoxy}pyridine (A-9)
[0054] A visually clean 50 L flask equipped with a thermocouple and mechanical stirrer was charged with a solution of A-8 (2.15 kg, 6.63 mol) in MTBE which was solvent switched to dichloromethane (11.40 L). This mixture was cooled to −2° C. with an ice/IPA bath. TFA (5.5 L, 71.4 mol) was then added slowly (over 40 minutes, T ° C.=−1.9° C. to 5.5° C., max 5.5° C.). Once addition was completed, the reaction was removed from the ice bath and warmed to room temperature with warm water (start 5.7° C., 50 minutes). The reaction was completed within 3.5 h. Concentration under reduced pressure and transfer of the resulting oil to a cooled stirring solution of NaOH (3.0 N, 1.1 eq., 28 L) in a 100 L extractor was followed by addition of 30 L of MTBE and the phases were separated. The organic layer was washed with 30 L of 2 N HCl and again with 10 L of 2 NHCL The aqueous layers were then cooled (9° C.) and 10 N NaOH was added until the pH was 13 (T°=21° C.). To this solution was added 25 L of MTBE and the layers were cut. Finally, the aqueous layer was back-extracted with 10 L of MTBE. Quantitative HPLC assay revealed 98% yield and >99.7% purity of A-9 used as is a subsequent reaction. Data for A-9: LRMS (M+H)=225.1.
5-fluoro-2-{[(3R,6R)-6-methylpiperidin-3-yl]methoxy}pyridine (A-9)
[0055] A 3-L, three-necked, round-bottomed flask equipped with a septum, nitrogen inlet adapter, mechanical stirrer, and thermocouple was charged with A-5 (87.0 g), 2,5-difluoropyridine (30.0 g), and 870 mL of DMSO (110 ppm water) at room temperature (23° C.). Sodium t-butoxide (50.1 g) was added portion wise over 4 min keeping the internal temperature below 29° C. The resulting reaction mixture was stirred at room temperature (ea. 25° C.) until HPLC analysis indicated less than 5% difluoropyridine compared to the desired product. (Agilent Eclipse XDB-C18 4.6×150 mm column; 35° C.; Mobile phase: (A) 0.1% H 3 PO 4 /water; (B) Acetonitrile. Linear gradient, Time 0: 95% A, 5% B; Time 6 min: 5% A, 95% B; Time 10 min: 5% A, 95% B. Flow rate, 1.5 mL/min. UV=210 tun; A-5 RT=2.8 min, A-9 RT=3.2 min, 2,5-difluoropyridine RT=4.1). The reaction mixture was then diluted with water (20 vol., 1740 mL) and EtOAc (10 vol., 870 mL). The organic layer was separated, washed with water (10 vol., 870 mL), and transferred to a 2-L round-bottomed flask. HCl (3.9 N solution in IPA) was slowly added via addition funnel over 30 min and the resulting white slurry was stirred at room temperature for 1 h. The crystals were collected, washed with EtOAc (3 vol., 2610 mL), and dried under vacuum with a nitrogen sweep to give 55.0 g of A-9 as white crystals.
Example B
[0056]
Methyl 2-iodo-5-methylbenzoate (B-1)
[0057] A visually clean 100 L flask equipped with a mechanical stirrer thermocouple and water chilled condenser was charged with MeOH (50 L). 2-iodo-5-methylbenzoic acid (5.85 kg, 22.32 mol) was then added while stirring. Concentrated sulfuric acid (0.595 L, 11.16 mol) was then added portion-wise which caused an increase in temperature from 17° C. to 22° C. This mixture was gradually brought to an internal temperature of 64.6° C. and aged overnight (˜18 h). The next morning the reaction had reached >98% conversion by HPLC. The flask was cooled to 16° C. by placing in an ice bath and 850 mL of 10 N NaOH (0.98 equiv.) was added slowly (over 10 minutes) while monitoring the pH. After the addition the pH was 5-6 (caution: bringing pH over 9 can result in saponification during the work-up). The solution was then concentrated to about 16 L and this suspension was transferred to a 100 L extractor. The flask was rinsed with 8 L of IPAc and 4 L of water which were also transferred to the extractor. 32 L of IPAc were added along with 10 L of 5 w % NaHCO 3 and 10 L of 15 w % Brine. The layers were cut and the aqueous layers were back-extracted with 20 L of IPAc. The organic layers were then combined and washed with 10 L of 15 w % Brine. The organic layers were collected to provide B-1 (6.055 kg, 2193 mol, 98% yield) in 98.3% purity. 1 H NMR (500 MHz, CDCl 3 , 293K, TMS): 7.84 (1 H, d, =8.07 Hz), 7.62 (1H, d, J=2.14 Hz), 6.97 (1H, dd, J=8.08, 2.14 Hz), 3.97-3.86 (3H, m), 2.33 (3H, s).
Methyl 5-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (B-2)
[0058] A solution of B1 (5.9 kg, 21.37 mol) in iPAc was charged in a visually clean 100 L reactor equipped with a mechanical stirrer and thermocouple. The solution was solvent switched to 2-MeTHF (˜35 L). Triethylamine (8.94 L, 64.1 mol) was added and the solution was degassed with N 2 . Pinacol borane (4.65 L, 32.1 mol) was added slowly (over 15 mins) to the stirring solution while maintaining the purge. The solution was further degassed for 10 min and tri-o-tolylphosphine (0.325 kg, 1.069 mol) was added followed by palladium (II) acetate (0.120 kg, 0.534 mol). This caused the reaction to turn black immediately with a slow exotherm from 11.5° C. to 30° C. At this point a delayed exotherm was observed and the reaction temperature increased to 60° C. (over 45 min). The reaction temperature was increased to 77° C. and aged for another 45 min. At this point, HPLC analysis of a reaction aliquot revealed complete consumption of the starting material. The heat source was removed and an ice bath was placed under the flask to cool the reaction over 1.5 h. A 26 w % ammonium chloride solution was added very slowly to control gas evolution and exotherm (over 60 minutes) which caused a black precipitated to form. The supernatant was transferred to an extractor which already contained 40 L of water. The black slurry remaining was filtered on Solka-Floc and washed with MTBE (˜20 L). The filtrate was loaded into the extractor. The layers were cut and assay of the organic layers revealed B-2 (4.45 kg, 16.11 mol, 75% yield) in 81.6% purity and was used as is in the following step. 1 H NMR (500 MHz, CDCl 3 , 293K, TMS): 7.75 (1H, s), 7.40 (1H, d, J=7.49 Hz), 7.32 (1H, d, J=7.56 Hz), 3.90 (3H, s), 2.37 (3H, s), 1.41 (12H, s).
Methyl 5-methyl-2-pyrimidin-2-ylbenzoate (B-3)
[0059] A solution of B-2 (4.38 kg, 15.84 mol) from the previous reaction was charged in a visually clean 100 L reactor equipped with a mechanical stirrer and a thermocouple. The mixture was solvent switched to 2-MeTHF (35 L). This was followed by addition of 2-chloropyrimidine (2.18 kg, 19.01 mop (endothermic 19 to 14° C.) and sodium carbonate (5.04 kg, 47.5 mal), To this stirring suspension was added water (11.67 L) (exothermic 15-24° C.). The thick slurry was degassed with N 2 for 40 minutes after which PdCl 2 (dppf)-CH 2 Cl 2 adduct (0.518 kg, 0.634 mol) was added which causes the reaction to become black. The internal temperature was set to 74° C. and aged for 16 h. An aliquot was taken for HPLC analysis and revealed near complete consumption of the starting boronate (>97% conv.). The reaction was cooled to room temperature, and 12 L of water and 24 L of MTBE were added while maintaining stirring for 10 minutes. This solution was filtered on Solka-Floc and transferred to a 100 L extractor. The flask was further rinsed with 4 L of both MTBE and water (×2) and then another 4 L of MTBE. The layers were cut and the aqueous layers were back-extracted with 21.5 L of MTBE. Assay of the organic layers showed the biaryl ester (2.76 kg, 12.09 mol, 76% yield). The organics were reloaded into the extractor and 1.26 kg of activated carbon (Darcy KB-G grade) was added and the mixture was stirred for 2 h and then filtered over Solka-Floc. The filter cake was washed with 3×10 L of MTBE. Heavy metal analysis revealed 427-493 ppm of Pd and 882-934 ppm of Fe. Assay was 2.381 kg of B-3 (66% overall, 86% recovery from DARCO). Data for B-3: 1 H NMR (500 MHz, CDCl 3 , 293K, TMS): 8.78 (d, T=4.87 Hz, 2H); 7.97 (d, 3=7.93 Hz, 1H); 7.51 (s, 1H); 7.39 (d, 3=7.99 Hz, 1H); 7.19 (t, 3=4.88 Hz, 1H); 3.75 (s, 3H); 2.44 (s, 3H).
5-Methyl-2-pyrimidin-2-ylbenzoic acid (B-4)
[0060] A solution of B-3 from the previous step was charged to a visually clean 100 L flask through an in-line filter, concentrated and solvent switched to 2-MeTHF (˜15 L). To this solution was added water (20 L) and then sodium hydroxide (10 N) (2.60 L, 26.0 mol). After the addition the reaction turned red and the heat source was set to 72° C. The mixture was aged at this temperature for 1.5 h after which complete conversion was observed by HPLC analysis. The reaction was cooled and transferred to a 50 L extractor. The flask was rinsed with 4 L of water and 10 L of MTBE which was added to the stirring mixture in the extractor. The layers were cut, and the aqueous phase was washed twice with 10 L of MTBE. The aqueous layer was then re-introduced into the reactor (100 L) through an in-line filter for the acidification. 2.3 L of 12 N HCl was added slowly to the cold mixture which causes an exotherm from 7 to 10° C. This caused a beige precipitate to form (pH=1). This precipitate was filtered. The beige filter cake was washed twice with 3 mL/g of cold water. Then the cake was washed with 3 mL/g of cold 15% MTBE/Heptane and 15% PhMe/Heptane. Finally it was washed with 1.5 mL/g of room temperature MTBE and twice with room temperature 3 mL/g Heptane. The solid was then dried under a stream of N 2 for 2 days to provide B-4 as a light beige powder (2.15 kg, 10.04 mol, 97% yield). HPLC analysis reveals the product to be 99.2% purity. Heavy metal analysis revealed 264 ppm of Pd and 19.7 ppm of Fe. Data for B-4: 1 H NMR (500 MHz, DMSO-d 6 ): 12.65 (s, 1 H); 8.85-8.82 (m, 2H); 7.78 (dd, J=7.89, 2.34 Hz, 1H); 7.49-7.37 (m, 3H); 2.40 (s, 3H).
2-{2-[((2R,5R)-5-{[(5-Fluoropyridin-2-1 oxy]methyl}-2-methylpiperidin-1-yl)carbonyl]-4-methylphenyl}pyrimidine (B-5)
[0061] The solution of A-9 (1 kg, 4.46 mol) was charged in a visually clean and dry 50 L flask equipped with a thermocouple and mechanical stirrer and was solvent switched to DCM (11.00 L). DIPEA (2 L, 11.45 mol) is added and then B-4 (1.22 kg, 5.67 mol) was added to this stirring solution. This solution was cooled with an ice bath (12° C.). To this stirring solution was added T3P (7.87 L, 13.38 mol) through an addition funnel keeping the reaction temperature <21° C. over 1 h. Once addition was completed, the reaction became yellow and heterogenous. To facilitate stirring 2 L of DCM were added. The reaction was heated to 44° C. (small exotherm at 42° C., which caused the temperature to rise to 46.7° C. and maintain that temperature for 30 min). The reaction was aged at this temperature overnight. After 17 h the reaction was not complete and T3P (1.1 L, 1.870 mol) was added to accelerate conversion. The next day (42 h) the reaction was deemed complete by HPLC and was cooled in an ice bath to 4° C. 20 L of water was added (slowly for the first 1.5 L then pretty fast) keeping the reaction temperature under 17° C. This mixture was stirred at room temperature for 30 min. Then the mixture was transferred into a 50 L extractor charged with 20 L of MTBE. The flask was rinsed with an additional 2 L of water and 4 L of MTBE. The layers were cut and the organics are washed with 20 L 1N NaOH and then 10 L of 1N NaOH. Finally, the organics were washed twice with 10 L of brine 15%. The organic fractions (quantitative HPLC assay at 1.65 kg) were then treated with ˜50 w % of Darco KB (750 g) for 1.75 h, filtered on Solka-Floc and rinsed with 10 mL/g of MTBE (1.559 kg, 94.5% recovery). To a visually clean and dry 50 L RBF equipped with a mechanical stirrer, a thermocouple, a reflux condenser and a nitrogen inlet was charged the crude material from above (B-5 solution and all solvents used were filtered using a 1 μm in-line filter). The reaction mixture was solvent switched to IPAc and the final volume was adjusted to 7.5 L (about 4 mL/g of IPAc). The reaction mixture was warmed to 75° C. (all soluble), cooled to room temperature slowly and seeded at 45° C. with 18 g of B-5 (in IPAc/heptane), stirred overnight (16 h) at room temperature, then heptane was added (6 mL/g) over 60 min. The reaction mixture was aged for 1 h before to be cooled to 5° C. and stirred for 30 min. The suspension was then transferred onto a filter pot and rinsed with IPAC/heptane (2×3 mL/g of cold 15% IPAc) and heptane (5 mL/g). The residual beige solid was dried under a flow of nitrogen for 18 h (the product was found to be dry with <0.3 wt % of solvents). 1.2 kg of B-5 was isolated as a light beige solid (99.4 LCAP, >99.5% ee, >99.5% dr, Pd level of 8 ppm and KF of 0.1). Data for B-5: HRMS m/z (M+H): 421.2067, found; 421.2035, required.
[0062] While the invention has been described and illustrated with reference to certain particular embodiments thereof, those skilled in the art will appreciate that various adaptations, changes, modifications, substitutions, deletions, or additions of procedures and protocols may be made without departing from the spirit and scope of the invention. | The present invention is directed to processes for preparing a pyridyl piperidine compound which is an antagonist of orexin receptors, and which is useful in the treatment or prevention of neurological and psychiatric disorders and diseases in which orexin receptors are involved. | 2 |
BACKGROUND
This invention relates to the art of calendering thermoplastic materials into sheet-like form. More particularly, the present invention relates to an improved method and apparatus for removing the hot thermoplastic material from the calender.
Calendering of thermoplastic materials into film or sheet-like form is well known, and may be briefly described in relation to the manufacture of unplasticized ("rigid") polyvinyl chloride sheet. The PVC formulation--which generally comprises PVC resin, an impact modifier, a thermal stabilizer, one or more lubricants for "internal" and "external" lubrication, and pigments as well as various other processing additives--is mixed to distribute the additives throughout the PVC resin. Mixing may be accomplished using either large bulk mixers such as ribbon blenders or high speed mixers. The blended PVC formulation is then fluxed into one of several possible forms including small strands, chunks, and continuous ribbons. Typically, the fused PVC formulation is then passed between at least one set of mixing rolls--normally operated at from about 170° to about 180° C.--which serves to convert the fluxed PVC formulation into a relatively narrow, thick strip of material which is then passed to the calender by a conveyor.
Calenders are well known to those in the art and may be described as a series of rotating cooperating rollers or bands between Which is forced a thermoplastic material which, due to the action of the calender, assumes the shape of a sheet, film or web of specified width and thickness. Rigid PVC calenders usually consist of four rolls, although both three and five roll calenders are known. The surface of the formed sheet, film or web may be smooth or matte, depending on the finish of the final two calender rolls. As indicated above, there is a great variety possible in the number and configuration of rolls in a calender train. Those of ordinary skill in the calender arts will be familar with 2-roll, 3-roll, 4-roll or 5-roll types, which can be arranged for example in 2-roll vertical, 2-roll inclined, 2-roll horizontal, 3-roll vertical, 3-roll 120°, 3-roll inverted "L", 3-roll triangular, 4-roll stack, 4-roll "L", 4-roll inverted "L", 4-roll flat "Z", 4-roll inclined "Z", 4-roll vertical "Z", or 5-roll "L" configurations. For the processing of thermoplastics, particularly rigid PVC, the most commonly used calenders are the 4 - or 5-roll "L" or inverted "L" types, or the 4-roll inclined "Z" type (also known as an "S" calender).
The calendered PVC sheet is typically removed from the last roll of the calender by two to four stripper rolls, passed over two to six cooling drums, scanned by a beta ray gauge measuring device, cut by an edge trimming system and finally wound or stacked.
Embossing units are sometimes used in the manufacture of rigid PVC sheet, especially matte-finish products. An embossing unit typically comprises a rubber nip roll running against a patterned or matte finish steel roll.
Rigid PVC calenders typically operate from about 180° to 200° C. The object is to process the PVC formulation as quickly as possible through the calender line before it decomposes or sticks to the calender rolls. Unfortunately, adhesion of hot PVC to the last calender roll at the point it is stripped off the roll remains a problem. Some of the design and processing variables which affect the degree of adhesion are calender roll temperature, roll surface, the PVC formulation, plastic draw, and the design of the stripping section. Unfortunately, minimizing film adhesion by lowering roll temperature, using gloss calender rolls, and employing high draw ratios between the calender and the stripping rolls may lead to a commercially unacceptable PVC product. For example, low roll temperatures increase haze in transparent films and may cause other processing problems. High draw ratios between the calender and the stripping roll may create machine direction shrinkage in the film and increase gauge profile variations. In short, the basic problem in typical calendering operations is to remove the hot calendered thermoplastic sheet from the last calender roll and cool it without disturbing its lay-flat, gauge profile, surface characteristics or shrinkage properties.
These properties, especially lay-flat or curl resistance, and low levels of shrinkage generally, have become increasingly important in certain applications of calendered plastic materials. For example, calendered polyvinyl chloride is used to manufacture floppy disk jackets and also in blister packaging. Floppy disk jacket applications have increasingly demanded PVC sheets which will not curl or wrinkle upon exposure to temperatures up to about 160° F. Blister packaging thermoformers require a shrinkage resistant film which will not curl in machines which do not restrain the film edges during heating. PVC resin which has been calendered tends to stick to the last roll of the calender and must be pulled off the roll. This tends to impart machine direction thermal shrinkage in the PVC sheet, rendering the film unattractive for floppy disk jacket and blister packaging applications.
One solution to this problem is proposed by F. Nicoll, "Manufacture of Continuous Plastic Sheets," U.S. Pat. No. 4,311,658 (Jan. 19, 1982), which is expressly incorporated by reference in its entirety. Nicoll '658 discloses rotation of the stripper rolls in the same direction as the direction of rotation of the last calender roll in order to minimize problems associated with the release of the hot PVC resin from the last calender roll, including the problem of surface uniformity in matte sheet manufacture and the problem of residual strain in general. Nicoll '658 does not directly address the problems associated with an unstable "stripping line", however.
The tendency of the hot calendered PVC film to stick to the last calender roll can result in a non-linear and/or a fluctuating "stripping line," which is the line across the last calender roll formed by the last point of film contact. A stable, linear stripping line is critical to production of high quality calendered film. A curved stripping line generally imparts a tendency to curl to the calendered film. A fluctuating stripping line caused by sporadic sticking of the film generally imparts web shrinkage variability to the film. The present invention should substantiallY eliminate the need for production personnel to constantly monitor the "stripping line" of the calendered film to ensure that it is stable.
SUMMARY OF THE INVENTION:
The present invention relates to an apparatus for the manufacture of a continuous sheet or film of thermoplastic material consisting essentially of a plurality of calender rolls in coeperating relationship, at least one stripper roll, means for imparting rotational movement to said calender rolls and said stripper roll whereby the last calender roll is operated at the same or greater rotational speed than the preceding calender roll, an endless belt which is in close contact with and travels around said stripper roll and the last of said calender rolls, and means for continously removing calendered material from said endless belt in the vicinity of said stripper roll.
In another aspect, the present invention is a process for the manufacture of a continuous sheet or film of thermoplastic material consisting essentially of
heating a thermoplastic material to a thermoplastic state;
forming said thermoplastic material into a flexible sheet or film by means of a calender having a plurality of rolls, the last of which is in close contact with an endless belt which travels around said calender roll and which endless belt is in close contact and travels around a stripper roll;
removing said flexible sheet from said calender by contacting said flexible sheet with said endless belt rather than the last roll of the calender and conveying said flexible sheet away from the calender;
continously cooling said flexible sheet; and
continously removing said cooled flexible sheet from said endless belt.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings are diagrammatic side elevations of calender and associated stripper roll assemblies, in accordance with the prior art and in accordance with the present invention. It will be understood that those drawings which depict, in schematic form, apparatus according to this invention are intended only to be illustrative thereof and not limitative thereof.
FIG. 1 represents a bottom-fed "L" calender, with three stripper rolls according to the prior art.
FIG. 2 represents a top-fed inverted "L" calender, with three stripper rolls according to the prior art.
FIG. 3 represents a top-fed "F" calender, with three stripper rolls according to the prior art.
FIG. 4 represents a bottom-fed inclined "Z" calender, with four stripper rolls according to the prior art.
FIG. 5 depicts a bottom-fed "L" calender, with an endless belt in close contact with the last calender roll and the first stripper roll, in accordance with the present invention.
FIG. 6 depicts a top-fed inverted "L" calender with an endless belt in close contact with the last calender roll and the first stripper roll, in accordance with the present invention.
FIG. 7 illustrates a top-fed "F" calender with an endless belt in close contact with the last calender roll and the first stripper roll, in accordance with the present invention.
FIG. 8 represents a bottom-fed inclined "Z" calender, with an endless belt in close contact with the last calender roll and the first stripper roll, in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Although the method and apparatus of this invention are believed particularly useful in calendering polyvinyl chloride (PVC), and its use will be exemplified in connection therewith, the scope of the invention is not limited thereto and embraces the calendering of any material which is capable of being calendered, including such thermoplastic materials as ABS, cellulose acetate, cellulose butyrate, cellulose propionate, ethylene/ethyl acrylate copolymers, alloys of PVC and acrylate ester polymers, chlorinated PVC, polyolefins, and so forth. As uSed herein, the term "pVC" includes vinyl chloride homopolymers, copolymers and terpolymers, both plasticized and unplasticized, and compounds thereof containing any of the conventional additives such as impact modifiers, stabilizers, lubricants, fillers, colorants, and so on.
As summarized above, the present invention relates to an apparatus and method for stripping hot, tacky calendered material from a calender by means of an endless belt traveling around the last calender roll and at least one stripper roll. It is believed the present invention permits efficient stripping of the calendered material without significantly affecting the shrinkage properties of the calendered material.
The calender rolls employed in the present invention are conventional in nature. Such rolls are typically manufactured from either chilled cast iron or forged steel, with forged steel rolls predominating for calenders over two meters wide due to the higher modulus of forged steel, which is important in controlling roll deflection. The surface of calender rolls used to produce "gloss" film (smooth, clear product) must have a surface finish or rating of RMS-1; such rolls are typically chrome plated. By contrast, unchromed rolls are typically employed to produce "matte" finish products.
The physical form and size of the stripper rolls to be used in the practice of this invention will not differ in any significant manner from conventional stripper rolls. Thus they will generally be made of a ferrous metal, and may advantageously be chrome plated. The surface can be smooth or matte, can be sand blasted, chemically etched, metal sprayed, Teflon® coated, and so on, in known manner. In the case of plasticized PVC it is sometimes advantageous to cover the stripper rolls with a felt or a textile fabric. The material of construction of the stripper roll and the surface treatment thereof is not a part of the invention. The diameter of the stripper rolls is not critical. A diameter in the range of from about 4 inches to about 10 inches is generally satisfactory, but smaller or greater diameters can be used if desired without departing from the scope of the invention. As will be obvious to those skilled in the art, the width of the stripper rolls will be determined by the width of the calender with which they are to be used.
Similarly, the means for imparting rotational movement to the calender rolls and the stripper rolls will be conventional in nature. All the rolls in a typical calender may be individually speed controlled. Normally each roll is run slightly faster than the preceding roll since a hot sheet will "follow" the faster running roll, and thus sheet transfer between rolls is enhanced. Calender rolls are usually driven by DC motors operating through reduction gears. The speed differential or friction between each calender roll pair is normally from 0 to 30%. Calender roll speeds can range up to 100 meters per minute on the final roll. Stripper rolls are also driven by DC motors operating through reduction gears. Stripper rolls typically rotate at least the speed of the final calender roll and generally somewhat faster in order to strip or remove the hot calendered material from the last calender roll. Conventional stripper roll speeds can range up to four times the speed of the final calender roll. In the practice of the present invention, the rotational speed of the first stripper roll must be substantially the same as the rotational speed of the final calender roll in the present invention since an endless band travels around both rolls.
The endless band of the present invention must be flexible, capable of efficent heat transfer, not be subject to significant elongation or shrinkage, and must have good tensile strength. Stainless steel, polyimide film, and polyethylene terephthalate film all may be used to fabricate the endless belt of the present invention, with stainless steel being preferred for commercial production calenders. Metallic bands formed from beryllium/copper alloy, copper/cobalt/beryllium alloy, or copper/nickel/beryllium alloys may have utility as the endless band. Endless belts formed from such alloys are described in U.S. Pat. No. 4,537,810, which is expressly incorporated by reference in its entirety.
Polymeric films produced from polyaryl ether ketones and/or polyaryl ether sulfones may also have utility as the endless band; such polymers are described in U.S. Pat. Nos. 3,442,857 3,441,538, and 3,751,398, each of which is expressly incorporated by reference in its entirety.
The purpose and function of the endless belt is to supplant the working surface of the last calender roll. Rather than contacting the surface of the final calender roll, the hot tacky thermoplastic resin will come into contact with the surface of the endless belt, be carried partially around the final roll, and toward the stripper roll by the endless belt. Since there will be no contact with the final calender roll, the problem of excessive film adhesion to the calender roll with its attendant deliterious effects upon the film's mechanical properties, especially shrinkage and elongation, should be obviated. As the hot tacky film is carried away from the final calender roll it will begin to cool under the influence of the cooling means described below, thereby losing some of its adhesive property. This will permit efficient stripping of the calendered sheet from the endless band without influencing the sheet's mechanical properties.
"The last calender roll," as used herein and in the claims, is defined as the last calender roll which the calendered material is carried upon prior to removal from the calender. In some calenders, such as the bottom-fed "L" calender depicted in FIG. 1, the top-fed inverted "L" calender depicted in FIG. 2, and the bottom-fed inclined "Z" calender depicted in FIG. 4, the last roll on the calender is actually the last roll which the calendered material is carried upon prior to the removal from the calender. In other calender configurations, this is not the case. FIG. 3 depicts a top-fed calender in which calendered material is removed from the third calender roll as opposed to the fourth and final calender roll.
The working surface of the endless belt (ie. that surface which comes into contact with the calendered thermoplastic material) may be smooth in order to produce "gloss" or smooth calendered sheet, or it may be roughened or patterned in order to produce calendered sheet having a "matte" finish.
As the endless belt travels away from the last calender roll and toward the stripper roll, the belt and the hot calendered sheet supported by the belt are cooled. This may be accomplished by running the endless belt over cooling pipes or by blowing cooling air against the belt or the calendered sheet. Alternatively, cooling may be accomplished by merely exposing the belt and the hot calendered sheet to ambient air. As the calendered sheet cools it will become less tacky and less adhesive, thereby enabling removal of the calendered sheet from the endless belt without significantly affecting its lay-flat, gauge profile, surface characteristics or shrinkage properties.
The calendered sheet may be conveniently removed from the endless belt in the vicinity of the first stripper roll, and more specifically in the zone where the endless belt makes contact with the stripper roll and begins to travel around the roll and back towards the final calender roll. Stripping of the calendered sheet may be performed using conventional equipment in much the same manner that calendered material is stripped from the final calender roll by a stripper roll or rolls.
The invention may be further illustrated by examination of the drawings. As discussed above, FIGS. 1 through 4 depict conventional calender configurations and stripping sections. Such apparatus would typically be operated in combination with PVC resin blenders, fluxers, mixing rolls, cooling drums, trimming systems and winders, all of which are conventional and not shown in the drawings. Referring to FIG. 1, a bottom-fed "L" calender is diagrammatically depicted with three stripper rolls. The calender comprises four calender rolls l0, 11, 10(a) and 11(a) and rotational means therefor (not shown). As depicted by the arrows indicating the direction of individual rotation, calender rolls 10 and 10(a) rotate clockwise, while calender rolls 11 and 11(a) rotate counter-clockwise. The stripper section comprises stripper rolls 12, 13, and 12(a) and rotational means therefor (not shown). As depicted by the arrows indicating the direction of individual rotation, stripper rolls, 12 and 12(a) rotate clockwise, while stripper roll 13 rotates counter-clockwise.
In conventional operation, the fluxed thermoplastic resin is fed to the first nip of the calender formed by rotating calender rolls 10 and 11. A first bank of thermoplastic resin is formed in this nip. The thermoplastic resin is forced between calender rolls 10 and 11, thereby adopting a sheet-like form. The calendered thermoplastic sheet adheres to calender roll 11 and is carried by rotation of same to the nip between calender rolls 11 and 10(a). A second, smaller bank of thermoplastic resin is formed in the second nip. The thermoplastic resin is forced between calender rolls 11 and 10(a), thereby adopting a thinner, sheet-like form than the calendered thermoplastic sheet emerging from the nip formed by calender rolls 10 and 11. The twice-calendered sheet adheres to calender roll lO(a) and is carried by rotation of same to the nip formed by calender rolls 10(a) and 11(a). A third, still smaller bank of thermoplastic resin may form in this third nip. The thermoplastic resin is forced between calender rolls 10(a) and 11(a), thereby adopting yet a thinner, sheet-like form than the calendered thermoplastic sheet emerging from the second nip of the calender apparatus. The thrice-calendered adheres to calender roll 11(a) and is carried by rotation of same partially around calender roll 11(a). The thrice-calendered resin is then removed from the working surface of calender roll 11(a) by the action of the stripping rolls 12, 13 and 12(a). The calendered sheet travels around these rolls to slitting and winding means not shown in FIG. 1.
In the conventional calendering process just described the thermoplastic material becomes progressively hotter and more adhesive with each passage through a calender nip. By the time the calendered material is forced through the nip formed by calender rolls 10(a) and 11(a), it is hot and adheres strongly to calender roll 11(a) (the "last calender roll"). Removal of the adhesive calendered sheet from calender roll 11(a) requires force to be exerted by the stripper rolls, and may impart undesirable orientation to the otherwise unoriented calendered sheet, especially if an undesirable "stripping line" is created.
The present invention modifies the above-described bottom-fed "L" calender and calendering process in the manner illustrated by FIG. 5, which depicts the same calender apparatus modified by the addition of an endless band 14 which travels around calender roll 11(a) and stripper roll 12. This requires that stripper roll 12 rotate counter-clockwise, as does calender roll 11(a). Consequently, stripper roll 13 rotates clockwise and stripper 12(a) rotates counter-clockwise.
In operation, the thermoplastic resin will be fed to the calender in conventional manner. The thermoplastic resin will be forced through the first and second nips of the calender in similar fashion to the conventional process. As the thermoplastic resin adheres to calender 10(a) it will be carried to, and forced between, a nip formed by calender roll 10(a) and the working surface of endless band 14. The thermoplastic resin will thereby adopt a thinner sheet-like form and adhere to the endless belt, which will carry it towards stripper roll 12.
During the calendering process just described, the thermoplastic resin will become progressively hotter and more adhesive with each passage through a calender nip. In a manner analogous to the conventional process described above, thermoplastic resin which is calendered according to the process and apparatus illustrated by FIG. 5 will emerge from the last nip (formed by calender roll 10(a) and the working surface of endless band 14) in a hot, adhesive state. As the endless band 14 carries the calendered sheet toward stripper roll 12, the sheet will begin to cool and become less adhesive.
As the cooled thermoplastic calendered sheet reaches stripper roll 12 and is carried partially around same by the endless belt 14, the calendered sheet will be efficiently removed from the endless belt by stripper roll 13. Since the calendered sheet will be relatively cool, it should be more resistant to orientation caused by the pulling force of stripper roll 13.
FIGS. 2 through 4 are analogous to FIG. 1 and illustrate various conventional calender configurations. Similarly, FIGS. 6 and 8 are analogous to FIG. 5, and depict how the present invention would modify these calender configurations.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention may be employed upon a wide variety of calenders in the production of a wide range of thermoplastic materials. The use of the invention as applied to a four-roll, top-fed, inverted "L" calender for the production of unplasticized polyvinyl chloride sheet is a preferred embodiment of the invention.
The preferred embodiment of the invention is illustrated in FIG. 6, which depicts endless belt 14 in close contact with the last calender roll [roll number 11(a)] and the first stripper roll 12. ln operation, thermoplastic PVC F will be fed to the first nip of the calender. A first bank of thermoplastic PVC will form in the nip. The thermoplastic PVC will be forced between calender rolls 10 and 11 thereby adopting a sheet-like form. The calendered thermoplastic PVC sheet will then "follow" calender 11 to the nip between calender roll 11 and calender roll 10(a). A second bank of thermoplastic PVC will be formed in the second nip. The thermoplastic PVC will be forced between calender rolls 11 and 10(a), thereby adopting a thinner sheet-like configuration than the calendered PVC sheet emerging from calender rolls 10 and 11. The twice calendered thermoplastic sheet will "follow" calender roll 10(a) to the nip between calender roll 10(a) and the endless belt 14 which will travel around calender roll 11(a). A third bank of thermoplastic PVC may be formed in the third nip. The twice calendered thermoplastic PVC will be forced between the calender roll 10(a) and the endless belt, thereby forcing the thermoplastic material to adopt an even thinner sheet-like form. The thrice calendered PVC sheet, which will be hot (typically above 140° C.) and tacky, will adhere to the endless belt as the belt travels around calender roll 11(a), leaves the roll surface, and travels toward the first stripper roll 12. As the calendered PVC is carried toward the first stripper roll by the endless belt, the calendered PVC will begin to cool under the influence of ambient air. As the PVC sheet cools, it will become less tacky and adhesive, thereby permitting the PVC sheet to be stripped or removed from the endless belt 14 as it reaches and begins to travel around the first stripper roll 12 without degrading the mechanical properties of the calendered PVC sheet. The endless roll, now free of the PVC sheet, will travel around the first stripper roll back towards calender roll 11(a). The cooled and stripped PVC sheet may then travel over several more rolls prior to stacking or winding.
One of ordinary skill ln the art will recognize that the above described invention should significantly enhance the desirable properties of calendered film, such as lay flat and shrinkage resistance, thereby permitting wider commercial acceptance of calendered thermoplastics for floppy disk jacket and blister packaging applications. Additionally, the problem associated with an unstable "stripping line" should be reduced if not eliminated. | An improved apparatus and method for calendering of thermoplastic material are disclosed. An endless belt is interposed between the calendered material and the last calender roll which belt conveys the thermoplastic calendered sheet around the last calender roll and toward the stripper roll. The thermoplastic calendered sheet does not come into contact with the final calender roll surface. After cooling the film should strip easily off the endless belt. Consequently, problems originating in sheet adhesion to the final calender roll will be reduced if not eliminated. | 1 |
CROSS REFERENCE TO PRIOR APPLICATIONS
[0001] This application is a continuation of application Ser. No. 14/236,908, filed on Feb. 4, 2014, which is a U.S. National Phase application under 35 U.S.C. §371 of International Application No. PCT/EP2012/064199, filed on Jul. 19, 2012 and which claims benefit to German Patent Application No. 10 2011 052 429.0, filed on Aug. 5, 2011. The International Application was published in German on Feb. 14, 2013 as WO 2013/020788 A1 under PCT Article 21(2).
FIELD
[0002] The present invention relates to a device for removing sea bed having a conveying line operated according to the airlift method, or using feed pumps, which is at least partially surrounded by sea water, and by which removed sea bed can be transported in the conveying direction to the surface.
BACKGROUND
[0003] The “airlift method” is understood as the method for transporting removed sea bed. The airlift method provides a supply of compressed air into the bottom area of the conveying line. The air bubbles that rise on the inside of the conveying line create the effect of an upward flow on the inside of the drilling line that transports removed sea bed to a marine unit above the water line.
[0004] When such a conveying apparatus is employed for transporting mineral raw materials, such as, for example, manganese nodules from a water depth of approximately 5,000 m, the volume portion of the material transported inside the conveying line can constitute up to 10% of the internal volume of the conveying line. The conveying line can, for example, have an inside diameter of 40 cm.
[0005] It is regularly possible to generate a stronger upward flow if feed pumps are used. The volume fraction of the conveyed material is then greater, however, the method tends to be even more susceptible to clogging.
[0006] If the conveying operation of removed sea bed comes to a standstill (irrespective of the reason therefor), the sea bed material that is inside the conveying line sinks very quickly to the bottom because it has a considerably higher density than sea water. Assuming a water depth of 5,000 m and a volume fraction of removed sea bed of 10%, the result is a 500 m long plug clogging the line. Freeing the conveying line of the plug by regular means is then either impossible, or only possible with great difficulty. Similarly, it is no longer possible to salvage the conveying line due to the large mass of the plug, which can be as much as 1,500 to 2,000 t in the given example. In a worst case scenario, this means that the conveying line may need to be abandoned following such an interruption of the conveying operation.
[0007] A reason for such an interruption can be, for example, a failure of a transport of flow inside of the conveying line. Such a failure can be caused by deposits of removed sea bed on the interior lining of the conveying line which gradually increase until they create a blockage of the complete internal cross-section or of the conveying line. Another conceivable reason for a blockage is an energy supply failure or a compressor failure which results in the compressed air necessary for the operation of the airlift process no longer blowing into the conveying line. If the sea bed is first pumped via solid-material pumps from a clearing vehicle to an interim station, which is also referred to as a “buffer,” and transported from there via the conveying line to the marine unit above the water line, defects on the submarine unit can also result in a failure of flow transport. Extreme environmental events having a propensity of causing an interruption in flow transport are moreover conceivable.
[0008] DE 2008384 A describes a dual pipe conveying facility that has an annular pipe line with pipes that are routed as a sink pipe from the ocean surface down to the ocean floor and as a lift pipe for the transported material back up to the ocean surface. Pressurized water preferably circulates inside this annular pipe line as a transport fluid, wherein the pressurized water is circulated by pumps. The conveyed material is fed into the annular pipe line via a pressure lock on the ocean floor. The pressure of the pressurized fluid is dimensioned such that the conveyed material fed into the annular line is raised inside the lift pipe all the way to the water surface.
SUMMARY
[0009] An aspect of the present invention is to improve a device, as was described in the introduction above, where the clogging risk by the formation of a plug, accompanied by an interruption of operations or a failure of the transport of flow, is substantially reduced.
[0010] In an embodiment, the present invention provides a device for removing sea bed which includes a conveying line at least partially surrounded by sea water and an emergency emptying device arranged in the conveying line. The conveying line is configured to have a sea bed be removed therethrough so that a removed sea bed is transportable to a surface in a conveying direction. The emergency emptying device is configured so that the removed sea bed moving in a direction counter to the conveying direction in the conveying line is dischargeable from the conveying line into the sea water.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The present invention is described in greater detail below on the basis of embodiments and of the drawings in which:
[0012] FIG. 1 shows a schematic representation of a view of a region of the conveying line around an emergency emptying opening, as seen in a partial longitudinal section; and
[0013] FIG. 2 shows a representation of the hydraulic diagram of an embodiment of the device according to the present invention.
DETAILED DESCRIPTION
[0014] The conveying line of the device according to the present invention comprise an emergency emptying means by which removed sea bed, which is transported counter to the conveying direction, can be discharged from the conveying line and into the sea water. This measure prevents the removed sea bed, which is present inside the conveying line at the time of the interruption or the failure of the transport flow, from forming a plug of the kind described above that becomes deposited in the line and clogs the bottom end of the conveying line.
[0015] In embodiment of the device according to the present invention, the emergency emptying means can, for example, comprise at least one emergency emptying means that can be opened and closed, and through which removed sea bed material moving against the direction of transport can be discharged into the surrounding sea water.
[0016] To further accelerate such a discharge in order to further reduce down-times and any residual clogging risk, a plurality of emergency emptying openings can, for example, be provided and, for example, disposed approximately at regular intervals over the length of the conveying line.
[0017] In an embodiment of the present invention, the openings can, for example, be spaced every 200 m to 700 m, for example, at 400 m and 500 m intervals. Assuming that the removed sea bed inside the conveying line typically sinks at 0.5 m/s following such a disruption of flow, the emergency emptying openings would have to remain open, for example, for 13 to 17 minutes to provide an almost complete evacuation of removed sea bed from the inside of the conveying line.
[0018] In an embodiment of the device according to the present invention, an emergency emptying door can, for example, be provided on each emergency emptying opening. The emergency emptying door can be displaced into the interior of the conveying line so that any removed sea bed moving counter to the conveying direction can be discharged by the action of the emergency emptying door through the emergency emptying opening and into the sea water.
[0019] A piston/cylinder apparatus that can be operated by water-hydraulic means can, for example, be provided for actuating the displacement of the emergency emptying door between the open and the closed positions. An advantage of a water-hydraulic actuation is that it is environmentally safe. If leaks occur, no hydraulic oil can escape which could damage the environment. It is moreover possible to omit a closed system for circulating hydraulic fluid altogether, because, when pressure is to be relieved, the water is simply discharged into the environment and any return by way of a separate return line into the pressure reservoir can be omitted. The water-hydraulically operated apparatus can therefore be conceived as having only a single, central hydraulic supply for the totality of all piston/cylinder devices.
[0020] To avoid having to apply a continuous pressure to the water-hydraulically actuated piston/cylinder devices during the conveying operation, the piston/cylinder devices are spring loaded so that the emergency emptying doors move to their closed positions when no water-hydraulic pressure is in effect. This means that only one pressure application to the piston/cylinder devices is necessary when the transport of flow inside the conveying line comes to a halt due to a malfunction.
[0021] In an embodiment of the present invention, the hydraulic line can, for example, be connected to a water reservoir that supplies the water-hydraulic pressure. The hydraulic line can also include a closed water tank that is filled with compressed air above the water level. It is possible to connect the tank to a compressor that maintains the internal pressure inside the tank at a preset value.
[0022] In an embodiment of the present invention, the hydraulic line connected to a water reservoir can, for example, includes a free end that is closed by a check valve. The check valve is disposed so that it opens against the pressure that is present inside the hydraulic line. Using this hydraulic line, the piston/cylinder devices are connected for the purpose of actuating them against the spring force.
[0023] In an embodiment of the present invention, a switching valve can, for example, be disposed between the water reservoir and the hydraulic line that is able to execute the following switching positions:
Separation of the water reservoir from the hydraulic line by means of a check valve that opens against the water-hydraulic pressure provided by the water reservoir. This is the switching position of the switching valve during a normal operation of the device; i.e., when the desired conveyed flow is present inside the conveying line. Connection of the water reservoir to the hydraulic line. This switching position can be manually actuated and, provided the corresponding sensors are present, can automatically be actuated in the event of a failure. In this switching position, the pressure applied by the water reservoir to the water in the hydraulic line actuates the piston/cylinder devices against the spring pressure so that the emergency emptying doors are displaced to the inside of the conveying line for the purpose of discharging removed sea bed to the outside. Separation of the water reservoir from the hydraulic line and simultaneous closing of the water reservoir as well as opening of the hydraulic line to the environment. The switching valve is brought in this position when the conveying operation must be restarted after a disruption in the conveying operation has been remedied, and/or after the material that is inside the conveying line was discharged into the surrounding sea water by opening the emergency emptying openings.
[0027] The present invention will be described in further detail below based on the drawings.
[0028] The embodiment of a device according to the present invention, as depicted in the drawing, comprises a conveying line 1 , a section of which is shown in FIG. 1 . The conveying line 1 is approximately pipe-like with an inside diameter 2 of 2 to 40 cm. The conveying line 1 serves to transport removed sea bed to the surface using the so-called “airlift method.” Mineral raw materials are in particular conceivable as removable sea bed, such as, for example, manganese nodules that are mined at an underwater depth of approximately 5,000 m. The length of the conveying line 1 is therefore approximately 5,000 m.
[0029] Using the airlift method, an upward fluid flow is created on the interior 3 of the conveying line 1 , as symbolically indicated by the arrow S.
[0030] To avoid large quantities of removed sea bed becoming impacted at the lower end of the conveying line 1 and forming a plug if the operation is interrupted due to a failure in the transport of flow, emergency emptying means 4 are provided, respectively spaced at 500 m intervals.
[0031] The functionality of these emergency emptying means 4 shall be described in further detail below in reference to FIG. 1 , which depicts said emergency emptying means 4 in the activated state.
[0032] In section B, which is where the emergency emptying opening 5 is located, the conveying line 1 has an approximately oval cross-section. Below the emergency emptying opening 5 , a bearing means 7 is provided on the outside of the wall 6 of the conveying line 1 , where an emergency emptying door 8 of the emergency emptying means 4 is connected in an articulated manner and can be pivoted about a hinge axis T that is arranged transversely relative to the longitudinal extension L of the conveying line 1 . The emergency emptying door 8 can be pivoted from a closed position, in which the emergency emptying opening 5 is completely closed and the emergency emptying door 8 is substantially flush with the wall 6 of the conveying line 1 , to an open position, as depicted in FIG. 1 , in which the emergency emptying door 8 rests by the remote edge 9 thereof relative to the hinge axis T internally against the wall 6 on the side that is opposite the emergency emptying opening 5 , therein forming an opening angle α of approximately 30° with an opening plane.
[0033] A water-hydraulically powered piston/cylinder apparatus 10 is provided for the pivot actuation between the closed and the opened positions. The piston/cylinder apparatus 10 engages via a piston rod 12 via a lever 11 , which protrudes approximately perpendicularly from the surface of the emergency emptying door 8 . A cylinder-side end of the piston/cylinder apparatus 10 is fastened to a bearing projection 13 , again on the exterior of the wall 6 .
[0034] A compression spring 15 is disposed in the annular space between the piston rod 12 and a cylinder space 14 . The compression spring 15 causes the piston rod 12 to be supported in a retracted position when the emergency emptying door 8 is flush with the wall 6 so as to seal the emergency emptying opening 5 when no pressurized water is applied to the cylinder space.
[0035] In the position of the emergency emptying door 8 as depicted in FIG. 1 , removed sea bed is guided in the form of solid material particles 16 , which are symbolized by the circles as presently shown in FIG. 1 , while sinking as a result of a malfunction or interruption of the transport of flow within the meaning of the arrows P, and discharged toward the outside into the surrounding environment of the conveying line 1 . Due to the fact that a typical sink rate of the removed sea bed (as previously described) is approximately 0.5 m/sec, an accumulation of the sunken sea bed material in the ambient area surrounding the bottom end of the conveying line 1 can be precluded because even small ocean currents that are in effect outside of the conveying line 1 will cause the material to be distributed over a large terrain.
[0036] The apparatus that is provided for the water-hydraulic actuation of the piston/cylinder apparatus 10 and the emergency emptying door 8 shall be described in further detail below in reference to FIG. 2 .
[0037] In FIG. 2 , O designates the sea water surface. For actuation purposes, the cylinder chambers 14 of the piston/cylinder devices 10 are connected to a hydraulic line 18 via the supply lines 17 . As can be seen in the schematic sectional representation in FIG. 2 of the piston/cylinder devices 10 , the compression spring 15 operates in an embodiment according to FIG. 2 with an effect on the floor of the piston on a side that is opposite of the piston rod 12 . The cylinder volumes are correspondingly formed by the annular space that surrounds the piston rod 12 . This configuration, that is reversed in relation to the embodiment according to FIG. 1 , has the advantage of a lesser cylinder volume filled with hydraulic fluid, such that, due to the return displacement of the pistons that is effected by the compression springs 15 as well as for the displacement of the pistons due to the water-pneumatic pressure, only smaller amounts of water must be transported, whereby it is possible to reduce the actuation times.
[0038] The hydraulic line 18 is hydraulically connected to a water reservoir 20 by way of a switching valve 19 . A measurement means 21 is disposed between the switching valve 19 and the water reservoir 20 which measures the amount of the flow-through and the pressure that the water is subject to within the hydraulic line 18 .
[0039] The water reservoir 20 comprises a pressure tank 22 . The pressure tank 22 is filled with water to a filling level 23 . A freely movable piston 38 is disposed above the filling level 23 , and a compressed air cushion is in effect acting upon the same, whereby the air cushion is generated with the aid of a high-pressure piston compressor 24 that is connected via a high-pressure air accumulator 25 to the pressure tank 22 , which is also referred to as the “piston accumulator.” A pressure measurement instrument 26 and a pressure relief valve 27 are activated in the supply line to the pressure tank 22 . The pressure line that runs between the high-pressure piston compressor and the high-pressure air accumulators is also provided with corresponding means 28 .
[0040] The water reservoir 20 further comprises a fresh water tank 29 from which, via a line, which is protected with the aid of a check valve 30 against reflux, a high-pressure water pump 31 pumps pressurized water into the pressure tank 22 to achieve and/or maintain the desired filling level 23 . A bypass 32 is switched between the high-pressure water pump 31 and the hydraulic line 18 that leads to the fresh water tank 29 , which is connected to the line via a stop cock 33 and a pressure relief valve 34 .
[0041] If a malfunction or interruption of the transport of flow is detected in the conveying line 1 , triggering an emergency switch 35 that engages the switching valve 19 , which is actuated manually or via suitable sensors (which are not shown in the present drawings), and which measures the transported flow inside the conveying line 1 , results in the switching valve 19 being moved into the switching position III. In this switching position, the hydraulic line 18 is connected to the pressure tank 22 . Due to the pressure increase, water flows into the cylinder chambers 14 of the piston/cylinder apparatuses 10 which are thereby actuated against the effect of the compression springs 15 , thus causing the emergency emptying doors 8 to open. Sinking solid material particles 16 are deflected laterally through the emergency emptying openings 5 to the outside, as described above.
[0042] To close the emergency emptying openings 5 , employing suitable means, the switching valve 19 is moved into switching position II. In this position, the supply line from the pressure tank 22 is closed by the hydraulic line 18 . The hydraulic line 18 is open toward the environment and/or a fresh water reservoir, which can be a fresh water tank 29 . Due to the retractive forces generated by the compression springs 15 , the emergency emptying doors 8 are moved to the closed position with the aid of the piston rods 12 . After reaching said position, the switching valve 19 is moved into the resting position I as depicted in FIG. 2 , when the hydraulic line 18 is connected by a check valve 38 that opens against the water-hydraulic pressure as provided by the water reservoir 20 with a fresh water reservoir 29 .
[0043] The hydraulic line 18 includes an end 36 that is free relative to the environment. It is closed via a check valve 37 that must be opened against the pressure that is present inside the hydraulic line 18 .
[0044] The present invention is not limited to embodiments described herein; reference should be had to the appended claims.
LIST OF REFERENCE NUMBERS
[0000]
1 Conveying line
2 Inside diameter
3 Interior
4 Emergency emptying means
5 Emergency emptying opening
6 Wall
7 Bearing means
8 Emergency emptying door
9 Edge
10 Piston/cylinder apparatus
11 Lever
12 Piston rod
13 Bearing projection
14 Cylinder chamber
15 Compression spring
16 Solid particle materials
17 Supply lines
18 Hydraulic line
19 Switching valve
20 Water reservoir
21 Measurement means
22 Pressure tank
23 Filling level
24 High-pressure piston compressor
25 High-pressure air accumulator
26 Pressure measurement instrument
27 Pressure relief valve
28 Means
29 Fresh water tank
30 Check valve
31 High-pressure water pump
32 Bypass
33 Stop cock
34 Pressure relief valve
35 Emergency switch
36 End
37 Check valve
38 Check valve
α Opening angle
B Section
F Direction of transport
L Longitudinal extension
O Sea water surface
P Arrows
S Arrow
T Hinge axis | A device for removing sea bed includes a conveying line at least partially surrounded by sea water and an emergency emptying device arranged in the conveying line. The conveying line is configured to have a sea bed be removed therethrough so that a removed sea bed is transportable to a surface in a conveying direction. The emergency emptying device is configured so that the removed sea bed moving in a direction counter to the conveying direction in the conveying line is dischargeable from the conveying line into the sea water. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This patent application is a divisional application of patent application Ser. No. 13/326,340, filed on Dec. 15, 2011, entitled “LED PACKAGE AND METHOD FOR MANUFACTURING THE SAME,” which is assigned to the same assignee as the present application, and which is based on and claims priority from Chinese Patent Application No. 201110083148.2 filed in China on Apr. 2, 2011. The disclosures of patent application Ser. No. 13/326,340 and the Chinese Patent Application are incorporated herein by reference in their entirety.
BACKGROUND
[0002] 1. Technical Field
[0003] The disclosure relates to a method for manufacturing light emitting diode (LED) package, wherein the LED package has a good heat dissipation and a high luminous efficacy.
[0004] 2. Description of the Related Art
[0005] The many advantages of light emitting diodes (LEDs), such as high luminosity, low operational voltage, low power consumption, compatibility with integrated circuits, easy driving, long term reliability, and environmental friendliness have promoted their wide use as a light source. Now, light emitting diodes are commonly applied in environmental lighting. However, an encapsulation layer must be formed on the substrate during the manufacture of a common LED package structure. The common LED package structure does not have good thermal dissipation efficiency. Thus, the reliability and luminous efficacy of the common LED package will decrease.
[0006] Therefore, it is desirable to provide a method for manufacturing LED package which can overcome the described limitations.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] Many aspects of the disclosure can be better understood with reference to the drawings. The components in the drawings are not necessarily drawn to scale, the emphasis instead being placed upon clearly illustrating the principles of the present LED package. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the views.
[0008] FIG. 1 is a cross sectional view of an LED package in accordance with a first embodiment.
[0009] FIG. 2 is a top view of the LED package of FIG. 1 .
[0010] FIG. 3 is a cross sectional view of an LED package in accordance with a second embodiment.
[0011] FIG. 4 is a cross sectional view of an LED package in accordance with a third embodiment.
[0012] FIG. 5 is a top view of the LED package of FIG. 4 .
[0013] FIG. 6 is a process flow for manufacturing the LED package of FIGS. 1-2 .
[0014] FIG. 7 is a cross sectional view of the LED package in accordance with the third embodiment and a mold for manufacturing the LED package.
[0015] FIG. 8 is a cross sectional view of an LED package in accordance with a fourth embodiment.
DETAILED DESCRIPTION
[0016] Embodiments of an LED package and a method for manufacturing the LED package as disclosed are described in detail here with reference to the drawings.
[0017] Referring to FIGS. 1 and 2 , an LED package structure 100 includes an electrode 10 , a connection electrode 20 , an LED chip 30 , a lens 40 , and an insulation layer 50 .
[0018] The electrode 10 includes a first electrode 11 and a second electrode 12 . The first electrode 11 and the second electrode 12 are arranged with intervals mutually. A channel 13 is formed between the first electrode 11 and the second electrode 12 . The first electrode 11 and the second electrode 12 are rectangular.
[0019] The mass of the first electrode 11 exceeds that of the second electrode 12 . The first electrode 11 has a top surface 112 , and a cavity 111 is defined on the top surface 112 . The LED chip 30 is arranged inside the cavity 111 . Thus, the LED chip 30 is attached to the bottom surface of the cavity 111 . The bottom surface of the cavity 111 is a dished or curved surface. In this embodiment, the bottom surface of the cavity 111 is dished. The depth of the cavity 111 exceeds the thickness of the LED chip 30 . Thus, the LED chip 30 is totally within the cavity 111 . A reflection layer 114 is formed on the inside surface of the cavity 111 . The material of the electrode 10 is copper, and the material of the reflection layer 114 is silver.
[0020] The connection electrode 20 includes a first connection electrode 21 and a second connection electrode 22 . The first connection electrode 21 is a strip of electrically conductive material. The first connection electrode 21 includes a fixture end 211 and a free end 212 . The fixture end 211 connects with the top surface 112 of the first electrode 11 . The free end 212 extends to the top of the cavity 111 . The second connection electrode 22 is also a strip of electrically conductive material.
[0021] The second connection electrode 22 includes a fixture end 221 and a free end 222 . The fixture end 221 connects to the top surface of the second electrode 12 . The free end 222 extends to the top of the cavity 111 . A certain distance exists between the free end 212 of the first connection electrode 21 and the free end 222 of the second connection electrode 22 . The top surfaces of the first connection electrode 21 and the second connection electrode 22 are at the same horizontal level. A gap 23 is between the top surface 112 of the first electrode 11 and the second connection electrode 22 . The gap 23 communicates with the channel 13 and the cavity 111 . The material of the connection electrode 20 is the same as that of the electrode 10 .
[0022] In another embodiment, the first electrode 11 and the first connection electrode 21 are formed in one piece. Furthermore, the second electrode 12 and the second connection electrode 22 may be formed in one piece.
[0023] The LED chip 30 is arranged in the cavity 111 of the first electrode 11 . The LED chip 30 is attached at the bottom of the cavity 111 . The LED chip 30 has two electrodes (not shown). A welding spot 31 is arranged on each of the two electrodes. The welding spots 31 connect to the free ends 212 of the first connection electrode 21 and the free end 222 of the second connection electrode 22 . Thus, the LED chip 30 connects electrically to the first electrode 11 and to the second electrode 12 .
[0024] The lens 40 is transparent. The lens 40 includes a light incident surface 41 near the LED lens 40 , a light emitting surface 42 away the LED chip 30 , and a side surface 43 connecting to the light incident surface 41 and the light emitting surface 42 . The light incident surface 41 is flat. The light incident surface 41 is attached to the first connection electrode 21 and the second connection electrode 22 .
[0025] A space 44 exists between the light incident surface 41 and the top surface 112 of the first electrode 11 . The first light emitting surface 42 has at least one protrusion portion 421 . The protrusion portion 421 extends in a direction away the LED chip 30 . In another embodiment, the quantity and shape of the protrusion portion 421 can be changed according to specific needs. The side surface 43 is coplanar with the side surface defined by the first electrode 11 and the second electrode 12 . Thus, the lens 40 totally covers the first electrode 11 and the second electrode 12 . The lens 40 is made of silicon resin, epoxy resin, and silicon oxide.
[0026] The insulation layer 50 fills the channel 13 between the lens 40 , the first electrode 11 , and the second electrode 12 . Furthermore, the insulation layer 50 also totally fills the surround of the LED chip 30 in the cavity 111 and the space 44 between the lens 40 and the electrode 10 . The insulation layer 50 is made by the injection method. Moreover, a plurality of fluorescent powders is uniformly added to the insulation layer 50 . Thus, the light emitting characteristics of the LED package structure 100 are enhanced.
[0027] FIG. 3 shows an LED package structure 200 of a second embodiment. The only difference from the first embodiment is that a cavity 111 a defined at the top surface 112 of the first electrode 11 has an opening facing the second electrode 12 . The cavity 111 a communicates with to the channel 13 a via the opening of the cavity 111 a. In another embodiment, another cavity 121 (as shown in FIG. 8 ) is defined at the second electrode 12 . The opening of the other cavity 121 of the second electrode 12 faces the first electrode 11 .
[0028] Referring to FIGS. 4 and 5 , an LED package 300 of a third embodiment includes an electrode 10 , a connection electrode 20 , an LED chip 30 , and an encapsulating layer 60 .
[0029] The electrode 10 , the connection electrode 20 , and the LED chip 30 in the third embodiment are the same as in the first embodiment. The only differences from the first embodiment is that the encapsulating layer 60 includes an insulation layer 61 which fills the surrounding of the LED chip 30 and covers the connection electrode 20 , and a lens 62 on the insulation layer 61 .
[0030] The insulation layer 61 and the lens 62 are formed in one piece. The insulation layer 61 fills the channel 13 defined by the first electrode 11 and the second electrode 12 . The lens 62 includes a light emitting surface 621 away the LED chip 30 . A protrusion portion 622 is formed on the light emitting surface 621 of the lens 62 . The insulation layer 61 connects around the edge of the light emitting surface 621 . A cover 63 extends from the edge of the light emitting surface 621 towards the electrode 10 . The cover 63 encapsulating the side wall of the electrode 10 has a bottom which is coplanar with the bottom of the electrode 10 away the LED chip 30 .
[0031] The encapsulating layer 60 maintains a firm connection with the electrode 10 because of the formation of the cover 63 .
[0032] FIG. 6 shows the process flow of the LED package 100 in the first embodiment. The electrode 10 including the first electrode 11 , and the second electrode 13 , the channel 13 defined by the first electrode 11 and the second electrode 12 are to be provided. A cavity 111 is defined on the first electrode 11 . The cavity 111 communicates with the cavity 13 .
[0033] The LED chip 30 is arranged inside the cavity 111 . The LED chip 30 connects electrically to the first electrode 11 and the second electrode 12 .
[0034] A shield covering the first electrode 11 and the second electrode 12 is to be provided.
[0035] Inject a transparent insulating material(s) into the cavity 111 from the channel 13 by the injection method. The transparent insulating materials totally interconnect the first electrode 11 , the second electrode 12 , and the shield.
[0036] When transparent insulating material(s) solidify, the package is formed.
[0037] The shield can be the lens 40 in the first embodiment. The LED chip 30 connects with the electrode 10 by means of the connection electrode 20 . The connection electrode 20 includes the first connection electrode 21 and the second connection electrode 22 . The connection electrode 20 is pre-coated on the light incident surface 41 of the lens 40 . Then, the electrode 10 is attached on the lens 40 , and the LED chip 30 connects to the first connection electrode 21 and to the second connection electrode 22 by means of die bonding.
[0038] In another embodiment, the connection electrode 20 and the electrode 10 are formed in one piece out of one piece of electrically conductive material. The LED chip 30 is connected to the connection electrode 20 by die bonding. Then, the lens 40 is attached on the electrode 10 .
[0039] During the injection method, the transparent insulating material is injected into the channel 13 defined between the first electrode 11 and the second electrode 12 until the transparent insulating material totally fills the cavity 111 and the space 44 between the lens 40 and the electrode 10 . The insulation layer 50 is formed when the transparent insulating material solidifies. An amount of fluorescent powder(s) is added into the transparent insulating material before the injection process. Thus, the fluorescent powders will be uniformly mixed into the insulation layer 50 on solidification.
[0040] Referring to FIG. 7 , the shield can be a mold 70 . The mold 70 includes a receiving cavity 71 and a concave portion 72 . The size of the receiving cavity 71 exceeds the encircling size of the first electrode 11 and the second electrode 12 .
[0041] Thus, the first electrode 11 and the second electrode 12 are fixed within the receiving cavity 71 . Then, during the injection method, the transparent insulating material is injected into the channel 13 defined between the first electrode 11 and the second electrode 12 until the mold 71 is totally filled. The transparent insulating material in the concave portion 72 forms the protrusion portion 622 of the lens 62 of FIG. 4 .
[0042] Thus, the transparent insulating material in the mold 70 becomes the encapsulating layer 60 in the third embodiment.
[0043] The transparent material may be directly injected into the channel 13 defined between the first electrode 11 and the second electrode 12 . Thus, the packaged structure is completed. The packaging method is simple. The LED chip 30 is arranged inside the cavity 111 . The first electrode is a substrate carrying the LED chip 30 . The electrode 10 being made of metal results in good electrical and thermal conductivity by the first electrode 11 . Thus, any heat generated by the LED chip 30 can be efficiently dissipated via the first electrode 11 . The thermal dissipation efficiency of the LED package structure and the brightness of the LED product are increased.
[0044] While the disclosure has been described by way of example and in terms of exemplary embodiments, it is to be understood that the disclosure is not limited thereto. On the contrary, it is intended to cover various modifications and similar arrangements (as would be apparent to those skilled in the art). Therefore, the scope of the appended claims should be accorded the broadest interpretation so as to encompass all such modifications and similar arrangements. | A method of manufacturing an LED package including steps: providing an electrode, the electrode including a first electrode, a second electrode, a channel defined between the first electrode and the second electrode, the first electrode and the second electrode arranged with intervals mutually, a cavity arranged on the first electrode, and the cavity communicating with the channel; arranging an LED chip electrically connecting with the first electrode and the second electrode and arranged inside the cavity; providing a shield covering the first electrode and the second electrode; injecting a transparent insulating material to the cavity via the channel, and the first electrode, the second electrode, and the shield being interconnected by the transparent insulating material; solidifying the transparent insulating material to obtain the LED package. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to a video disk player. It particularly relates to a reproducing speed control system for a video disk player.
2. Background of the Invention
It is widely known that in conventional video disk players, special reproduction can be carried out in addition to normal play, for example, in a double-speed mode, a triple-speed mode, a still picture mode, a slow-motion mode, and so on. In those video disk players, however, there has been such a disadvantage that a fine change in speed cannot be achieved because in the reproduction it is possible to only set the speed to 1/2, 1/4, and so forth of the normal speed in a slow speed mode and only to the normal speed, a double speed, and a triple speed in a fast speed mode.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to eliminate the foregoing disadvantage in the prior art.
It is another object of the present invention to provide a reproducing speed control system for a video disk player in which reproduction at a desired speed can be realized.
The reproducing speed control system for a video disk player according to the present invention is characterized in that a reproducing speed m/n is set due to entry of a given integer m. A value of an integer portion of a real number obtained from the reproducing speed m/n is used as a base speed. The number of tracks to be jumped is calculated on the basis of the base speed. The information detection point is thereby controlled to perform the jumping operation by the calculated number of tracks to be jumped in synchronism with the vertical synchronizing pulse. Unity is added to the calculated number of tracks to be jumped every time a counter having a full scale of 2n is counted-up by a value of p which is an integer portion of a real number obtained from 2n/l where l is a remainder of the value of m/n.
BRIEF DESCRIPTION OF THE DRAWING
The above and other objects of the present invention will be apparent from the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a block diagram schematically showing a video disk player to which the reproducing speed control system according to the present invention is applied; and
FIGS. 2 and 3 are flowcharts for executing the processing procedures of the reproducing speed control system according to the present invention by the CPU.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
An embodiment of the reproducing speed control system according to the present invention will be described in detail with reference to the accompanying drawings hereunder.
FIG. 1 is a block diagram schematically showing a video disk player to which the reproducing speed control system according to the present invention is applied. In the drawings, information recorded on a video disk 1 is read out by a pickup 2. The read-out high frequency signal of the pickup 2 is demodulated by an FM demodulating circuit 3. The output signal or reproduced video signal from the FM demodulating circuit 3 is applied to a video output terminal as well as a vertical synchronizing separation circuit 4. A vertical synchronizing component contained in the reproduced video signal applied to the vertical synchronizing separation circuit 4 is separately extracted and supplied as a reproduced vertical synchronizing pulse to a central processing unit (CPU) 5 and counter 6 of a full scale of 2n (n being an integer), for example, of a full scale of 120. When an instruction of reproduction in a special mode such as a slow speed play mode, a fast speed play, a still picture mode, or the like, is generated from an operation panel 7, the CPU 5 operates to execute processing on the basis of a processing program written in advance in a read-only memory (ROM) 8. It thereby performs calculations to obtain the number of recording tracks (not shown) of the video disk 1 to be jumped by an information detection point (a light spot) of the pickup 2. The number of jumped tracks is determined in accordance with the designated reproducing speed in synchronism with the vertical synchronizing pulse on the basis of the count of the counter 6. Further, the CPU 5 operates to write into or from a random access memory (RAM) 9 and to read information necessary for executing the program.
The information as to the number of tracks to be jumped, which has been calculated by the CPU 5, is supplied to a jump control circuit 10. The jump control circuit 10 is arranged to send a jump pulse having a pulse width or a crest value corresponding to the number of tracks to be jumped to the pickup 2 in synchronism with the vertical synchronizing pulse. The pickup 2 is provided with a built-in tracking actuator for biasing the information detection point perpendicularly to the recording tracks so that a jumping operation of the information detection point with respect to the recording tracks is performed by the actuator. The jumping operation is executed, for example, on the basis of the method disclosed in Japanese Patent Application No. 8885/1985 filed by the same applicant as that of this application.
Next, referring to the flowcharts of FIGS. 2 and 3, a description will be made as to the procedure of the processing of the reproducing speed control system executed by the CPU 5 according to the present invention.
In FIG. 2, initializing is performed in Step S1 such that the counter 6 is reset and the state of a toggle TG is set to "0". In operation, the state of the toggle TG is alternately switched between "1" and "0" every time a vertical synchronizing pulse is applied to it. Upon entry from the operation section 7 of a reproducing speed and its direction (in Step S2), the operation waits in Step S3 for application of a vertical synchronizing pulse. The reproducing speed can be set as a multiple of 1/60 (=2/120) because the video disk player is provided with the counter 6 of a full scale of 120 (full scale of 2n) and one scene is composed of two fields in the video disk 1. The setting is made by entering a desired integral number m relative to n (n=60).
Assume now that, by way of example, "127" is entered as the value of m so that the reproducing speed is set to 127/60 (=m/n) times as high as a normal speed and the direction of the reproducing speed is forward. The count of the counter 6 is represented by VC and is compared against the full scale value 2n of the counter in Step S4. Upon application of the vertical synchronizing pulse, the operation is shifted to Step S5 through Step S4, so that the counter 6 of a full scale of 120 is counted up (in Step S5). Next, the toggle TG is changed which is performed by exclusive ORing between the preceding value "0" set in the toggle TG and the value "1" (in Step S6). In the initial pass through Step S6, TG is set to "1". If judgment proves that TG=1 in Step S7, the operation is shifted to the next Step S8 in which a calculation is to be made to obtain the number of tracks JC to be jumped. However, the calculation for obtaining a base speed BS has not been executed yet. Therefore, the operation is shifted from Step S8 to Step S10 through Step S9 while the state is left as it is.
In Step S10, setting of the reproducing direction and the calculation for obtaining the base speed BS are executed. The procedure of the calculation executed in Step S10 is described now in reference to the flowchart in FIG. 3.
The reproducing direction is set in Step S101 on the basis of the input information of the reproducing speed and its direction from Step S2. Then calculation is made to obtain a base speed BS and a fine adjustment acceleration speed l (in Steps S102 and S103). The base speed BS is obtained through the following expression of calculation
BS=[m/n]
where the square brackets [ ] is a Gaussian symbol which means a value of an integral portion of a real number obtained from the expression in the brackets. In the example of the embodiment, m=127 and n=60, and therefore the base speed BS=2 is obtained. The fine adjustment acceleration speed l is obtained through the following expression of calculation for the modulus l=mod (m, n), that is,
l=m-[m/n]*n
As a result, the fine adjustment acceleration speed l=7 is obtained. If the test in Step S104 proves that this fine adjustment acceleration speed l is smaller than n/2, the operation is shifted to the step S105 in which the integral value [2n/l] is calculated and a value p (p=17 in this case) obtained by the calculation is stored in a work register WK 0 incorporated in the CPU 5.
Next, the integral value [VC/P] is calculated on the basis of the count VC of the counter 6 and the value obtained by this calculation is stored in a first work register WK 1 (in Step S106). Further calculation is made for the expression [(VC-1)/P], and the integral value obtained by this calculation is stored in a second work register WK 2 (in Step S107). Here, the value of the first work register WK 1 is successively changed to be "0" when the count VC of the counter 6 is within the range of 1-16, to be "1" when the count VC is within the range of 17-33, to be "2" for the range of 34-50, to be "3" for the range of 51-67, etc. The value of the second work register WK 2 , on the other hand, is successively changed to be "0" when the count VC is within a range of 1- 17, to be "1" for the range of 18-34, to be "2" for the range of 35-51, to be "3" for the range of 52-68, etc.
If a test in Step S108 proves again that the fine adjustment acceleration speed l is smaller than n/2, the operation is shifted to Step S109 in which judgment is made as to whether or not the value of the first work register WK 1 is equal to that of the second work register WK 2 . These values are not coincident with each other when the count VC of the counter 6 takes any one of the seven boundary values "17", "34", "51", "68", "85", "102", and "119", but are coincident with each other when the count VC takes a value other than the foregoing seven boundary values. If a test in step S109 proves that the respective values of the work registers WK 1 and WK 2 are coincident with each other, the operation is shifted to Step S110 in which judgment is made as to whether or not the base speed BS is equal to "0". In this case B=2 and therefore the operation is shifted to Step S111 in which judgment is made as to whether or not the reproducing direction is the reverse one. Since the set direction is the forward one, the operation is shifted to Step S112 in which calculation is made to subtract "1" from the base speed BS to obtain BS=1 in this case. After establishment of BS=1, the operation is returned back to the main flow of FIG. 2.
If, on the contrary, the test in Step S109 proves that the value of the first work register WK 1 is not coincident with that of the second work register WK 2 , the operation is immediately shifted to Step S113 in which judgment is made as to whether or not the base speed BS is equal to "0". In this case BS=2, and therefore the operation is shifted to Step S114 in which judgment is made again as to whether or not the base speed BS is equal to "0". If the answer is no, the value "2" is added to the base speed BS to thereby obtain BS=4 in Step S115.
The operation is then shifted to Step S112 through the steps S110 and S111 to thereby obtain BS=3. Then the operation is returned back to the main flow of FIG. 2.
That is, in the case where the base speed BS is equal to "2", BS'=3 is set when the count VC of the counter 6 takes any one of the seven boundary values "17", "34", "51", "68", "85", "102", and "119", while BS'=1 is set when the count VC takes a value other than the abovementioned seven boundary values. Then, the operation is returned back to the main flow.
In the main flow of FIG. 2, upon completion of the calculation for obtaining the base speed BS in Step S10, the operation is returned back to Step S2. Further, the operation is shifted to Step S5 through Steps S3 and S4 and the counter 6 is incremented in Step S5. Next, the operation is shifted to Step S7 through Step S6 and a test is made as to whether or not TG=1 in Step S7. The state of the toggle TG is alternately switched over between "1" and "0" every time the counter 6 is incremented by the operation in Step S6. When the count VC of the counter 6 is an odd number, the operation is shifted to the step S8 in which the number of track jumping JC is obtained from the calculation of [BS'/2]. On the other hand, when the count VC is an even number, the operation is shifted to Step S11 in which the number of track jumping JC is obtained from the calculation of [(BS'+1)/2].
In the case where BS'=1, JC=0 is obtained when the count VC of the counter 6 is an odd number, while JC=1 is obtained when the count VC is an even number. The CPU 5 in the Step S9 sends the track number information respectively corresponding to JC=0 to the jump control circuit 10 when the count value VC of the counter 6 is an odd number or corresponding to JC=1 when the count value VC is an even number. As a result, one track jumping is performed every two vertical synchronizing pulses in synchronism with the vertical synchronizing pulse due to the operation of the jump control circuit 10.
In the case where BS'=3, on the other hand, JC=1 is obtained when the count VC of the counter 6 is an odd number, while JC=2 is obtained when the count VC is an even number. That is, the count VC of the counter 6 is counted up by one after the arithmetic operation of the base speed BS, so that the jumping is carried out with one additional track only when the count VC is a value one greater than the previously described boundary values, that is, any one of "18", "35", "52", "69", "86", "103", and "120".
The operation described above is repeated to thereby make it possible to realize reproduction at the speed of 127/60 times the normal speed. Further, when the count VC of the counter 6 has reached 2n in Step S4, the operation is shifted to Step S12 in which the counter 6 is cleared. Then the operation is shifted to Step S6.
Although the operation has been described for the case where the fine adjustment acceleration speed l is smaller than n/2 in the foregoing explanation, the operation will now be described for the case where the fine adjustment acceleration speed l is equal to n/2 or more.
In the flow of FIG. 3, if the test in Step S104 proves that l≧n/2, n-l is calculated and this value is substituted for the fine adjustment acceleration speed l in Step S116. The operation is shifted to Step S117 through Steps S105 to S108, and judgment in Step S117 is made as to whether or not the value of the first work register WK 1 is coincident with that of the second work register WK 2 . As opposed to the case where l<n/2, the operation is directly shifted to Step S110 when the values of the work registers WK 1 and WK 2 are not coincident with each other, while the operation is shifted to the Step S110 through Steps S114 and S115 when the values of the work registers WK 1 and WK 2 are coincident with each other. As a result, assuming that the fine adjustment acceleration speed l which is set again is, for example, "7", jumping is carried out over one additional track only when the count VC of the counter 6 is a value other than "18", "35", "52", "69", "86", "103" or "120".
Further, when the set reproducing speed is lower than the normal speed, the base speed BS obtained by the calculation in Step S102 of the flow in FIG. 3 is "0". Therefore, in the case where l<n/2 and WK 1 ≠WK 2 , the value "2" is added to the base speed BS to make BS=2 in Step S118 and then field adjustment is carried out in Step S119. In this case the reproducing speed is extremely low so that a so-called flapping of a reproduced scene is apt to be conspicuous. Therefore, in order to avoid this phenomenon, the field adjustment is carried out to cause reproduction to always be carried out from the first field. In the case where l≧n/2 and WK 1 =WK 2 , on the other hand, the reverse direction is set in Step S120. Further, in the case where BS=0 and the reproducing direction is the reverse one, an arithmetic operation is made to add "1" to the base speed BS in the Step S121. Then, the operation is returned back to the main flow of FIG. 2.
In the foregoing embodiment, the base speed BS' is an odd number or an even number when BS is respectively an even number or an odd number. Further, the respective values JC obtained by the arithmetic operations in the Steps S8 and S11 of FIG. 2 are not coincident with each other when the base speed BS is an even number, while the respective values JC are coincident with each other when the BS is an odd number. Therefore jumping control is changed-over between the case where the base speed BS is an even number and the case where the BS is an odd number on the basis of the calculated value JC. However, for example, arrangement may be made such that a step of judging whether the base speed BS is an odd number or an even number is inserted before Step S6 to thereby directly shift the operation to Step S8 when the base speed BS is an odd number.
As described above, in the reproducing speed control system according to the present invention, the set reproducing speed is divided into the base speed and the fine adjustment acceleration speed is not larger than a value of 1/2 times as high as the base speed. The number of tracks to be jumped is increased by one at a suitable interval obtained on the basis of this fine adjustment acceleration speed. Therefore, it is possible to desirably set the reproducing speed within a range of resolution of the counter for counting a vertical synchronizing pulse. | An apparatus for controlling the reproducing speed for a video disk player in fine speed increments. Every time a vertical synchronizing pulse is delivered the number of tracks to be jumped is determined based on a base speed derived from the integer part of the ratio of an entered speed parameter and half a full scale of a counter. An additional track is jumped when the product of the number of vertical synchronizing pulses and the remainder portion of the above ratio exceeds the full scale of the counter. | 8 |
This is a continuation-in-part of copending application Ser. No. 582,059, filed on Feb. 21, 1984, now abandoned. The entire disclosure of the parent application is incorporated by reference.
BACKGROUND OF THE INVENTION
This invention relates to a novel uniform solid-phase composition which makes possible simple and rapid determination of β-hydroxybutyric acid and to a method for preparing the said composition.
β-Hydroxybutyric acid, a kind of ketone body, is an intermediate product of fatty acid metabolism and is found in large quantities in the body fluids (blood, urine, etc.) of diabetes patients and diabetes animals. The invention is hereinafter described in detail on the case of determining β-hydroxybutyric acid in body fluids.
A carbohydrate metabolic disorder such as insulin deficiency due to pancreas incretion disorder causes fatty acid oxidation in the liver to increase. This results in abnormally increased ketone bodies such as acetone, acetoacetic acid, and β-hydroxybutyric acid, which are excessively accumulated in tissues, blood, and urine (ketosis state). It is necessary, therefore, in the case of high-degree pancreas incretion disorder, particularly serious diabetes, or when dosing a patient with carbohydrate limiting food, to pay attention to the ups and downs of the ketone bodies in the body fluid.
It is generally said that when ketosis state occurs in series diabetes, β-hydroxybutyric acid of these ketone bodies in the blood remarkably increases, resulting in increased (β-hydroxybutyric acid)/(acetone+acetoacetic acid) ratio, and thus most sharply indicates abnormal metabolism.
A known quantitative determination method of β-hydroxybutyric acid is the method by Williamson et al which uses a β-hydroxybutyric acid dehydrogenase (Biochemical Journal, Vol. 82, p. 90, 1962). In this method, β-hydroxybutyric acid is reacted with β-hydroxybutyric acid dehydrogenase and diphosphopyridine nucleotide (DPN), and the absorbance of the produced diphosphopyridine nucleotide of reduced type (DPNH) is measured at the specific absorption of 340 nm. The quantity of β-hydroxybutyric acid is determined from the molecular extinction coefficient. Accordingly, there are problems that a high-class ultraviolet spectrophotometer is required, and high skill and long period of time are needed in analysis.
To eliminate such drawbacks, there has been developed a simple colorimetry of high-sensitivity of ketone body in blood, which requires no ultraviolet spectrophotometer (Tokkai Sho 55-035232). In this method, β-hydroxybutyric acid is first acted with β-hydroxybutyric acid dehydrogenase and nicotineamideadenine dinucleotide (NAD) to be oxidized enzymatically into acetoacetic acid, and then reacted with p-nitrophenyldiazonium fluoroborate into an azo compound, together with the acetoacetic acid contained originally in the blood. The azo compound is reduced with hypophosphorous acid into a stable hydroazo compound, and the total acetoacetic acid is determined by colorimetry of the hydroazo compound by use of the wave length of 390 nm. Separately, only the acetoacetic acid originally contained in the blood is measured by similar colorimetry but without action of β-hydroxybutyric acid dehydrogenase. The above total quantity of acetoacetic acid is subtracted by this acetoacetic acid quantity to give the quantity of β-hydroxybutyric acid in the blood. This method, however, has still had a number of problems as a daily clinical examination method, requiring high skill and long time for measurement because of pretreatment (protein removal) of the blood sample and complex operation, and needing special utensils and a high-class spectrophotometer.
As the simpler examination measure, there is Owen's tester for determining β-hydroxybutyric acid (U.S. Pat. No. 4,351,899). Owen's tester has two absorptive test surfaces wherein the first absorptive test surface contains tetrazolium salt, NAD, and electron transporter, and dried residue of β-hydroxybutyric acid dehydrogenase, and the second absorptive test surface contains dried residue of pH buffer. In using the test indicator, the first test surface is put on the second test surface, and a material is dropped on them, and the concentration of β-hydroxybutyric acid in the material can be measured by reading the hue after 2 min from dropping. It maintains the stability of the test indicator that it has two absorptive test surfaces. Owen states that if tetrazolium salt, NAD, an electron carrier, β-hydroxybutyric acid dehydrogenase, and pH buffer for maintaining pH in alkaline side, which are reagents necessary for determining β-hydroxybutyric acid, are dissolved in one solution, color development occurs.
Owen's test indicator has surely made a progress in simplicity. However, it is troublesome that a sample has to be dropped on the two absorptive test surfaces put on each other after taken out from separate vessels for drying. Further, although both reagents on the first and second absorptive test surface have to be dissolved uniformly to advance the reaction quantitatively, only dropping a sample on the two absorptive surfaces put on each other can not provide a uniform reaction condition. Accordingly, Owen's test indicator is lacking in quantitativity as a major problem.
SUMMARY OF THE INVENTION
It is an object of the invention to provide a stable composition for β-hydroxybutyric acid determination which eliminates the drawbacks of the conventional techniques and can be used by physicians, nurses, as well as patients themselves quickly and simply without using special instruments.
Another object of the invention is to provide a method for preparing the said composition.
As the result of assiduous study to attain these objects, the inventors have found a stable composition for determining β-hydroxybutyric acid made in one united body by using high molecular polymer, in which β-hydroxybutyric acid is dehydrogenated by β-hydroxybutyric acid dehydrogenase at pH 7-9 under the presence of nicotineamideadenine dinucleotide (NAD), and the produced NAD of reduced type (NADH) reduces tetrazolium salt through electron transporter, and the color degree of the produced formazan is measured to determine β-hydroxybutyric acid.
Further, the inventors have found that the stablest composition of little background color can be obtained by using 1-methoxy PMS or diaphorase as electron transporter and using nitro-TB (3,3'-dimethoxy-4,4'-biphenylilene-bis[2-(p-nitrophenyl)-5-phenyl-2H.tetrazolium]) as tetrazolium salt.
In preparing the composition of the invention, β-hydroxybutyric acid dehydrogenase, NAD, electron transporter, and pH buffer for maintaining pH at 7-9 during the reaction are dissolved together with a high molecular polymer, then tetrazolium salt is dissolved, and then the solution is applied on a surface impermeable to liquid and dried.
Particularly, a stable test composition of no color development on the composition itself can be prepared by the following method. A solution, in which β-hydroxybutyric acid dehydrogenase, NAD, tetrazolium salt, and buffer are dissolved together with a hydrophilic high molecular polymer, is mixed with a solution dissolved a film forming polymer in organic solvent insoluble in water, and W/O emulsion formed by dispersing is uniformly applied on a supporter impermeable to water.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram showing the reaction time course by the recipe of Reference Example 1 according to the invention, and
FIG. 2 shows a calibration curve for the recipe of Reference Example 1 according to the invention.
(1) FIG. 1 (2) Absorbance (3) Reaction time(min) (4) FIG. 2 (5) β-Hydroxybutyric acid(mM)
DETAILED DESCRIPTION OF THE INVENTION
According to the measurement principle of the invention, β-hydroxybutyric acid is first dehydrogenated by β-hydroxybutyric acid dehydrogenase at pH 7-9 under the presence of an electron acceptor, NAD, into acetoacetic acid, as shown below. The reduced type NAD (NADH) produced here reduces tetrazolium salt through an electron transporter into colored formazan. The color comparison of this formazan gives the quantity of β-hydroxybutyric acid. ##STR1##
Making use of the principle, when a drop of the specimen is applied on the composition of the invention prepared dexterously, color corresponding to the concentration of β-hydroxybutyric acid in the specimen appears on the composition after several minutes. Only comparing this by the naked eye with the standard color table prepared in advance provides determination of the β-hydroxybutyric acid concentration. The composition may be added with various additives, as required, such as retaining agents, stabilizers, and reaction accelerators.
Owen (U.S. Pat. No. 4,351,899) states that in case β-hydroxybutyric acid dehydrogenase, NAD, electron transporter, tetrazolium salt, and pH buffer for providing a pH condition appropriate to the reaction, which are used for the measurement principle of the invention, are united into one solution, the solution developes color. The inventors examined this problem.
According to the recipe of Example 1 by Owen (U.S. Pat. No. 4,351,899), the impregnating solution for the first absorptive test surface and that for the second one were separately prepared, and when a mixed impregnating solution was prepared by uniting both solutions, immediately the solution was colored purple. When absorptive paper (corresponding to Eaton Dikeman Paper #204, Filter Paper #50 made in Toyoroshi) was dipped in this mixed impregnating solution and air dried, the prepared test indicator itself was colored dark purple, being entirely unusable as test paper. As Owen stated, the presence of buffer for pH 8.8 resulted in a unusable state because of the color development on the test surface.
The recipe of Example 1 by Owen (U.S. Pat. No. 4,351,899)
Impregnating solution for the first absorptive test surface
______________________________________(1) β-Hydroxybutyric acid dehydrgenase 60 IU/ml(2) NAD 21 mM(3) Meldola blue 0.25 mM(4) INT 8.9 mM(5) Tetrazolium reducing catalyst 0.1 mM (K.sub.2 PdCl.sub.4)(6) Formazan stabilizer 1% V/V Triton X-100______________________________________
Impregnating solution for the second absorptive test surface
______________________________________Glycine-sodium hydroxide 1 M (pH 8.8)BufferMonopotassium phospate-dipotassium phosphate 1 M (pH 8.8)BufferEquivolume mixture of the above both buffers______________________________________
The first and second absorptive test surfaces were prepared truly according to Example 1 in Owen's Patent, and both were put separately into airtight vessels shading the light in the presence of a sufficient amount of a drying agent (silicagel). In storing at 40° C., the color of the first absorptive test surface added purple to the original pale blue after 10 hr, and indicated deep purple after 20 hr, indicating the similar hue with one developed from the liquid sample containing relatively high concentration (2 mM) of β-hydroxybutyric acid. In storing at 25° C., the above mentioned hue was indicated after about 2 weeks. A tester with such degree of conservative stability is lacking in practicality as one for determining β-hydroxybutyric acid in body fluids, being unable to be offered to users as goods.
When serum containing 0.5 mmol/l of β-hydroxybutyric acid was applied on this tester and the color reaction was observed, it took 2 min until apparent color development and 6 min untill above a definite deepness of color, substantially requiring a longer reaction time than the tester of the invention. This is because the tester is composed of two test surfaces and the carrier of ingredients is paper.
In view of the above conditions, as the result of assiduous study to find a composition of excellent conservative stability for determining β-hydroxybutyric acid, the inventors have found that using NTB as diazonium salt and 1-methoxy PMS as electron transporter reduces the color of the solution itself even when all reagents necessary for the reaction are dissolved in a liquid.
Further, the inventors have found that using natural or synthesized film forming polymer as binder of ingredients of the composition in these reagents solutions improves the conservative stability, and found that a composition of excellent conservative stability and of no color on the composition itself can be prepared by dissolving lastly tetrazolium salt in preparing impregnating solution containing natural or synthesized binder and by applying immediately and drying. Only a hydrophilic binder may be used, or a hydrophilic binder dispersed in a hydrophobic binder may be used.
The β-hydroxybutyric acid dehydrogenase used in the invention may be any one which can oxidize β-hydroxybutyric acid into acetoacetic acid, including those derived from bacteria such as Rhodopseudomonas spheroides and Pseudomonas lemoigneis and those extracted from animal tissues such as the heart of cattle and liver of pig.
The NAD used in the process of the invention is a coenzyme which exhibits hydrogen atom acceptance action in oxidation-reduction system reaction, including those extracted from animal tissues such as the liver and kidney and from yeasts. Their sodium salts and lithium salts are also usable.
The electron transporter used in the invention may be any one which can activate the hydrogen donating action of produced NADH, typified by diaphorase, a kind of flavin enzyme, and intermediate electron transporters such as 9-dimethylaminobenzo-α-phenazoxonium chloride (shortened as Meldoa blue), N-methylphenazonium methosulfate (shortened as PMS), and 1-methoxy-5-methylphenazonium methylsulfate (shortened as 1-methoxy PMS). The particularly preferable are 1-methoxy PMS and diaphorase which are stable.
The tetrazolium salts are reduced to formazans, colored substance, under the presence of reducing substances and include many monotetrazolium salts and ditetrazolium salts. The typical examples of the former are 3-(p-iodophenyl)-2-(p-nitrophenyl)-5-phenyltetrazolium chloride (shortened as INT) and 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyl-2H-tetrazolium bromide (shortened as MTT). The typical examples of the latter are 3,3'-(3,3'-dimethoxy-4,4'-biphenylylene)-bis-(2,5-diphenyl-2H-tetrazolium chloride) (shortened as TB) and 3,3'-(3,3'-dimethoxy-4,4'-biphenylylene)-bis-[2-(paranitrophenyl)-5-phenyl-2H-tetrazolium] (shortened as nitro-TB). Of these compounds, preferable is nitro-TB which is readily soluble in water and relatively stable.
Hydrophilic natural or synthesized organic film forming polymers are gum arabic, alginic acid, gelatin, dextran, prulan, carboxymethylcellulose, hydroxypropylcellulose, polyvinyl alcohol, and sodium polyacrylate. Hydrophobic binders are ethylcellulose, celluloseacetate, ethylpolyacrylate, polyvinylbutyral, polyvinylacetate, and polyvinylcarbazole. Of these compounds, preferable hydrophilic binders are gelatin and polyvinyl alcohol, and preferable hydrophobic binders are ethylcellulose and polyvinylbutyral.
The pH buffer used in the invention may be any one which gives best pH conditions (7-9) to enzyme reaction and color reaction and includes phosphoric acid buffer, boric acid buffer, tris buffer, and Good's buffer which are able to maintain above pH conditions. Other additives can also be used.
The above reagents are dissolved, for example, in water, and the aqueous solution is applied with an addition of a binder on a supporter such as polyester film to a thickness. The supporter, after being dried, is cut, for example, to about 5 mm square to form a test piece and adhered to an end of a strip of plastic film.
When a sample of body fluid such as serum, blood plasma, and urine is dropped on the test piece, it develops color after several minutes. When the sample is a whole blood, forming a semipermeable layer which allows low-molecular substances such as β-hydroxybutyric acid to pass through it but does not allow macro substances such as red corpuscle, permits observation of the color on the test piece without interference by red color of the corpuscles, since the corpuscles can be washed or wiped off after color reaction. The developed color is compared by the naked eye with the standard color table which has been prepared in advance and gives the concentration of β-hydroxybutyric acid in the body fluid. It is possible to obtain a higher accuracy of the measurement by using a simple reflectmeter having a light source corresponding to the developed hue.
Examples found in the process of the study are described to help to understand the invention as Reference Examples in the following.
REFERENCE EXAMPLE 1
A reagent was prepared by dissolving 10 mg of β-hydroxybutyric acid dehydrogenase (origin: Pseudomonas lemoigneis, relative activity: 10 U/mg), 33 mg of NAD, 3 mg of an electron transporter (1-methoxy PMS), and 17 mg of tetrazolium salt (nitro-TB) in 100 ml of 0.1M-trishydroxyaminomethane-hydrochloric acid buffer solution (pH 8.5).
Each 3.0 ml of this reagent was put in test tubes, and each 20 μl of aqueous β-hydroxybutyric acid solution (standard solutions: 0, 2, 4, 6, 8, 10 mmol/l) was added to the respective test tubes. The absorbance of each mixture was measured after being held at 37° C. for 0.5, 1, 2, 3, 4, and 5 min by a colorimeter with monochromatic light of 520 nm. The results are shown in Table 1.
TABLE 1______________________________________Reaction time 0.5 min 1 min 2 min 3 min 4 min 5 min______________________________________0 mM 0.257 0.260 0.263 0.264 0.263 0.2642 mM 0.282 0.346 0.407 0.434 0.440 0.4414 mM 0.308 0.437 0.533 0.591 0.609 0.6086 mM 0.363 0.512 0.669 0.752 0.784 0.7828 mM 0.406 0.607 0.810 0.915 0.949 0.95210 mM 0.511 0.748 1.008 1.106 1.129 1.131______________________________________
To show the reaction time course, FIG. 1 was plotted with the reaction time as the abscissa and the absorbance as the ordinate. From FIG. 1, it was found that the reagent itself is little colored in view of the change of absorbance in the sample of 0 mmol/l and the reaction reaches the end point in about 4 min.
Further, a calibration curve (FIG. 2) was drawn up with the absorbance of each standard solution measured after 4 min where the reaction had reached the end point (subtracted by the absorbance 0.263 of 0 mol/l, a blank value) as the ordinate and the concentration of the standard solutions as the abscissa. A straight line up to 10 mol/l of β-hydroxybutyric acid through the origin was obtained.
Twenty microliters of a patient serum specimen was added to 3.0 ml of reagent of the above recipe, and the mixture was reached at 37° C. for 5 min. The absorbance of the mixture measured using a monochromatic light of 520 nm was 0.27. From the calibration curve of FIG. 2, the concentration of β-hydroxybutyric acid in the specimen is 3.10 mmol/l.
As revealed in this Example, β-hydroxybutyric acid can be determined even in a single reagents solution at pH 8.8 by using 1-methoxy PMS as electron transporter and nitro-TB as diazonium salt.
Thus, this method enables the determination of β-hydroxybutyric acid in the specimen by adding 20 μl of the specimen to 3.0 ml of the reagent of the above recipe, reacting the mixture at a certain temperature for 4-5 min, measuring the absorbance of a monochromatic light around 520 nm by the reacted mixture, and by reference of the absorbance to the calibration curve prepared in advance under the same conditions.
REFERENCE EXAMPLE 2
To reveal the difference between the tester described in Example 1 by Owen and the composition of the invention, a test piece wherein all reagents necessary for determining β-hydroxybutyric acid were impregnated in one absorptive carrier was prepared by using 1-methoxy PMS as electron transporter and nitro-TB as tetrazolium salt and by adding cattle serum albumin.
One milligram of 1-methoxy PMS, 100 mg of cattle serum albumin as stabilizer, and 50 U of β-hydroxybutyric acid dehydrogenase (origin: Pseudomonas lemoigneis) were dissolved in 10 ml of 0.1M boric acid-borax buffer solution (pH 8), and then nitro-TB was dissolved, and immediately filter paper was dipped in this solution and air-dried at room temperature. In this time, the filter paper so slightly colored blue as not to give an influence on the determination of β-hydroxybutyric acid.
The dried filter paper was cut into a 5-mm square test piece and adhered to the end of a 5×70 mm strip of PVC film with double coated adhesive tape. The test piece was dipped in the specimen or a drop of the specimen was applied on the test piece. After 3 min of reaction, blue-purple color was developed on the test piece.
The concentration of β-hydroxybutyric acid in the specimen could be determined by comparing the hue of the developed color with the standard color table, prepared in advance, showing the hue of developed color corresponding to 0, 0.1, 0.2, 0.5, 1.0, 2.0, 5,0, and 10.0 mmol/l of β-hydroxybutyric acid.
The test piece, however, prepard in this Example is so unsatisfactory in stability as showed in Example 4 that it cannot be offered to users as goods.
EXAMPLE 1
One point five milligrams of 1-methoxy PMS, 1.5 g of gelatin, 8 mg of NAD, and 100 U of β-hydroxybutyric acid dehydrogenase (origin: Rhodopseudomonas spheroides) were dissolved in 10 ml of 0.1M tris-hydroxyaminomethanehydrochloric acid buffer solution (pH 8), and then 100 mg of nitro-TB was dissolved in the solution. Immediately, the solution was applied in uniform 0.4 mm thickness on polyester film using a doctor knife and dried at 25° C. for 2 hr.
The dried film was cut into a 5×7 mm test piece and adhered to an end of a 5×90 mm strip of PVC film to form a test strip. A drop of patient serum containing various concentration of β-hydroxybutyric acid was applied on the test piece of the test strip. After 2 min of reaction, excessive serum was lightly sucked up with absorptive paper. After further 3 min when the developed color was stabilized, it was compared by the naked eye with the standard color table, prepared in advance, showing the hue of developed color corresponding to 0, 0.1, 0.2, 0.5, 1.0, 2.0, 5.0, and 10.0 mmol/l of β-hydroxybutyric acid in the patient serum.
Table 2 shows the result of β-hydroxybutyric acid concentration determined by the method of the invention (measurement x) and by that described in Japanese Tokkai Sho 55-35232 specification (measurement y) on the same serum samples. Both the measurements show good correlationship with a correlation coefficient of 0.988 and regression line equation:
y=1.06x-0.02
TABLE 2______________________________________Specimen No. x y Specimen No. x y______________________________________1 0.05 0.07 16 0.1 0.042 0.5 0.47 17 0.15 0.203 0.2 0.25 18 0.1 0.074 0.7 0.73 19 0.1 0.095 0.3 0.51 20 0.2 0.246 1.5 1.36 21 0.3 0.297 1.5 1.52 22 0.5 0.438 0.2 0.23 23 0.5 0.629 0.3 0.25 24 0.5 0.5710 2.0 2.31 25 0.1 0.111 2.0 1.76 26 0.05 0.0812 3.0 3.05 27 0.1 0.1213 3.0 2.76 28 0.25 0.3214 5.0 4.84 29 0.3 0.2715 5.0 6.17 30 1.0 1.07______________________________________
EXAMPLE 2
The composition of Reference Example 2 was added with 1 g of ethyl cellulose dissolved in 10 ml of chloroform and 1.5 ml of 20% aqueous gelatin solution, and formed W/O emulsion being dispersed by strong stirring. This emulsion was uniformly applied by use of a doctor blade 0.15 mm thick on polyester film, and gave porous semipermeable membrane after being dried for 45 min at 30° C.
The obtained membrane was processed into a tester similar to that in Reference Example 2. One drop of a whole blood sample was applied on the test piece of the test strip. When surplus sample was wiped off after 3 min with absorbent cotton, the corpuscle component was removed and blue-purple color corresponding to the concentration of β-hydroxybutyric acid in the whole blood was revealed.
EXAMPLE 3
A solution (1) was prepared by dissolving 120 mg of NAD, 4000 U of diaphorase, 60 mg of nitro-TB, 2000 U of β-hydroxybutyric acid dehydrogenase (origin: Pseudomonas lemoignei), and 1 g of gelatin in 10 ml of 0.2M-monopotassium phosphate--borax buffer solution (pH 8). To a solution (2) of 1 g of ethylcellulose dissolved in 10 ml of chloroform, 3.0 ml of the above solution (1) was added, and formed W/O emulsion being dispersed by strong stirring. This emulsion was uniformly applied by use of a doctor blade 0.15 mm thick on polyester film, and gave porous semipermeable membrane after being dried for 45 min at 30° C.
This test strip could measure the concentration of β-hydroxybutyric acid in the whole blood sample in 3 min according to the method showed in Example 2.
Since diaphorase was used as electron transporter in the composition of this Example, the composition had the conservative stability of 6 months at 25° C. Further, the concentration of β-hydroxybutyric acid in blood in the whole blood sample could be measured without making serum (or plasma) by separating corpuscles. The developed blue-purple color corresponding to the concentration of β-hydroxybutyric acid on the test surface was more uniform than that on a tester surface of paper carrier, a measurement result of high accuracy being acquired.
EXAMPLE 4
The results of the examination of conservative stability of the compositions prepared in Reference Example 2 and Example 1-3 (periods until the judgement of the concentration of β-hydroxybutyric acid became difficult because the test surfaces were colored dark blue-purple from original cream color) are showed in Table 3.
TABLE 3______________________________________Tester Store at 40° C. 25° C. 4° C.______________________________________Example 1 by Owen 20 hrs 14 days 30 daysReference Example 2 1 day 7 days 15 daysExample 1 2 days 15 days 3 monthsExample 2 4 days 30 days 12 monthsExample 3 4 days 30 days 15 months______________________________________
Compared with Example 1 by Owen, the stability of test pieces united in the presence of buffer also was nearly equal in Reference Example 2, improved in Example 1, and definitely better in Example 2 and 3. From the above results, the conservative stability is improved by adding a hydrophilic binder. Further, a stable composition usable as goods for determining β-hydroxybutyric acid can be prepared by applying and drying W/O emulsion formed by dispersing in a hydrophobic binder.
While the described Examples represent the preferred form of the invention, it is to be understood that the invention is not limited thereto and various modifications can be made without departing from the spirit of the invention. For example, proteins and polysaccharides are used as a stabilizer of enzyme and color producing agent and hydrazine compounds and magnesium compounds are used as a reaction accelerator. Various additives such as consistency agent and surfactant can also be used. The solvent may be various organic solvents, not only being water. Each material may be dispersed in the solvent in the form of suspension or emulsion, not necessarily be dissolved. Further, the invention can be applied to the quantitative analysis of β-hydroxybutyric acid in food additives and other specimens, in addition to the above described clinical examination field.
As detailed above, the invention comprises a uniform solid-phase composition of reagents by which β-hydroxybutyric acid can be determined, and also comprises a method for preparing the said composition. In the invention, β-hydroxybutyric acid is determined according to the following method.
β-Hydroxybutyric acid is dehydrogenated at pH 7-9 under the presence of NAD by β-hydroxybutyric acid dehydrogenase, NADH produced here reduces tetrazolium salt through an electron transporter into colored formazan in proportion to the quantity of β-hydroxybutyric acid, and the quantity of β-hydroxybutyric acid is determined by comparison of the developed color of formazan with the standard color table.
The method of the present invention, unlike the conventional methods, is very easy to use without requiring pretreatment of specimen (particularly blood), special equipment, complex operation, and special skill, and gives results in short time.
The composition of the invention realizes quick and simple operation and minimized the use of specimen, essential requirements for daily examination in the clinical field, requiring only one drop of specimen applied on the composition and completing the color development in several minutes. Particularly, in combination with the urine sugar and blood sugar test pieces available on the market, it permits measurement of both sugar and β-hydroxybutyric acid concentrations in urine and blood by similar operation. This is very convenient for doctors and nurses, and further for diabetes patients who have to be examined in their homes. Thus, the composition has very large practical value. | This invention relates to a composition for determining β-hydroxybutyric acid, usable for doctors, nurses, and patients themselves simply and quickly without use of special instruments, and also relates to a method for preparing the said composition.
The composition of the invention oxidizes β-hydroxybutyric acid under alkaline conditions and the presence of nicotineamide adenine dinucleotide (NAD) by β-hydroxybutyric acid dehydrogenase, and the produced reduction-type NAD (NADH) reduces tetrazolium salt through an electron carrier to produce formazan developing color. The composition permits accurate measurement quickly and simply, and has excellent conservative stability, because it is a uniform solid-phase composition prepared by applying reagents necessary for the reaction of film impermeable to water together with a natural or synthesized film forming polymer. The invention further provides a method for preparing the said composition by applying, on a supporter impermeable to water, W/O emulsion which is formed by dispersing alkaline buffer, β-hydroxybutyric acid dehydrogenase, NAD, electron carrier, and tetrazolium salt in an organic solvent insoluble in water together with a natural or synthesized film forming polymer. | 8 |
FIELD OF THE INVENTION
The present invention relates to a process for producing pitch (which is a raw material for producing carbon fibers having a high modulus of elasticity), using a petroleum heavy residual oil.
BACKGROUND OF THE INVENTION
In pitches which are used as a raw material for producing carbon fibers having excellent strength and excellent modulus of elasticity, optical anisotropy is observed by a polarizing microscope. More specifically, such pitches are believed to contain a mesophase as described in U.S. Pat. No. 3,974,264. Further, it has recently been disclosed in Japanese Patent Application (OPI) No. 160427/79 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application") that carbon fibers having a high modulus of elasticity can be produced with a pitch containing a neomesophase. By heating such pitches for a short time optical anisotropy is observed in them. Further, pitches used as a raw material for carbon fibers need not possess only optical anisotropy but must also be capable of being stably spun. However, it is not easy to produce pitches having both properties. In order to produce carbon fibers having excellent strength and excellent modulus of elasticity, it is not always possible to use any material as the raw material for making pitches. Materials having specified properties have been required.
It should be noted that in many published patents, for example, as described in U.S. Pat. Nos. 3,976,729 and 4,026,788, the raw material is not specified in the claims of patent specifications. Furthermore, such patents indicate that pitches used as a raw material for carbon fibers can be produced only by carrying out thermal modification of a wide variety of raw materials. However, according to the detailed descriptions and examples in such patents, the desired pitches can only be produced by using specified raw materials.
For example, U.S. Pat. No. 4,115,527 discloses that substances such as chrysene, etc., or tarry materials by-produced in high temperature cracking of petroleum crude oil are suitable for producing the pitch, i.e., a carbon fiber precursor, but conventional petroleum asphalts and coal tar pitches are not suitable. Further, U.S. Pat. No. 3,974,264 discloses that an aromatic base carbonaceous pitch having a carbon content of about 92 to about 96% by weight and a hydrogen content of about 4 to about 8% by weight is generally suitable for controlling a mesophase pitch. It has been described that elements excepting carbon and hydrogen, such as oxygen, sulfur and nitrogen, should not be present in an amount of more than about 4% by weight, because they are not suitable. Further, Example 1 of the same patent publication discloses that the precursor pitch has properties comprising a density of 1.23 g/cc, a softening point of 120° C., a quinoline insoluble content of 0.83% by weight, a carbon content of 93.0%, a hydrogen content of 5.6%, a sulfur content of 1.1% and an ash content of 0.044%. Even if a density of 1.23 g/cc in these properties is maintained, it should be noted that it is difficult to obtain conventional petroleum heavy oil having such a high density. Examples as described in the other U.S. Pat. Nos. 3,976,729, 4,026,788 and 4,005,183 also disclose that the pitch is produced with a specified raw material.
The properties of heavy petroleum oils depend essentially upon the properties of crude oils from which they were produced and the process for producing the heavy oil. However, generally, it is rare that heavy oils having the suitable properties described in the above described Examples are produced, and, in many cases, they cannot be obtained. Accordingly, in order to produce carbon fibers industrially in a stabilized state, which have excellent strength and excellent modulus of elasticity with petroleum heavy oils, it is necessary to develop a process for producing a pitch wherein the finally resulting pitch has properties which are always within a specified range even if the properties of the raw material for the pitch vary.
SUMMARY OF THE INVENTION
Therefore, one object of this invention is to provide a process for producing a pitch useful as raw material for carbon fibers having an excellent strength and a high modulus of elasticity.
Another object is to provide a process for producing a pitch which can be used for producing carbon fibers having the above excellent properties industrially in a stabilized state.
Still another object is to provide a process for producing a pitch used as raw material for carbon fibers with an easily available petroleum heavy residual oil.
These objects of this invention are effectively accomplished with a process for producing a pitch used as a raw material for carbon fibers which comprises carrying out solvent extraction of a solvent deasphaltened oil which is prepared by solvent deasphaltening of a reduced pressure distillation residual oil prepared by reduced pressure distillation of a petroleum heavy residual oil, or solvent extraction of a reduced pressure distillate oil prepared by reduced pressure distillation of the petroleum heavy residual oil. The resulting solvent extraction component which is rich in aromatic components is then thermally modified.
DETAILED DESCRIPTION OF THE INVENTION
Examples of petroleum heavy residual oils which are used as a raw material include heavy residual oils such as atmospheric pressure distillation residual oils of crude oil, hydrogenating desulfurization residual oils, hydrocracking residual oils, thermal cracking residual oils and catalytic cracking residual oils. A distillate having a boiling point of 300° to 550° C. at atmospheric pressure and a reduced pressure residual oil having a boiling point of higher than 500° C. at atmospheric pressure are taken out of the petroleum heavy residual oil by means of a reduced pressure distillation apparatus conventionally used in the field of petroleum industry. Then, the reduced pressure residual oil having a boiling point higher than 500° C. prepared by reduced pressure distillation is subjected to solvent deasphaltening treatment to remove an asphaltene component which contains vanadium and nickel, etc., in large amounts. The solvent deasphaltening treatment is carried out with saturated hydrocarbon compounds having 3 to 5 carbon atoms, e.g., one or more of propane, butane and pentane, as a solvent under a condition comprising a ratio of solvent to oil of 3 to 15:1, a temperature of 50° to 150° C. and a pressure of 5 to 50 kg/cm 2 G, by which a deasphaltened oil is taken out. Then, the deasphaltened oil is subjected to solvent extraction treatment with furfural as a solvent to obtain a component (extract) which is rich in aromatic components.
The furfural extraction treatment is carried out under conditions comprising a ratio of solvent to oil of 1 to 4:1, a temperature of 45° to 145° C. and a pressure of 0.1 to 2.0 kg/cm 2 G. If necessary, the distillate oil having a boiling point of 300° to 550° C. prepared by reduced pressure distillation can be subjected to furfural extraction treatment without carrying out deasphaltening treatment. The specific conditions necessary for obtaining the best results for the reduced pressure distllation, deasphaltening treatment and furfural extraction treatment depend on the properties of the raw material and properties of the extraction component. By carrying out a series of these processes, differences in properties become small, even if there are great differences in properties of the raw material, by which the properties become suitable for carrying out the subsequent thermal modification.
The resulting furfural extraction component is then subjected to thermal modification at a temperature of 390° to 450° C. for 1 to 30 hours to produce a pitch used as a raw material for carbon fibers having high modulus of elasticity. The thermal modification period is necessary for control so that no infusible substances are formed which obstruct spinning when carrying out melt-spinning of the pitch.
The properties of the petroleum heavy residual oils used as the raw material vary largely each other. Accordingly, it is generally difficult to produce pitch which can be used as a raw material for making carbon fibers having high strength and high modulus of elasticity directly from every kind of petroleum heavy residual oil by only carrying out the thermal modification. However, some oils can be used for directly producing pitch which is used as a raw material for carbon fibers having high strength and high modulus of elasticity. The present invention is characterized by the fact that a pitch used as a raw material for making carbon fibers can be produced industrially and stably with various kinds of petroleum heavy residual oils. Useful oils include petroleum heavy residual oils which cannot yield a pitch which is useful as a raw material for making carbon fibers by only the conventional thermal modification. However, such oil can be made useful by carrying out a series of processings comprising reduced-pressure distillation→solvent deasphaltening→furfural extraction→thermal modification.
In the following, the present invention is illustrated in greater detail by examples. However, this invention is not limited to these examples.
EXAMPLE 1
An atmospheric pressure distillation residual oil was prepared by distilling Middle East crude oil A by an atmospheric pressure distillation apparatus. The residual oil was subjected to reduced pressure distillation to take out a fraction having a boiling point of higher than 500° C. The resulting reduced pressure distillation residual oil was subjected to solvent deasphaltening treatment with propane as a solvent under conditions comprising a ratio of solvent to oil of 6:1, a temperature of 75° C. and a pressure of 40 kg/cm 2 G to take out a deasphaltened oil. The resulting deasphaltened oil was subjected to solvent extraction treatment with furfural as a solvent under conditions comprising a ratio of solvent to oil of 3:1, a temperature of 120° C. and a pressure of 0.5 kg/cm 2 G. The resulting extraction component was subjected to thermal modification at a temperature of 410° C. for 15 hours to obtain a pitch which can be used as a raw material for making carbon fibers.
The properties of the atmospheric distillation residual oil of Middle East crude oil A used as a raw material and the properties of the extraction component after the furfural extraction treatment as well as the properties of the pitch which can be used as a raw material for carbon fibers are shown in Table 1. Further, carbon fibers which were obtained by melt-spinning of the above described pitch at 370° C., infusiblizing at 260° C. in air and carbonizing at 1,000° C. had a tensile strength of 9 tons/cm 2 and a modulus of elasticity of 900 tons/cm 2 . When carbonized fibers prepared by carbonizing at 1,000° C. were additionally graphitized at 1,900° C., they had a tensile strength of 13 tons/cm 2 and a modulus of elasticity of 2,200 tons/cm 2 .
EXAMPLE 2
An atmospheric pressure distillation residual oil was prepared by distilling Middle East crude oil B by an atmospheric pressure distillation apparatus. The residual oil was subjected to reduced pressure distillation to take out a fraction having a boiling point above 500° C. The resulting reduced pressure distillation residual oil was subjected to solvent deasphaltening treatment with propane as a solvent under conditions comprising a ratio of solvent to oil of 6:1, a temperature of 76° C. and a pressure of 40 kg/cm 2 G to take out a deasphaltened oil. The resulting deasphaltened oil was subjected to solvent extraction treatment with furfural as a solvent under conditions comprising a ratio of solvent to oil of 3.5:1, a temperature of 120° C. and a pressure of 0.5 kg/cm 2 G. The resulting extraction component was subjected to thermal modification at a temperature of 405° C. for 17 hours to obtain a pitch which can be used as a raw material for making carbon fibers.
The properties of the atmospheric distillation residual oil of Middle East crude oil B used as a raw material, and the properties of the extraction component after the furfural extraction treatment as well as the properties of the pitch which can be used as a raw material for carbon fibers are shown in Table 1. Further, carbon fibers which were obtained by meltspinning of the above described pitch at 345° C., infusiblizing at 260° C. in air and carbonizing at 1,000° C. had a tensile strength of 9.5 tons/cm 2 and a modulus of elasticity of 850 tons/cm 2 . When carbonized fibers prepared by carbonizing at 1,000° C. were additionally graphitized at 1,900° C., they had a tensile strength of 13 tons/cm 2 and a modulus of elasticity of 2,250 tons/cm 2 .
EXAMPLE 3
An atmospheric pressure distillation residual oil was prepared by distilling Middle East crude oil A by an atmospheric pressure distillation apparatus. The residual oil was subjected to reduced pressure distillation to take out a fraction having a boiling point of 390° to 450° C. The resulting reduced pressure distillate oil was subjected to solvent extraction treatment with furfural as a solvent under conditions comprising a ratio of solvent to oil of 1.2:1, a temperature of 110° C. and a pressure of 0.5 kg/cm 2 G. The extraction component was subjected to thermal modification at a temperature of 420° C. for 10 hours to obtain a pitch which can be used as a raw material for making carbon fibers.
The properties of the atmospheric distillation residual oil of Middle East crude oil A used as a raw material, and the properties of the extraction component after furfural extraction treatment as well as the properties of the pitch which can be used as a raw material for carbon fibers are shown in Table 1. Further, carbon fibers which were obtained by melt-spinning of the above described pitch at 350° C., infusiblizing at 260° C. in air and carbonizing at 1,000° C. had a tensile strength of 10 tons/cm 2 and a modulus of elasticity of 820 tons/cm 2 . When carbonized fibers prepared by carbonizing at 1,000° C. were additionally graphitized at 1,900° C., they had a tensile strength of 14 tons/cm 2 and a modulus of elasticity of 2,300 tons/cm 2 .
COMPARATIVE EXAMPLE 1
An atmospheric pressure residual oil of the Middle East crude oil A was subjected to thermal modification at a temperature of 410° C. for 15 hours. The properties of the atmospheric pressure distillation residual oil of the Middle East crude oil A used as a raw material and those of the pitch are shown in Table 1. Further, fibers which were prepared by melt-spinning the pitch at 370° C., infusiblizing in air and carbonizing at 1,000° C. had a tensile strength of 3.0 tons/cm 2 and a modulus of elasticity of 250 tons/cm 2 . When the fibers prepared by carbonizing at 1,000° C. were additionally graphitized at 1,900° C., they had a tensile strength of 2.8 tons/cm 2 and a modulus of elasticity of 240 tons/cm 2 .
TABLE 1______________________________________ Ex- Ex- Ex- ample ample ample Comparative 1 2 3 Example 1______________________________________Properties ofraw materialSpecific gravity 0.955 0.982 0.955 0.955@ 15/4° C.Kinematic viscosity 230 1,344 230 230cSt @ 50° C.Residual carbon 8.5 13.73 8.5 8.5content (wt %)Sulfur content (wt %) 3.0 4.3 3.0 3.0Carbon content (wt %) 85.2 84.3 85.2 85.2Hydrogen content 11.2 10.6 11.2 11.2(wt %)Ash (wt %) 0.01 0.02 0.01 0.01Properties of furfuralextraction componentSpecific gravity 0.990 1.01 1.02@ 15/4° C.Kinematic viscosity 1.629 744 210cSt @ 50° C.Residual carbon 6.8 10.2 0.56content (wt %)Sulfur content (wt %) 4.0 5.0 5.1Carbon content (wt %) 82.2 84.0 84.1Hydrogen content 10.3 10.5 10.1(wt %)Ash (wt %) 0.00 0.00 0.00Properties of pitchSpecific gravity 1.31 1.30 1.30 1.30@ 25/25° C.Softening point (°C.) 330 315 320 330Quinolin insoluble 28.1 26.2 25.6 35.4content (wt %)______________________________________
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. | A process for producing a pitch which can be utilized as a raw material for producing carbon fibers is disclosed. The process involves distilling a petroleum heavy residual oil under reduced pressure to produce a reduced pressure distillation residual oil or a reduced pressure distillate oil. The distillation residual oil is subjected to a solvent deasphaltening treatment to produce a solvent deasphaltened oil. The solvent deasphaltened oil or the reduced pressure distillate oil is subjected to solvent extraction to obtain a solvent extraction component. The solvent extraction component is thermally modified to produce the pitch. The pitch can be utilized in a melt-spinning process in order to produce carbon fibers having desirable characteristics. | 2 |
BACKGROUND OF THE INVENTION
The present invention relates to an improved vehicle barrier construction for stopping unauthorized passage of vehicles.
By way of background, there are numerous vehicle barrier constructions known wherein a pivotal barrier member is movable from a retracted position in which a vehicle can pass over it to an extended position in which it obstructs vehicles. This general type of vehicle barrier is shown in U.S. Pat. Nos. 1,949,295, 2,362,912, 2,741,859 and 4,152,871. It is with an improvement over the foregoing type of vehicle barrier that this invention is concerned.
SUMMARY OF THE INVENTION
It is one object of the present invention to provide a vehicle barrier which can be detached from its mounting when it experiences an impact force above a predetermined value so that it will throw a vehicle into the air and thus disable it against further movement.
Another object of the present invention is to provide an improved vehicle barrier which is fabricated so as to absorb the energy of vehicle impact and thus stop a vehicle more efficiently.
A further object of the present invention is to provide an improved vehicle barrier which can be installed in an extremely simple and efficient manner. Other objects and attendant advantages of the present invention will readily be perceived hereafter.
The present invention relates to a vehicle barrier comprising a barrier having a roadway surface and a barrier surface, means mounting said barrier for movement between a retracted first position where said roadway surface lies substantially flush with a roadway and an extended second position where said barrier surface obstructs a vehicle on said roadway, and release means for permitting said barrier to pivot beyond said second position in the event said barrier surface receives an impact force above a predetermined value from a vehicle to thereby tend to raise said vehicle off of said roadway.
The present invention also relates to a vehicle barrier comprising a housing, a barrier having a roadway surface and a barrier surface, means for mounting said barrier for movement between a retracted position where said roadway surface lies substantially flush with a roadway and an extended position where said barrier surface obstructs a vehicle on said roadway, motor means effectively located between said housing and said barrier for moving said barrier between said retracted position and said extended position, and cooperating means on said housing and on said barrier for effecting automatic alignment between said barrier and said motor means upon installation of said barrier means into said housing.
The present invention also relates to a vehicle barrier comprising a housing, a barrier having a roadway surface and a barrier surface, means for mounting said barrier for movement between a retracted position where said roadway surface lies substantially flush with a roadway and an extended position where said barrier surface obstructs a vehicle on said roadway, and energy absorber means on said barrier for absorbing the energy of impact of a vehicle, said energy absorber means comprising a plurality of deformable members behind said barrier surface.
The various aspects of the present invention will be more fully understood when the following portions of the specification are read in conjunction with the accompanying drawings wherein:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plan view, partially broken away, of the improved vehicle barrier of the present invention;
FIG. 1a is a fragmentary cross sectional view taken substantially along line 1a--1a of FIG. 1 and showing the constructional details of the supporting struts which underlie the upper surface of the barrier;
FIG. 2 is a cross sectional view taken substantially long line 2--2 of FIG. 1, with parts partially broken away and showing the details of the barrier ribs;
FIG. 3 is a side elevational view taken from the right of FIG. 1;
FIG. 4 is a cross sectional view taken substantially along line 4--4 of FIG. 1, with parts partially broken away, showing the barrier in a fully retracted position;
FIG. 5 is a view similar to FIG. 4 and showing the barrier in a fully extended position;
FIG. 6 is a cross sectional view taken substantially along line 6--6 of FIG. 4 and showing the structure at the bottom of the housing;
FIG. 7 is a cross sectional view taken substantially along line 7--7 of FIG. 4 with certain parts omitted in the interest of clarity and showing various details of the barrier ribs;
FIG. 8 is a cross sectional view taken substantially along line 8--8 of FIG. 4 and showing essentially the relationship between the planar upper surface of the barrier and the barrier ribs;
FIG. 9 is a fragmentary cross sectional view taken substantially along line 9--9 of FIG. 4 and showing the structure of the lower portion of the barrier;
FIG. 10 is a view taken substantially in the direction of arrows 10--10 of FIG. 14 and showing the structure of the bearing supports mounted on the rear wall of the housing;
FIG. 11 is a view taken substantially in the direction of arrows 11--11 of FIG. 10 and showing the bearing structure mounted relative to the rear wall of the housing;
FIG. 12 is a view taken substantially in the direction of arrows 12--12 of FIG. 14 and showing the relationship between the pivot shaft and the ribs of the barrier;
FIG. 13 is a fragmentary cross sectional view taken substantially along line 13--13 of FIG. 1 and showing the relationship between the upper front edge of the barrier and the upper edge of the front wall when the barrier is in a fully retracted position;
FIG. 14 is a fragmentary cross sectional view taken substantially along line 14--14 of FIG. 1 and showing the relationship between the pivot shaft, the bearing supports therefor, and the barrier ribs when the barrier is in a fully retracted position;
FIG. 15 is a fragmentary cross sectional view taken within the enclosed area denoted FIG. 15 of FIG. 5 and showing the relationship between the front wall of the housing and the breakaway lip on the barrier when the barrier is in its fully extended position;
FIG. 16 is a fragmentary cross sectional view taken substantially along line 16--16 of FIG. 5 and showing the relationship between the bottom wall of the housing and the barrier when the barrier is in its fully extended position; and
FIG. 17 is a fragmentary cross sectional view showing the support for the cylinder on the bottom wall of the housing.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Summarizing briefly in advance, the improved barrier of the present invention is movable from a fully retracted position, such as shown in FIG. 4, wherein its planar upper surface serves as a roadway, to a fully extended position, as shown in FIG. 5, wherein the arcuate surface of the barrier is in a position to obstruct the passage of vehicles. The barrier is collapsible to absorb the energy of impact, provided the total force of impact is below a predetermined value. However, if it exceeds the predetermined value, the barrier will pivot upwardly beyond its fully extended position and will tend to lift and overturn the vehicle which has struck it. Furthermore, the barrier itself is easily mountable and demountable from its associated housing for purposes of replacement and repair.
The improved vehicle barrier 10 of the present invention includes a housing 11 consisting of front wall 12, rear wall 13, side walls 14 and 15, and bottom wall 16. Walls 12 and 13 converge downwardly toward each other. The same is true of walls 14 and 15. Thus, there is a draft in the housing so that when it is set in cement 17 with a suitable lubricant between the walls and the cement, the housing 11 may be pulled out of the ground, if required, for replacement or repair. Angles 19, 20, 21 and 22 are welded to the upper edge portions of walls 12, 13, 14 and 15, respectively, to rigidize the walls in this area. The apices of the angles are substantially flush with the level of roadway 23 over which vehicles travel. Lifting lugs 24 (FIGS. 1 and 3) are welded at the junctions of angles 19 and 20 and walls 12 and 13, respectively, for receiving hooks for lifting the housing, as required, for both installing the housing into its associated pit and removing it therefrom. Channels 25 and 26 are welded to the inside surface 27 of front wall 12 and extend substantially the entire distance between side wall 14 and partition 29 (FIGS. 2 and 6) which extends between walls 12 and 13. Reinforcing channels 30 and 31 (FIGS. 2 and 4) are welded to the inside surface 32 of side wall 14 and extend substantially the entire distance between front wall 12 and rear wall 13. Reinforcing channels 33 and 34 are welded to side wall 15 and extend substantially the entire distance between front wall 12 and rear wall 13. Reinforcing channel 35 is welded to rear wall 13 and it extends substantially the entire distance between side wall 14 and partition wall 29. Channels 36 and 37 (FIG. 2) are welded to rear wall 13 and extend substantially the entire distance between partition 29 and side wall 15. All of the foregoing channels rigidize the wall sides of the housing against warping and they reinforce the walls against the fluid pressure exerted thereon by the concrete 17 when it is poured around housing 11 after the latter has been placed in a pit in the ground.
I-beams 40 and 41 are welded to the inside surface 42 of bottom wall 16. Channels 43 and 44 are welded to bottom wall 16 and extend between I-beams 40 and 41. An I-beam 45 is also welded to bottom wall 16 and extends between I-beams 43 and 44. A metal block 46 is welded to the top of I-beam 45 and extends substantially the entire distance between I-beams 40 and 41 (FIG. 6). The I-beams and channels welded to bottom wall 16 rigidize it. A conduit shielding housing 47 (FIGS. 1, 2 and 3) provide an enclosure for electrical and hydraulic conduits 49 which pass through end wall 15.
All of the walls of the housing are of heavy gauge steel approximately 1/4 inch thick and are welded to each other to provide a fluid-tight enclosure. A sump 39 (FIGS. 2 and 6) extends downwardly from bottom wall 16 to collect liquid which may drop into housing 11, and a suitable sump pump and associated hose are associated with sump 39 to periodically drain it.
A retractible and extendible barrier 50 is pivotally mounted within housing 11 and is movable between the retracted position of FIG. 4 and the extended position of FIG. 5, upon the actuation of the fluid motors 51 which effectively extend between bottom wall 16 and barrier 50. Barrier 50 includes a plurality of substantially parallel ribs 52 which are suitably joined to each other. Each rib 52 consists of an upper I-beam 53 and a lower I-beam 54 spaced therefrom. I-beams 53 and 54 converge and are welded to each other at their point of convergence. A gusset 55 is welded between I-beams 53 and 54. An I-beam 56 has its opposite ends welded to I-beams 53 and 54. Channels 57 and 59 have their opposite ends welded to I-beams 53 and 54 and curved channel 60 also has its opposite ends welded to I-beams 53 and 54.
Ribs 52 are joined to each other as follows: A pivot shaft 62 is suitably welded to the ends of I-beams 53 and 54 as shown. A templet 63 is welded to opposite sides of each web of each I-beam 53 to increase the rigidity thereof proximate pivot shaft 62. A templet 64 is welded to the web on the opposite side of each I-beam 54 proximate pivot shaft 62 in the same manner. A plurality of struts 65 (FIGS. 1 and 1a) have their opposite ends welded to channels 53 at 66. Struts 65 are in the form of channels having a base 67 and legs 69. Bases 67 are flush with the top surfaces 70 of I-beams 53. This is achieved by cutting away the bases 67 to accommodate the flanges of the I-beams, as can be visualized from FIG. 1a. Thus, the top surfaces 70 of the I-beams and the outer surfaces of struts 65 lie in a single plane. Plates 71 (FIGS. 4 and 7) are welded across the flanges of the outer two I-beams 56 of the barrier. Also, a plate 72 (FIGS. 2 and 9) is welded across the ends of the three inner I-beams 54. Additional plates 73 are welded across the ends of the outer I-beams 54.
An outer steel plate 74 forms a planar roadway surface across the top of the grid formed by I-beams 53 and struts 65. The end of plate 74 is bent to the shape shown at 75 (FIG. 13) and is secured by welding to the outer ends of I-beams 53. The underside of plate 74 is spot-welded to the gridwork of I-beams 53 and struts 67 at select points where they contact each other.
A steel plate 76 of arcuate shape is spot-welded at select locations to the outer edges of curved channels 60. Plate 76 extends across all of the channels 60 and its upper edge 77 is located in contiguous relationship to edge 79 of portion 75 of upper plate 74 (FIG. 13). The lower edge 80 of plate 76 terminates immediately above the ends of I-beams 54 (FIG. 2). End plates 81 of sector shape are screwed by screws 78 to brackets 82 and 83 at the ends of barrier 50. Openings 85 are located at the junctures of plates 75 and 81 for receiving hooks for lifting barrier 50 in and out of housing 11.
The barrier 50 is supported within housing 11 in the following manner: Three central bearings 87 and two end bearings 89 are mounted on rear wall 13 for receiving spaced portions of pivot shaft 62. Each central bearing 87 includes a plurality of gusset-like plates 89 (FIGS. 10, 11 and 14) having their vertical edges 90 welded to surface 91 of plate 88 welded to rear wall 13. Bearing material 93 is suitably affixed to cylindrical backer member 94 which is welded to the upper portions of each support member 89. Gusset-like members 89', which are of the same shape as members 89, support bearings 93' which mount the ends of pivot shaft 62. An angle 94' (FIGS. 10 and 14) extends across and is welded to the surface 95 of each of the gusset-like members 89 and 89'.
A break-away plate 97 (FIGS. 4, 5 and 15) has its end portion 99 (FIG. 15) welded to the underside of the three central I-beams 54 so that the outer portion 100 extends outwardly from curved plate 76. A round bar 101 is welded to portion 99 of member 97 and it rests on the top of square block 46 when the barrier 50 is in the retracted position (FIG. 4). Bar 101 extends across only the three central ribs 52. A plurality of spaced round bars 102 are welded to upper plate 74 at 103 and they rest on the upper surface 104 of angle 105' when the barrier 50 is in the retracted position, angle 104 being secured to plate 105, which extends the entire distance between partition 29 and side wall 14, by means of a plurality of spaced screws 106. Angle 104 is also supported by bar 107 welded to plate 105 which is welded to front wall 12. Thus, when the barrier 50 is in it fully retracted position, it is supported (1) by pivot shaft 62 mounted in bearings 93, (2) by rod 101 resting on bar 46, and (3) by rods 102 bearing on angle 104.
The barrier 50 is raised from its fu11y retracted position of FIG. 4 to its fully extended position of FIG. 5 by spaced hydraulic motors 51 comprising cylinders 109 and pistons 110. The lower ends of cylinders 109 are pivotally mounted at 111 on brackets 112 which are welded to bottom wall 16. Supports 112' have their bases suitably attached to bottom wall 16, as by welding, and enlarged rings 113 loosely encircle cylinders 109. When the barrier 50 is not installed in housing 11, cylinders 109 will rest against plates 114 of supports 112'.
In order to install barrier 50 into housing 11, pistons 110 are retracted into cylinders 109. Hooks are applied to holes 85 of barrier 50 and a chain lift is used to lower barrier 50 into housing 11. During this lowering, shaft 62 is aligned with bearings 93 and rods 102 are aligned with angles 104. As the barrier 50 is lowered, a point will be reached where balls 115 at the ends of piston rods 110 will enter frustoconical funnel-shaped members 116 welded to channels 117 which in turn are welded to I-beams 53. The frustoconical funnel members 116 will guide balls 115 into mating engagement with sockets 119 at the ends of members 116. Thus, the ends of piston rods 110 are self-aligning with barrier 50 as it is lowered into position. During the installation, as balls 115 move into position, cylinders 109 will move away from plates 114 of supports 112'.
Normally roadway surface 74 of barrier 50 lies substantially even with roadway 23 when the barrier is in its fully retracted position of FIG. 4. However, as the need arises, motors 51 are actuated and the barrier is caused to pivot about the axis of pivot shaft 62 to the position of FIG. 5. It will continue its movement until the upper surface 120 of break-away plate 97 abuts the undersurface of plate 105. Plate 76 of barrier 50 will obstruct traffic traveling on roadway 23 in the direction of arrow 121 (FIG. 5). If the vehicle has a momentum less than a predetermined value, impact with plate 76 will cause it to buckle to the right in FIG. 5 to thereby deform this plate, and also deform the curved channels 60 which back up the plate, thereby absorbing the energy of impact. If the momentum is greater, channels 59 will also be deformed, and if the momentum is still greater, channels 57 will be deformed. The deformation of the various channels absorbs the energy of impact to thereby stop the vehicle. However, if the momentum of the vehicle exceeds a predetermined value, a point will be reached where break-away plate 97 fractures at weakened grooved portion 122, which may extend the entire length of plate 97. After fracture of plate 97, the impact of the vehicle will cause the barrier 50 to rotate clockwise about the axis of pivot shaft 62 beyond its fully extended position shown in FIG. 5. The continued movement of the vehicle to the right in FIG. 5 along with the pivotal motion of barrier 50 as it is supported on its pivot shaft 62 will cause the vehicle to be lifted from the ground and thrown upwardly, thereby upsetting it and causing it to stop before its forward motion causes it to move any appreciable distance beyond barrier 50. In other words, the barrier 50 may in certain instances severely damage the underside of the vehicle by ripping its oil pan, mutilating its transmission, or breaking its drive shaft. Also, it may cause the vehicle to tip over as a result of throwing it into the air. In any event, if the barrier 50 does not stop the vehicle before the break-away plate 97 fractures, it will tend to stop the vehicle by severely damaging it or turning it over after the break-away plate 97 has fractured. By way of example, and not of limitation, the break-away plate 97 may be designed to fracture when struck by a six-ton vehicle traveling at 35 mph. Below this impact value, the barrier 50 will be deformed to the degrees set forth above. However, it will be appreciated that break-away plate 97 may be designed to fracture at any desired impact value.
The various operating components, such as the pumps, motors, accumulators and various controls are mounted in a frame 124 (FIGS. 2 and 6) which is removable from housing 11. More specifically, frame 124 includes a pair of spaced channels 125 having holes at their opposite ends which receive pins 126 which extend upwardly from bottom wall 16. The frame also includes upstanding angles 127 having their bottom edges welded to channels 125. Cross braces, such as 129, bridge the upper ends of members 127 and a plate, such as 130, extends across channels 125 to support various pieces of equipment thereon. A cover 131 is suitably mounted on housing 11 and is supported on angles 132. When cover 131 is removed, a crane may be used to lift frame 124 out of the housing and replace it with another frame carrying substitute equipment.
An opening (not shown) is located in partition 29 for permitting various hydraulic conduits to pass from the hydraulic components to the fluid otors 51. Also openings are located in partition 29 proximate bottom wall 16 to permit drainage from the entire wall 16 to enter sump 39.
By way of example and not of limitation, the dimension A (FIG. 5) of the planar surface 74 may be about 50 inches, and the dimension B (FIG. 1) of planar surface 74 may be any desired value, depending on the width of the roadway to be obstructed. The remainder of the dimensions of the device of FIG. 5 can be readily visualized inasmuch as FIG. 5 is essentially drawn to scale, so that when the barrier 50 is in the extended position of FIG. 5, its uppermost portion at 102 is about 34 inches above the roadway level.
It can thus be seen that the improved barrier construction of the present invention is manifestly capable of achieving the above enumerated objects, and while preferred embodiments have been disclosed, it will be appreciated that the present invention is not limited thereto but may be otherwise embodied within the scope of the following claims. | A vehicle barrier including a housing located in a pit, a barrier pivotally mounted on the housing and having a roadway surface and a barrier surface, hydraulic motors for moving the barrier from a retracted position where said roadway surface lies substantially flush with the roadway to an extended position where the barrier surface obstructs a vehicle on the roadway, energy absorbing members in the barrier, a break-away member effectively located between the barrier and the housing for permitting the barrier to pivot beyond its normal extended position when subjected to a vehicular impact above a predetermined value to thereby lift a vehicle off of the ground and throw it upwardly, and self-aligning structure between the barrier and the housing for effecting engagement between the hydraulic motors and the barrier upon installing the barrier into the housing. | 4 |
FIELD OF THE INVENTION
The present invention relates to a portable communication device comprising an antenna. Such portable communication devices are generally known. Examples of such portable communication devices are hand sets for mobile and cordless telephony and pagers.
BACKGROUND OF THE INVENTION
In prior art portable communication devices, the antenna and the portable communication device are matched for free space conditions. The matching between the portable communication device and the antenna deteriorates when a disturbing object, such as the human body, :s present near the antenna. This effect is known as the proximity effect. As a result of this effect, in the transmitting situation as well as in the receiving situation considerable signal losses may occur.
In European Patent 0 341 238, some ways to avoid the proximity effect are described. In column 2, lines 1-16, it is described that the antenna and the communication device are matched in the situation, that the antenna is "on" the body. This solution, has the drawback, that the performance in free space conditions is bad. Another solution described in EP 0 341 238 is to adaptively match the antenna and the communication device, in dependence on the situation. This solution has the drawback, that extra means are necessary, for measuring the quality of matching between the antenna and the communication device and changing the impedances of the communication device and/or antenna, when matching is bad. This makes that such a communication device complicated.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a portable communication device, which has an acceptable performance, when a disturbing object is near the antenna and also in free space conditions and which is not complicated.
Thereto a portable communication device according to the present invention is characterized in that, the communication device and the antenna are mismatched within a frequency band of interest, for equalizing a transmission loss between the antenna and the communication device as a function of a distance between a disturbing object and the antenna. The transmission loss between the antenna and the communication device is a measure for the performance of the communication device. As a result of the equalization of this transmission loss as a function of the distance between a disturbing object and the antenna, the portable communication device has an acceptable performance in the vicinity of such a disturbing object and in free space conditions. This means that, received signals and transmitted signals have to be amplified less than in the prior art devices. This means that in the portable communication device according to the invention, less power dissipation takes place than in prior art portable communication devices. This has as a result, that smaller batteries can be used or, if the same batteries are used, that their lives will be longer.
An embodiment of the portable communication device according to the present invention is characterized in that, the mismatch is arranged so as to lower the transmission loss between the antenna and the communication device in comparison with the transmission loss when the communication device and the antenna are matched, in the situation that the distance between the antenna and a disturbing object is small. The situation, that the distance between a disturbing object, as for example the human body or the human head, and the antenna is small, is a particularly important one for a portable communication device, since this is the situation in which it finds itself most of the time. When a user makes a call, the portable communication device finds itself near the head of the user. When the user carries the portable communication device with him, it finds itself near the user's body. The mismatch according to this embodiment leads to a slight deterioration of the transmission loss in the free space condition, in comparison with the prior art communication devices. However, the performance in the free space condition remains satisfactory. A satisfactory performance in free space conditions is necessary for the following reasons:
When the communication device is left on wooden table or near another object, which is not very disturbing, the communication device finds itself practically in free space conditions. When a call comes in, the performance of the communication device needs to be good enough to receive the call properly.
Perform type approval tests in anechoic chambers in free space conditions. If the free space performance were not acceptable, the communication device would not pass the type approval tests.
A further embodiment of the portable communication device according to the present invention is characterized in that, a ratio between an antenna impedance of the antenna and a device impedance of the portable communication fulfils the following conditions:
a first one of these impedances has a substantially real value for free space conditions,
a second one of these impedances has a real part having a value in the range of 35%-70% of the value of the first impedance and an imaginary part in the range of 15%-30% of the value of the first impedance, within the frequency band of interest, the imaginary part of the second impedance having a sign opposite to the sign of the imaginary part of the first impedance when the antenna is 0.2λ from a disturbing object. When the ratio of the antenna impedance and the device impedance is made like this, a very good equalization of the transmission loss is obtained as a function of the distance between a disturbing object and the antenna.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be further explained with reference to the drawings in which,
FIG. 1 shows a block diagram of a portable communication device,
FIG. 2 shows the value of the antenna impedance of a dipole antenna as a function of the distance between the antenna and a disturbing object,
FIGS. 3, 5 and 7 show the value of the transmission loss between the antenna and the communication device as a function of the distance between the antenna and a disturbing object for three different embodiments of the communication device of the present invention compared with the value of the transmission loss as a function of the distance between the antenna and the disturbing object, in case that the antenna impedance and the impedance of the communication device are matched, as in prior art devices, and
FIGS. 4, 6 and 8 show the difference in transmission loss between the communication device according to the invention and a prior art communication device, in which the antenna and the communication device are matched for free space conditions, for these three embodiments.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 shows in a general way a block diagram of a portable communication device 10, such as for example a hand set for mobile or cordless telephony. The portable communication device comprises an antenna 11, an controlled switch 12, an RF-transmitting stage 13, an RF-receiving stage 14, a frequency synthesizer 15, a first and a second mixer 16,17, a controller 18, a baseband processing unit 19, a codec 20, a loudspeaker 21 and a microphone 22. Such portable communication devices are widely known. They work at frequencies in the range between several tens of MHz and a few GHz, depending on the system for which they are meant (GSM, DECT etc.). By switching the switch 12, the communication device transmits or receives signals. The first mixer 16 mixes a high frequency wave, generated by the frequency synthesizer 15 with a baseband signal in order to obtain an RF-signal to be transmitted via the RF-transmitting stage 13. The second mixer 17 mixes a high frequency wave with an RF-signal, received via the RF-receiving stage 14 in order to obtain a baseband signal. The controller 18 and the codec 19 are arranged for processing and coding of the analog signal coming in via the microphone 22 so as to obtain a baseband signal (digital) and decoding the baseband signal so as to obtain an analog signal, to be reproduced by the loudspeaker 21.
FIG. 2 shows the value of the antenna impedance of a dipole antenna as a function of the distance between the antenna and a disturbing object. The distance between the disturbing object and the antenna is expressed in wavelengths (λ) belonging to the frequency for which the dipole antenna has been designed. The real part of the antenna impedance is indicated by R A and the imaginary part by X A . For large distances between the disturbing object and the antenna the antenna impedance has a real value R A of about 73 ohms and an imaginary value X A of approximately zero. When the distance between the disturbing object and the antenna is small, the antenna impedance has a quite different value. In prior art devices, where the antenna impedance and the impedance of the communication device are matched for free space conditions, this has as a result, that, when the distance between the disturbing object and the antenna is small, the transmission loss between the antenna and the communication device is high. This can clearly be seen in graph a in FIGS. 3,5 and 7. Because portable communication devices usually are worn near the body of the user and the fact that the user's body is a quite disturbing object, this situation is quite important in practice.
In the portable communication device according to the invention, a deliberate mismatch is arranged between the antenna impedance and the impedance of the communication device, which is in the transmitting situation the output impedance of the transmitting stage 13 and in the receiving situation the input impedance of the receiving stage 14. This deliberate mismatch equalizes the transmission loss between the antenna and the communication device as a function of the distance between the antenna and a disturbing object. The transmission loss TL is defined as follows:
TL=-10 log T (1)
in which ##EQU1## wherein Z C =the impedance of the communication device, which is in the transmitting situation the output impedance of the RF-transmitting stage 13 and in the receiving situation, the input impedance of the RF-receiving stage 14,
Z A *=the complex conjugated value of Z A , and
Z A =the antenna impedance.
FIG. 3 shows the value of the transmission loss between the antenna and the communication device in decibels as a function of the distance between the antenna and a disturbing object, in wavelengths (λ) belonging to the frequency of interest. Curve a shows the transmission loss, in case that the antenna impedance and impedance of the communication device are matched for free space conditions. Curve b shows the transmission loss of a first embodiment of the communication device according to the present invention, in which the free space antenna impedance is 73 Ohms and the impedance of the communication device at the frequency of interest is 24-3i Ohms. FIG. 4 shows the difference in transmission loss between curve a and b for this embodiment. The following conclusions can be drawn from FIGS. 3 and 4. At distances smaller than 0.12λ, the transmission loss of the communication device according to the present invention is smaller than that of the prior art device. A wavelength at 900 MHZ, the frequency band of GSM, is approximately 33 cm, so at this frequency for distances smaller than 4 cm, the communication device according to the invention has a clearly better performance than the prior art communication device. The increased transmission loss at larger distances is only to such an extent that the communication device still has an acceptable performance in that situation, so that calls can be received properly and type approval tests will be passed. In the case according to FIG. 3, the impedance of the communication device is chosen to arrive at a maximum transmission loss TL MAX of 2 dB. As already explained, a portable communication device finds itself most of the time near a disturbing object, so the extra performance for small distances is very useful.
In FIG. 5 the transmission losses between the antenna and the communication device are shown for a prior art device in which the antenna impedance and the impedance of the communication device are matched for free space conditions (curve a) and for a second embodiment of the communication device according to the present invention, in which the antenna impedance has a value of 73 Ohms and the impedance of the communication device has a value of 30-8i Ohms (curve b). FIG. 6 shows the difference in transmission loss between curve a and b for this embodiment. At distances smaller than 0.147λ, the transmission loss of the communication device according to the present invention is smaller than that of the prior art device. However, the difference in transmission loss between this embodiment and the prior art device is smaller than for the first embodiment. In the case according to FIG. 3, the impedance of the communication device is chosen to arrive at a maximum transmission loss TL MAX of 1.5 dB. This results in less deterioration of the transmission loss for larger distances.
In FIG. 7 the transmission losses between the antenna and the communication device are shown for a prior art device in which the antenna impedance and the impedance of the communication device are matched for free space conditions (curve a) and for a third embodiment of the communication device according to the present invention, in which the antenna impedance has a value of 73 Ohms and the impedance of the communication device has a value of 37-10i Ohms (curve b). FIG. 8 shows the difference in transmission loss between curve a and b for this embodiment. For distances smaller than 0.20λ the communication device according to the present invention has a smaller transmission loss than the prior art communication device. The difference in transmission loss between this embodiment and the prior art device is even smaller than for the first and second embodiment. In the case according to FIG. 7, the impedance of the communication device is chosen to arrive at a maximum transmission loss TL MAX of 1 dB. However, the deterioration of the transmission loss for larger distances is smaller, too.
From FIGS. 3 to 8 follows that a smaller transmission loss at small distances results in a higher transmission loss at large distances. A trade off between them can be made.
It is also possible, in a communication device according to the present invention, to make the impedance of the communication device real and the impedance of the antenna complex, or to use other mismatching impedance combinations.
The present invention has been described with a dipole antenna. It is, however, also usable with antennas of different types, having different antenna impedances, like for example complex ones. In case that the antenna impedance is complex, also the impedance of the communication device may be made complex, if this leads to a good equalization of the transmission loss as a function of the distance between the antenna and a disturbing object. | A portable electronic apparatus is disclosed having an antenna and a communication circuit. The antenna impedance is chosen to be a predetermined value which is deliberately mismatched to the impedance of the communication for a predetermined frequency band. This mismatch is chosen to optimize the signal loss between the antenna and the communication circuit when the antenna is far and near a disturbing source. The imaginary part of the antenna impedance has a sign opposite to the sign of the circuit impedance when the antenna is a predetermined distance from the disturbing source. | 7 |
BACKGROUND OF THE INVENTION
[0001] The present invention relative to a wheel driven mechanism and more particularly to such a wheel driven mechanism specially designed for driving a vehicle without a motor.
[0002] Referring to FIG. 1 , a conventional handwheel for electric wheelchair is shown. As illustrated, the handwheel 10 comprises a wheel rim 11 , a plurality of brackets 14 , a plurality of permanent magnets 13 , and a plurality of electromagnets 16 , wherein the permanent magnets 13 are arranged along the wheel rim 11 , each bracket 14 has its one end connected to the axle center 17 of the wheel rim 11 and the electromagnets 16 are arranged at the other ends of the brackets 16 . During operation, the user can hold and rotate the wheel rim 10 . The permanent magnets 13 are arranged in NS pole pairs and evenly located on the inner surface of the wheel rim 11 to face toward the axle center 17 . Further, the permanent magnets 13 of N-S poles are in alternate arrangement. As shown in FIG. 1 , the permanent magnets 13 of N-S poles are evenly and alternatively arranged over the whole inner surface of the wheel rim 11 in radial direction to face toward the axle center 17 of the wheel rim 11 .
[0003] The electromagnets 16 are disposed corresponding to the inner side of the wheel rim 11 . During operation, power supply is provided to the electromagnets 16 , causing the electromagnets 16 to create a magnetic field relative to the permanent magnets 13 of NS pole pairs. The magnetic coupling interaction between the electromagnets 16 and the permanent magnets 13 causes the wheel rim 11 to rotate relative to the axle center 17 .
[0004] In FIG. 1 , the electromagnets 16 are radially arranged to face toward the permanent magnets 13 at the inner side of the wheel rim 11 . The electromagnets 16 are divided into two groups, namely, the first electromagnet group 121 and the second electromagnet group 123 . The first electromagnet group 121 is arranged at one end of a first bracket 141 , which has its other end located on the axle center 17 of the wheel rim 11 . Similarly, the second electromagnet group 123 is arranged at one end of a second bracket 143 , which has its other end located on the axle center 17 of the wheel rim 11 . Thus, the first electromagnet group 121 and the second electromagnet group 123 are symmetric relative to the axle center 17 .
[0005] Further, a gap 15 is defined between the electromagnets 16 and the permanent magnets 13 so that the wheel rim 11 carrying the permanent magnets 13 is rotatable relative to the electromagnets 16 at the brackets 14 . However, when the user operates the handwheel 10 , the fingers or a part of the body of the user may be jammed in the gap 15 accidentally, causing injury.
[0006] Further, after a certain period of time in use, the wheel rim 11 may be deformed, resulting in a variation of the gap 15 between the electromagnets 16 at the brackets 14 and the permanent magnets 13 at the wheel rim 11 . When this condition occurs, the magnetic coupling interaction between the electromagnets 16 and the permanent magnets 13 will be changed, causing wheel rim performance drop or wheel rim damage.
[0007] Therefore, there is a strong demand for a wheel driven mechanism, which eliminates the aforesaid problems.
SUMMARY OF THE PRESENT INVENTION
[0008] It is, therefore, an object of the present invention to provide a wheel driven mechanism, which comprises a rotor defining therein an accommodation chamber, a stator having at least one stator segment, and at least one electromagnet set arranged at the at least one stator segment in which a manner that the electromagnet set and/or the stator segment is disposed in the accommodation chamber, preventing jammed fingers during operation.
[0009] It is another object of the present invention to provide a wheel driven mechanism, which further comprises a bearing arranged between the rotor and the stator to maintain the gap between the permanent magnets at the stator and the electromagnet set at the stator during relative motion between the rotor and the stator, facilitating smooth relative motion between the rotor and the stator.
[0010] It is still another object of the present invention to provide a wheel driven mechanism, which further comprises at least one adjustment unit arranged between the stator segment and the bracket of the stator to maintain the relative positioning between the permanent magnets at the rotor and the electromagnet set at the stator segment, assuring high reliability of the operation performance of the wheel driven mechanism.
[0011] It is still another object of the present invention to provide a wheel driven mechanism, which further comprises at least one waterproof gasket arranged between the rotor and the stator to protect the accommodation chamber of the rotor against outside moisture, avoiding contact between the outside moisture and the electromagnet set and/or the permanent magnets in the accommodation chamber and prolonging the working life of the wheel driven mechanism.
[0012] To achieve these and other objects of the present invention, the present invention provides a wheel driven mechanism, comprising: a rotor defining therein an accommodation chamber; a plurality of permanent magnets mounted inside the accommodation chamber of the rotor; a stator comprising at least one stator segment; and at least one electromagnet set arranged at the stator segment and disposed inside the accommodation chamber of the rotor and facing toward the permanent magnets.
[0013] In one embodiment of aforesaid wheel driven mechanism, further comprises a gap defined between the permanent magnets at the rotor and the electromagnet set at the stator segment.
[0014] In one embodiment of aforesaid wheel driven mechanism, further comprises at least one bearing set between the rotor and the at least one stator segment.
[0015] In one embodiment of aforesaid wheel driven mechanism, wherein the stator comprises a bracket, and the stator segment is located on the bracket.
[0016] In one embodiment of aforesaid wheel driven mechanism, further comprises at least one adjustment unit set between the bracket and the stator segment and controllable to adjust the relative positioning between the electromagnet set at the stator segment and the permanent magnets at the rotor.
[0017] In one embodiment of aforesaid wheel driven mechanism, further comprises at least one waterproof gasket set between the rotor and the stator to watertightly seal the accommodation chamber into an enclosed space.
[0018] In one embodiment of aforesaid wheel driven mechanism, further comprises a drainage passage set between the rotor and the stator.
[0019] In one embodiment of aforesaid wheel driven mechanism, wherein the drainage passage is disposed between the waterproof gasket and the stator.
[0020] In one embodiment of aforesaid wheel driven mechanism, wherein each the electromagnet set comprises at least one coil and at least one magnetic flux conducting unit, the at least one coil being respectively wound on the at least one magnetic flux conducting unit.
[0021] In one embodiment of aforesaid wheel driven mechanism, wherein the rotor is an annular member, and the accommodation chamber is an annular chamber defined in the rotor.
[0022] In one embodiment of aforesaid wheel driven mechanism, wherein the rotor is a tube handwheel of a wheelchair.
[0023] In one embodiment of aforesaid wheel driven mechanism, wherein the rotor is a driving wheel of a vehicle.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is a schematic drawing illustrating the structure of a handwheel of a conventional electric wheelchair.
[0025] FIG. 2 is a schematic perspective front view of a wheel driven mechanism in accordance with a first embodiment of the present invention.
[0026] FIG. 3 is a schematic sectional view of the wheel driven mechanism in accordance with the first embodiment of the present invention.
[0027] FIG. 4 is a schematic sectional view of a wheel driven mechanism in accordance with a second embodiment of the present invention.
[0028] FIG. 5 is a schematic perspective front view of a wheel driven mechanism in accordance with a third embodiment of the present invention.
[0029] FIG. 6 is a schematic sectional view of the wheel driven mechanism in accordance with the third embodiment of the present invention.
[0030] FIG. 7 is a schematic sectional view of a wheel driven mechanism in accordance with a fourth embodiment of the present invention, illustrating, a waterproof gasket and a drainage passage provided between a rotor and a stator.
[0031] FIG. 8 is a schematic perspective front view of a wheel driven mechanism in accordance with a fifth embodiment of the present invention, illustrating a configuration of one stator segment and one electromagnet set.
[0032] FIG. 9 is a schematic perspective front view of a wheel driven mechanism in accordance with a sixth embodiment of the present invention, illustrating a configuration of three stator segments and three electromagnet sets.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0033] Please referring to FIGS. 2 and 3 , a schematic perspective front view and a schematic sectional view of a wheel driven mechanism in accordance with a first embodiment of the present invention are shown. As illustrated, the wheel driven mechanism 20 comprises a rotor 21 , a plurality of permanent magnets 23 , and a stator 25 . The stator 25 comprises at least one stator segment 251 and at least one bracket 253 . The stator segment 251 is supported on the bracket 253 . The stator segment 251 holds at least one electromagnet set 27 . The electromagnet set 27 at the stator segment 251 corresponds to the permanent magnets 23 at the rotor 21 . A gap 24 is defined between the electromagnet set 27 at the stator segment 251 and the permanent magnets 23 at the rotor 21 so that the rotor 21 is rotatable relative to the stator 25 .
[0034] The rotor 21 defines therein an accommodation chamber 22 . In this embodiment, the rotor 21 is an annular member so that the accommodation chamber 22 has an annular profile. The stator segment 251 and the electromagnet set 27 are accommodated in the accommodation chamber 22 in such a manner that the electromagnet set 27 at the stator segment 251 faces toward the permanent magnets 23 at the rotor 21 . Further, the electromagnet set 27 at the stator segment 251 is periodically in a magnetic flux coupling relationship with the permanent magnets 23 at the rotor 21 .
[0035] The permanent magnets 23 in this embodiment are arranged in the accommodation chamber 22 of the rotor 21 in NS pole pairs over the whole or a part of the inner surface of the rotor 21 . Further, the N or S pole of each permanent magnet 23 is disposed in axial direction. Further, the permanent magnets 23 of N-S poles are in alternate arrangement.
[0036] The bracket 253 of the stator 25 is fixedly mounted at the axle center 29 of the wheel driven mechanism 20 . Each of the two opposite ends of each bracket 253 has stator segment 251 arranged thereon. Each stator segment 251 carries electromagnet set 27 . Thus, the electromagnet set 27 and/or the stator segment 251 is arranged in a symmetrical manner relative to the axle center 29 . Further, each electromagnet set 27 comprises a plurality of, for example, 6 electromagnets 271 .
[0037] In actual application, if a three-phase power supply is to be provided to the wheel driven mechanism 20 , the number of the electromagnets 271 of the electromagnet set 27 should be a multiple of 3, for example, 3, 6, 9, etc. If a two-phase power supply is to be provided to the wheel driven mechanism 20 , the number of the electromagnets 271 of the electromagnet set 27 should be a multiple of 2, for example, 2, 4, 6, etc.
[0038] The electromagnets 271 of each electromagnet set 27 are made from coils. When electrically conducted, the electromagnets 271 of each electromagnet set 27 create a magnetic field. In different embodiments, coils can be wound around a magnetic flux conducting unit, for example, a cylindrical magnetic flux conducting core prepared by ferrite (Fe), cobalt (Co) or nickel (Ni), for creating a high strength of magnetic field to enhance the torque of the wheel driven mechanism 20 .
[0039] According to the present invention, the electromagnet set 27 and/or the stator segment 251 is accommodated in the accommodation chamber 22 of the rotor 21 so that the gap 24 between the stator 25 and the rotor 21 will not be apparently exposed to the external structure of the wheel driven mechanism 20 , preventing the user's fingers from being jammed between the stator 25 and the rotor 21 during operation and increasing the level of safety of the use of the wheel driven mechanism 20 .
[0040] To enhance the efficiency of the wheel driven mechanism 20 , at least one bearing 26 may be set between the stator segment 251 of the stator 25 and the rotor 21 . The bearing 26 each can be a ball bearing or needle bearing. In actual application, the bearing 26 can be arranged at the stator segment 251 of the stator 25 or the rotor 21 . Subject to the arrangement of the bearing 26 , the gap 24 between the permanent magnets 23 at the rotor 21 and the electromagnet set 27 at the stator segment 251 of the stator 25 is maintained during relative motion between the rotor 21 and the stator 25 , facilitating smooth relative motion between the rotor 21 and the stator 25 .
[0041] In this first embodiment, the bracket 253 is adjustably connected to the stator segment 251 by at least one adjustment unit 255 . By means of the adjustment unit 255 , the user can adjust the relative positioning between the electromagnet set 27 at the stator segment 251 of the stator 25 and the bracket 253 to compensate the amount of deformation of the roundness of the wheel driven mechanism 20 . The adjustment unit 255 has a deformation characteristic. For example, each adjustment unit 255 can be a spring member or sliding block.
[0042] Normally, the wheel driven mechanism 20 may deform due to uneven external pressure after a certain period of time in use, resulting in non-roundness of the rotor 21 . Following shape change of the rotor 21 , the overlapped area between the electromagnet set 27 at the stator segment 251 and the permanent magnets 23 at the stator 21 may be contracted, affecting the performance of the wheel driven mechanism 20 .
[0043] Subject to the use of the adjustment unit 255 and/or the bearing 26 , the relative positioning between the permanent magnets 23 at the rotor 21 and the electromagnet set 27 at the stator segment 251 of the stator 25 is constantly maintained unchanged, avoiding deformation of the rotor 21 or affecting the operation performance of the wheel driven mechanism 20 .
[0044] Referring to FIG. 4 , a wheel driven mechanism in accordance with a second embodiment of the present invention is shown. As illustrated, the wheel driven mechanism 30 comprises a rotor 21 , a plurality of permanent magnets 23 , a stator 25 comprising at least one stator segment 251 , and at least one electromagnet set 27 installed in the stator segment 251 of the stator 25 . Further, the electromagnet set 27 comprises a plurality of electromagnets 271 . The rotor 21 defines therein an accommodation chamber 22 . The electromagnet set 27 and/or the stator segment 251 of the stator 25 is accommodated in the accommodation chamber 22 of the rotor 21 . The electromagnet set 27 faces toward the permanent magnets 23 with a gap 24 left therebetween so that the rotor 21 is rotatable relative to the stator 25 .
[0045] In this embodiment, the wheel driven mechanism 30 further comprises a waterproof gasket 36 set between the rotor 21 and the stator 25 . The waterproof gasket 36 can be mounted at the rotor 21 or stator 25 to watertightly seal the accommodation chamber 22 of the rotor 21 , avoiding permeation of external moisture into the accommodation chamber 22 to wet the at least one electromagnet set 27 in the accommodation chamber 22 .
[0046] The wheel driven mechanism 30 further comprises a drainage passage 38 disposed between the rotor 21 and the stator 25 for expelling water out of the accommodation chamber 22 by means of a centrifugal force generated during the rotation of the rotor 21 . The drainage passage 38 can be set between the waterproof gasket 36 and stator 25 so that a part of moisture can be guided by the drainage passage 38 to the outside of the accommodation chamber 22 before touching the waterproof gasket 36 , lowering the chance of moisture intrusion into the accommodation chamber 22 . Further, the internal air pressure in the rotor 21 will become higher than the external air pressure to lower the chance of moisture intrusion into the accommodation chamber 22 upon a rise in temperature in the accommodation chamber 22 due to conduction of an electric current through the electromagnets 271 .
[0047] As the electromagnets 271 and the permanent magnets 23 are mainly prepared by ferrite (Fe), cobalt (Co) or nickel (Ni), the electromagnets 271 or the permanent magnets 23 may be rusted or damaged when putting into contact with moisture for a long period of time. By means of the arrangement of the waterproof gasket 36 and/or the drainage passage 38 , the electromagnets 271 and the permanent magnets 23 are isolated from external moisture, effectively prolonging the working life of the wheel driven mechanism 30 .
[0048] Please referring to FIG. 5 and FIG. 6 , a schematic perspective front view and a schematic sectional view of the wheel driven mechanism in accordance with a third embodiment of the present invention. As illustrated, the wheel driven mechanism 40 comprises a rotor 41 , a plurality of permanent magnets 43 , a stator 45 comprising at least one stator segment 451 , and at least one electromagnet set 47 comprising a plurality of electromagnets 471 arranged at the at least one stator segment 451 . The rotor 41 defines therein an accommodation chamber 42 . The electromagnet set 47 and/or the stator segment 451 is accommodated in the accommodation chamber 42 of the rotor 41 . Further, the electromagnet set 47 faces toward the permanent magnets 43 in the accommodation chamber 42 with a gap 44 left therebetween so that the rotor 41 is rotatable relative to the stator 45 .
[0049] In this embodiment, the rotor 41 comprises a bracket 411 , and the permanent magnets 43 are mounted at the bracket 411 . The stator segment 451 is configured to surround the permanent magnets 43 , keeping the electromagnet set 47 at stator segment 451 to face toward the permanent magnets 43 at the bracket 411 . For example, the stator segment 451 can be configured to have a U-shaped profile for surrounding the permanent magnets 43 at the bracket 411 .
[0050] Further, the U-shaped stator segment 451 can be arranged to surround a part of the bracket 411 with at least one bearing 49 set between the stator segment 451 and the bracket 411 , enhancing the relative positioning stability between the permanent magnets 43 and the electromagnet set 47 and the operation performance of the wheel driven mechanism 40 .
[0051] Further, the permanent magnets 43 in this embodiment are arranged in NS pole pairs. Further, the N or S pole of each permanent magnet 43 is disposed in radial direction.
[0052] In actual application, a waterproof gasket 46 and/or a drainage passage 48 can be provided between the rotor 41 and the stator 45 , as shown in FIG. 7 , keeping the accommodation chamber 42 of the rotor 41 in an enclosed condition to lower the chance of moisture intrusion into the accommodation chamber 42 . Further, the internal air pressure in the rotor 41 will become higher than the external air pressure to lower the chance of moisture intrusion into the accommodation chamber 42 and to prolong the working life of the wheel driven mechanism 40 upon a rise in temperature in the accommodation chamber 42 due to conduction of an electric current through the electromagnets 471 .
[0053] Further, the winding condition of the electromagnet sets 27 / 47 and the relative arrangement of the permanent magnets 23 / 43 enables the air gap flux to be axially or radially direction. For example, the air gap flux of electromagnet sets 27 and permanent magnets 23 of the wheel driven mechanism 20 / 30 in FIG. 3 and FIG. 4 are axially directed where the windings of the electromagnet sets 27 extend in a parallel manner relative to the wheel driven mechanism 20 / 30 , and the axle center of the rotor 21 and/or stator 25 . The air gap flux of electromagnet sets 47 and permanent magnets 43 of the wheel driven mechanism 40 in FIGS. 5-7 are radially directed where the windings of the electromagnet sets 47 extend along the radius direction of the wheel driven mechanism 40 , rotor 41 and/or stator 45 . The aforesaid two winding methods can be selectively used to make the wheel driven mechanism subject to actual requirements.
[0054] In the aforesaid various embodiments, the wheel driven mechanism 20 / 30 / 40 mainly comprises two stator segments 251 / 451 and two electromagnet sets 27 / 47 respectively located on the two ends of the bracket 253 . However, in the embodiment shown in FIG. 8 , only one stator segment 251 / 451 and one electromagnet set 27 / 47 are provided. Further, the number of the stator segments 251 / 451 and the number of the electromagnet sets 27 / 47 can be more than 2. For example, in the embodiment shown in FIG. 9 , the wheel driven mechanism comprises three stator segments 251 / 451 and three electromagnet sets 27 / 47 .
[0055] The aforesaid wheel driven mechanisms 20 / 30 / 40 are designed for driving a vehicle, for example, a wheelchair, electric bicycle, motorcycle, etc., wherein the rotor 21 / 41 can be the driving wheel of a vehicle or the tube handwheel of a wheelchair. | A wheel driven mechanism adapted for driving a vehicle without motor is disclosed to include a rotor defining therein an accommodation chamber, a plurality of permanent magnets arranged in the accommodation chamber of the rotor, a stator having one or a number of stator segments, and one or a number of electromagnets located on the stator segment(s) within the accommodation chamber and facing toward the permanent magnets at the stator to enhance the convenience of use of the wheel driven mechanism. | 7 |
This is a division of application Ser. No. 08/315,554 filed Sep. 30, 1994 and now U.S. Pat. No. 5,429,956.
BACKGROUND OF THE INVENTION
(1) Field of the Invention
The present invention relates to the formation of integrated circuit devices on semiconductor substrates, and more particularly a method of fabricating a field effect transistor having a self-aligned anti-punch-through implantation.
(2) Description of the Prior Art
In recent years advances in semiconductor processing technology as resulted in Ultra Large Scale Integration (ULSI) on the semiconductor substrate. For example, advances in high resolution photolithographic techniques and advances in plasma etching have resulted in feature sizes that are less than a half micrometer in size. One application of this down scaling on the semiconductor chip where the reduction in size dramatically improves performance of the circuit and increases device density on the chip is the formation of the gate electrode of the field effect transistor (FET). The reduced width of the gate electrode has resulted in channel lengths under the gate electrode becoming submicrometer in size.
Although the down scaling improves circuit density and performance, a number of short channel effects can occur that adversely affect device performance. For example, the major transistor phenomena that are affected by down scaling and degrade the transistor behavior include channel-length modulation, velocity saturation, mobility degradation, source/drain resistance, punchthrough, drain induced barrier lowering and dependence of threshold voltage (V t ) on device geometry.
When the channel length is reduced and is comparable in length to the source/drain junction depth, a considerable amount of the space charge, under the gate electrode, is linked to the source/drain junction depletion region. This results in less charge in the space-charge region being coupled or linked to the gate and the threshold voltage V t of the FET decreases. To minimize the threshold voltage V t variation with reduced channel length, it is common practice in the semiconductor industry to fabricate FET structures with Lightly Doped Drains (LDD). These LDD regions are formed adjacent to the gate electrode by doping using ion implantation. Sidewall insulating spacer on the gate electrode then mask the LDD region from further doping, while the heavier doped source/drain contacts are formed.
However, other short channel effects, such as punchthrough, still remain a serious problem. In this effect when the sum of the source and drain depletion widths formed in the substrate become greater than the channel length, the source and drain are electrically shorted together and the basic transistor action, as a switch is lost. Another short channel length effect that is closely related to the widening of the depletion width at the drain for a FET device that is turned-off, is Drain-Induced Barrier Lowering (DIBL) that occurs at the source end of the channel. This barrier lowering effect can result in increased leakage currents when the FET is in the off or non-conducting state. This can cause failure in dynamic circuits, and especially in DRAMs where charge retention is critical.
One method that is commonly practice in the semiconductor industry to prevent punchthrough is to form an anti-punchthrough buried implant channel in the substrate by ion implantation in the device area. This method is best understood by referring to the prior art as depicted in FIGS. 1 through 3. starting with FIG. 1, a patterned silicon nitride/pad oxide stack is formed on the substrate 10 by photolithographic techniques and etching, leaving portions of the silicon nitride layer 14 and pad oxide layer 12 on the device areas and removing the stack layer elsewhere on the substrate where the Field Oxide (FOX) isolation is to be formed. A deep anti-punchthrough buried channel 16 is formed in the substrate, for example, by implanting boron ions, such as isotope (B 11 ) and depicted in FIG. 1 by the down ward pointing arrows.
A conventional LOCOS (LOCal Oxidation of Silicon) method is then used to form the field oxide (FOX) structure. The method consisting of thermally oxidizing the substrate using the silicon nitride layer 14 as a barrier to oxidation over the device area. After forming the field oxide (FOX) structure 18 , as shown in FIG. 2, the silicon nitride layer 16 and pad oxide 12 are removed and a good quality gate oxide layer 20 is thermally grown on the device area. The gate electrode 22 of the FET is then formed by depositing and patterning a polysilicon layer 22 using a patterned photoresist layer 24 and plasma etching.
As shown in FIG. 3, the photoresist is stripped and Lightly Doped Drain (LDD) source/drain regions 26 are formed by ion implantation of arsenic or phosphorus ions. The field effect transistor (FET) is then completed by forming sidewall spacers 28 over the LDD regions adjacent to the gate electrode and then forming the N + doped source/drain contact 30 .
Although the anti-punchthrough buried implant channel reduces punchthrough from drain to source, the increased junction capacitance resulting from the anti-punchthrough channel extending under the source/drain contact 30 , degrades the circuit performance. Therefore, there is still a strong need in the semiconductor industry for improved methods of forming anti-punchthrough buried implant channels with reduced capacitance.
SUMMARY OF THE INVENTION
It is the principle object of this invention to provide a method for forming anti-punchthrough buried channels with reduced capacitance.
It is another object of this invention to provide this reduced capacitance by a method for self-aligning the anti-punchthrough channel to the FET channel.
It is still another object of the invention to formed this self-aligned anti-punchthrough buried channel by a technique of implanting the channel using a selectively deposited silicon oxide implant blockout mask formed by Liquid Phase Deposition (LPD).
In accordance with these objectives the invention provides a new field effect transistor structure having a buried anti-punchthrough implant region or channel aligned to and under the gate electrode of the FET. The invention also teaches a method for forming said improved FET structure by ion implantation using an implant blockout mask formed by selectively depositing a silicon oxide layer by Liquid Phase Deposition (LPD).
The method begins by providing a semiconductor substrate, such as a P − doped single crystal silicon having a <100> crystallographic orientation. A thick field oxide (FOX) is then thermally grown by the conventional method of LOCOS (LOCal Oxidation of Silicon) to electrically isolate the device areas wherein the FETs are constructed.
A thin gate oxide layer is then formed on the device areas, such as by thermal oxidation in an oxygen containing ambient. A polysilicon layer is deposited on the substrate and then patterned by conventional photolithographic techniques and plasma etching to form the gate electrodes, of the FETS, over the gate oxide layer in the device area, and at the same time forming electrical interconnecting lines over the field oxide areas, such as the word lines for dynamic random access memory (DRAM).
With the photoresist is still in place on the gate electrode and interconnecting lines, a silicon oxide is selectively deposited by Liquid-Phase Deposition (LPD) over the field oxide areas and over the exposed portions of the gate oxide areas. However, the LPD oxide does not deposit on the photoresist. The deposition is achieved by immersing the substrate in a supersaturated solution of, for example, hydrofluosilicic acid (H 2 SiF 6 ) made supersaturated by dissolving silicon oxide (SiO 2 ) powder therein. Although the detail mechanism is not well understood, it is believed that a dehydration reaction occurs at the silicon oxide surface making the selective adsorption of siloxane (Si—O—Si) oligomers on the oxide surfaces possible, thereby resulting in the selective deposition of Sio 2 on the oxide surface. A more detail description of the method for liquid-phase deposition of SiO 2 can be founds in the paper by T. Homma et al, entitled “A Selective SiO2 Film-Formation Technology Using Liquid-Phase Deposition for Fully Planarized Multilevel Interconnections” and published in the Journal of the Electrochemical Society, Vol. 140, No. 8, August 1993.
The LPD silicon oxide is grown to a thickness that is greater than the polysilicon layer from which the gate electrode is formed and of sufficient thickness to mask the high energy ion implant that will be later used to form the self-aligned anti-punchthrough buried channel of this invention. The patterned photoresist layer is now removed from over the patterned polysilicon layer, for example, by plasma ashing or wet stripping, and thereby forms a recess in the LPD silicon oxide layer that is self-aligned to the gate electrode of the FET. A sidewall spacer is formed on the sidewalls in the recessed LPD silicon oxide by depositing a silicon oxide, such as by Low Pressure Chemical Vapor Deposition (LPCVD) and then etching backing anisotropically. This further narrows the implant window in the LPD oxide and protects the edge of the gate electrode at the polysilicon/LPD oxide interface from implant damage.
The anti-punchthrough buried channel is now formed under and aligned to the polysilicon gate electrode by performing a high energy ion implantation in the LPD oxide window or recess, while the thick LPD oxide and CVD oxide sidewalls provide an mask to implant elsewhere on the substrate. The confinement of the anti-punchthrough channel under the gate electrode is effective at preventing drain to source punchthrough during operation of the circuit while substantially reducing junction capacitance under the source/drain contact area and thereby improving circuit performance.
The LPD silicon oxide is now removed from the substrate, such as by wet etching in a hydrofluoric acid solution, and then the FET devices are completed by forming the lightly doped drain (LDD), the sidewall spacers on the gate electrode and the source/drain contact implant.
BRIEF DESCRIPTION OF THE DRAWINGS
The object and other advantages of this invention are best explained in the preferred embodiment with reference to the attached drawings that include:
FIGS. 1 through 3, which is a schematic cross sectional view illustrating the process for a field effect transistor of the prior art having a conventional anti-punchthrough buried implant channel with a large junction capacitance.
FIGS. 4 through 9, which is a schematic cross sectional view illustrating the process and structure of this invention for a FET having an improved self-aligned anti-punchthrough implanted channel with a reduced junction capacitance.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now more particularly to FIGS. 4 through 9 there is shown an embodiment for fabricating a field effect transistor (FET) having the self-aligned anti-punchthrough buried implant channel. The new FET structure with improved punchthrough properties can be used to manufacture, for example, ULSI circuits such as DRAMs, SRAM micro-processor circuits and the likes.
Referring now to FIG. 4, a cross sectional view of the starting substrate 10 is schematically shown. The preferred substrate is typically composed of a P-type single crystal silicon with a <100> crystallographic orientation. A thick Field OXide (FOX) structure is formed surrounding and electrically isolating the active device areas, wherein the field effect transistor (FET) devices having the improved self-aligned anti-punchthrough implant channel, of this invention, is to be built. The method commonly practiced in the industry for forming the Field OXide (FOX) consists of using a thin thermal oxide (pad oxide) layer 12 having a thickness of between about 300 to 500 Angstroms and a thicker silicon nitride layer 14 , deposited, for example, by chemical vapor deposition (CVD), and having a thickness of between about 1000 to 2000 Angstroms, the silicon nitride layer 14 serving as a barrier mask to thermal oxidation. The required areas where the field oxide is required are etched open in the oxide/nitride layer using conventional photo-lithographic techniques and plasma etching and then a field oxide structure 18 is thermally grown, as shown in FIG. 4, typically to a thickness of about 4500 to 5500 angstroms.
The silicon nitride layer 14 is now removed from the device areas, for example, by wet etching in a heated solution of phosphoric acid (H 3 PO 4 ), and the pad oxide is removed, for example, by etching in a buffered solution of hydrofluoric acid. The substrate 10 is then thermally oxidized to form the gate oxide layer 20 on the device area for the FET. The gate oxide 20 is typically between about 100 to 200 Angstroms thick.
Next, as shown in FIG. 5, the gate electrode structure 22 , for the N-channel FET, is now formed by depositing a polysilicon layer 22 , for example, by performing a low pressure chemical vapor deposition (LPCVD). The preferred thickness of layer 22 is usually in the range from between about 2000 to 4000 Angstroms. The polysilicon layer 22 is then made more electrically conducting by doping with N-type impurities, either by in situ doping during the LPCVD deposition or by depositing the polysilicon undoped and then ion implanting the dopant. Typically the N-type dopant species is arsenic or phosphorus having a concentration of between about 1 E 19 to 1 E 21 atoms/cm 3 .
The polysilicon layer 22 is then coated with photoresist layer 24 and is patterned by photolithographic techniques to provide the etch mask layer over the polysilicon gate electrode and interconnecting conducting lines areas while exposing the polysilicon layer 22 elsewhere on the substrate. An anisotropic plasma etch, such as in a low pressure reactive ion etcher (RIE) containing a reactive etch gas mixture such as chlorine/argon or gas mixtures containing for example CCL 2 F 2 . After patterning the polysilicon layer 22 the patterned photoresist mask layer remains on the polysilicon gate electrode structure 22 , as shown in FIG. 5., and provide an important function for the selective deposition of a silicon oxide layer 26 by Liquid Phase Deposition.
Now as shown in FIG. 6, the selective silicon oxide layer is deposited by Liquid Phase Deposition (LPD), by immersing the substrate in a supersaturated solution of, for example, hydrofluosilicic acid (H 2 SiF 6 ) made supersaturated by dissolving silicon oxide (SiO 2 ) powder therein. Although the detail mechanism is not well understood, it is believed that a dehydration reaction occurs at the oxide surface making the adsorption of siloxane (Si—O—Si) oligomers possible, and thereby resulting in the selective deposition of SiO 2 on the silicon oxide surfaces while not depositing on the non-oxide surfaces, such as photoresist.
The LPD silicon oxide layer 26 is deposited by a timed deposition until the desired LPD silicon oxide thickness is achieved. Now as shown in FIG. 6, the LPD oxide layer is deposited having a thickness that substantially exceeds the thickness of the gate electrode, formed from the polysilicon layer 22 . The preferred thickness of the LPD silicon oxide layer 26 is between about 3000 to 6000 Angstroms. The thickness of the LPD silicon oxide layer 26 is critical to the invention, because it must be sufficient thick to serve as an ion implant block out mask, at the later step in the process, when the anti-punchthrough implant channel is formed under the gate electrode 22 by a high energy ion implantation.
To continue the process, the photoresist layer 24 is now removed, for example, by plasma ashing in an oxygen ambient of by conventional photoresist stripping. This results in a recess in the LPD silicon oxide layer 26 which is over and aligned to the patterned polysilicon layer 24 . Typically, the depth of the recess step in layer 26 to the top surface of the gate electrode 22 is between about 1500 to 4000 Angstroms.
Referring now to FIG. 7, a first sidewall oxide layer 28 is deposited on the substrate forming a conformal layer over the recess steps in the LPD silicon oxide layer 26 . The layer 28 is preferably a silicon oxide layer and having a thickness, preferably between about 500 to 7000 Angstroms. For example, the silicon oxide 26 can be formed by low pressure chemical vapor deposition using tetraethoxysilane (TEOS) at a temperature in the range of about 650 to 900° C. The sidewall oxide layer 28 is then etched back anisotropically to form sidewall spacer 30 on the sidewall of the recesses in the LPD oxide layer 26 , as shown in FIG. 8 . The etch back can be accomplished with a reactive plasma etcher of various design and using an appropriate gases mixture. For example, the etching can be performed in a gas mixture of carbon tetrafluoride and hydrogen (CF 4 /H 2 ). Alternatively, a gas mixture containing trifluoromethane (CHF 3 ) can also be used.
The sidewalls 30 further narrows the self-aligned opening 34 over the gate electrode area that will be later used for implanting the buried anti-punchthrough implant channel in the substrate under the gate electrode 22 . The sidewall spacer also protects the gate oxide 20 at the edge of the gate electrode 22 from implant damage that would otherwise degrade the reliability of the FET. The sidewall spacers also reduce the width of the anti-punchthrough implant channel, thereby further reducing the source and drain junction capacitance and improves circuit performance.
Still referring to FIG. 8, the self-aligned anti-punchthrough implant channel 40 is now formed in the substrate 10 under the polysilicon gate electrode 22 by high energy ion implantation. The ion implant species for the N-channel FET formed in a P − substrate is of the same polarity as the substrate dopant and is preferably the boron isotope B 11 . The preferred tilt angle, for the implant, is about 0 degrees, that is the implant is normal to the substrate surface. However, the implant parameters, such as the implant energy, should be tailor to the product process parameters, such as, the gate electrode thickness and the source/drain junction depths. However, by way of example only, if the thickness of the gate electrode is about 2000 Angstroms and the source/drain junction depth, after final processing is about 0.2 micrometers deep, then the preferred ion implant dose is between about 2 E 12 to 5 E 12 ion/cm 2 and the ion implant energy is between about 120 to 180 KeV. At these implant and process parameters, the projected ion range in the silicon substrate is then about 0.2 to 0.35 micrometers below the gate oxide layer 20 .
After forming the anti-punchthrough channel implant, the implant blockout mask composed of the LPD silicon oxide layer 26 and the sidewall spacers 30 are removed from the substrate, for example by wet etching in a buffered hydrofluoric acid solution (BHF).
The FET is now completed, as shown in FIG. 9, by first forming a lightly doped source/drain region 60 in the device area, adjacent to the gate electrode 22 . This doping is usually accomplished by implanting an N-type dopant species, such as arsenic or phosphorous, in the P-substrate device area. For example, a typical ion implantation for the LDD of the N-channel FET might consist of a phosphorous P 31 at a dose of between 1 to 10 E 13 atoms/cm 2 and with an energy of 30 to 80 Kev.
After forming the LDD areas, the sidewall spacers 50 are formed on the sidewall of the gate electrode structures 22 . These spacers are formed by depositing a second sidewall oxide layer 50 , for example, by LPCVD, and then using an anisotropic plasma etch to etch back to the source/drain surface, leaving portions of the silicon oxide layer 50 on the gate electrode sidewalls, and thereby forming the sidewall spacers 50 , as shown in FIG. 9 . The method for forming the sidewalls of the gate electrode is similar to the method used previously for forming the sidewalls spacers 30 on the sidewalls of the LPD oxide layer 26 , and the process details are not here repeated. The FET source/drain contacts 62 are then formed by ion implantation to complete the N-channel FET having a self-aligned anti-punchthrough buried channel.
As is clearly seen in FIG. 9, the anti-punchthrough channel 40 , of this invention, is essentially eliminate from under the source/drain areas and the junction capacitance associated therewith is substantially reduced.
While the invention has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention. For example, self-aligned anti-punchthrough implant channels can be formed in N − doped substrates for P-channel FETs by simply reversing the dopant polarity. It is also possible to use additional photoresist blockout mask to form both types of anti-punchthrough implant channels on the same substrate having both P-channel and N-channel devices, such as might be used for forming CMOS circuits. | A structure and method for fabricating a field effect transistor (FET) having improved drain to source punchthrough properties was achieved. The method utilizes the selective deposition of silicon oxide by a Liquid Phase Deposition (LPD) method to form a self-aligning implant mask. The mask is then used to implant a buried anti-punchthrough implant channel under and aligned to the gate electrode of the FET. The buried implant reduces the depletion width at the substrate to source/drain junction under the gate electrode but does not increase substantially the junction capacitance under the source/drain contacts, thereby improving punch-through characteristic while maintaining device performance. | 7 |
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates to a watch having a crown for setting the hands as well as a device, which can be driven by the hour wheel of the watch movement, for automatically displaying the month and the day of the month in accordance with the Gregorian calendar, the day-of-the-month display being adapted to be driven by a date wheel of the device and the month display being adapted to be driven by a month wheel of the device.
In such known watches, a correction of the individual calendar displays is effected by correction buttons. In order to equalize the differences in the number of days in the month, particularly for February and also with due consideration of leap years, the advancing connection from the date wheel to the month wheel is provided with suitable mechanical programming.
Upon a correction of the calendar displays after the watch has been standing for a particularly long period of time it may happen that the mechanical programming of the advancing connection does not agree with the actual date, particularly with respect to the number of days in the month.
SUMMARY OF THE INVENTION
It is an object of the invention therefore to create a watch embodying the foregoing features in which the correct display of the calendar dates is assured.
According to the invention, a year wheel (17) of a year display and a decade wheel (26) of a decade display, and possibly a century wheel of a century display, form, together with the wheelwork of the month display (57) and the day-of-the-month display (56), a closed, coupling-less calendar wheelwork train whose date wheel (13) can be set by a correction means. Since, in addition to the month and the day of the month, the number of the year and possibly even an indication of the century are displayed, and at the same time no individual adjustment of the different displays is possible, a dependable correction can always be effected by simultaneous monitoring of the display. The association of the individual displays with each other cannot be changed since the calendar wheelwork train is adjustable only as a whole by adjustment of the smallest display unit, namely the day of the month.
A reduction of the number of actuating elements can be obtained in the manner that the crown forms the correction means and is movable axially into a time-setting position for adjusting the time and into a correction setting position for correcting the calendar.
In one simple development, a shift finger (24) can be arranged fixed on the month wheel (22), a two-part, turnably mounted intermediate wheel (25) being adapted to be advanced by it, the two parts of the intermediate wheel (25) having the same pitch circle and the same pitch, the (first part of the) intermediate wheel (25) being provided completely with teeth and the second (part of the) intermediate wheel (25) having one-tenth the number of teeth that the first (part of the) intermediate wheel (25) has, the year wheel being adapted to be driven by the first part of the intermediate wheel (25) and the decade wheel (26) by the second part of the intermediate wheel (25). In this connection, the shift finger (24) can be adapted to be driven one revolution a year and the first part of the intermediate wheel (25), the year wheel and the decade wheel (26) each have ten teeth.
A construction which has only a small number of simple parts is obtained in the manner that the year wheel and the decade wheel (26) are arranged coaxially to each other and that the year wheel is firmly connected to a coaxial year display ring (27) which is surrounded by a decade display ring (28) which is firmly connected to the decade wheel (26).
An additional display of the century is possible in simple manner by providing on the decade wheel (decade display ring 28) a shift cam (30) by which a century slide (33) which is tangential to the decade display ring (28) and to the path of rotation of the shift cam (30) is displaceable.
In order to obtain also a display of the days of the week which is always correctly in agreement with the other displays, a day-of-the-week wheelwork of a day-of-the-week display (58) can form a closed, coupling-less wheelwork train together with the calendar wheelwork train. In this case, a swing lever (40) can be driven one swing deflection per day by the watch movement, by which a day-of-the-week wheel (44) which is turnable around a shaft can be advanced via a shift lever (42). The day-of-the-week wheel (44) preferably has seven teeth.
A simultaneous display of the phase of the moon which also is always in correct agreement with the calendar displays is obtained in the manner that a moon-phase drive of a moon-phase display forms a closed, coupling-less moon-phase wheelwork train with the calendar wheelwork train.
In order to keep the number of parts small, the moon-phase drive can be driven by the day-of-the-week drive, a moon phase wheel (46) being preferably firmly connected coaxially to the day-of-the-week wheel (44).
For the driving of the moon-phase display, the moon-phase drive can have a moon-phase intermediate wheel (47) which can be driven by the moon-phase wheel (46) and bears a step-down wheel (48) by which a display drive wheel (49) which is firmly connected to the moon-phase display can be driven. In this case, the moon-phase display can in a simple embodiment, have a moon disk (50) which is firmly connected coaxially to the display drive wheel (49).
If the transmission ratio of the day-of-the-week wheel (44) to the display drive wheel (49) is 8,4375:1 and if the moon disk (50) has two diagonally opposite moons (51), then such a high precision of the drive of the moon phase is obtained that the need for correction by only one day occurs only after 122 years.
The watch of the invention thus has a perpetual calendar with perpetual moon-phase display, they being jointly displaceable by merely a single total-correction device. The complete display of the calendar dates, including the century number, permits verification that all calendar and moon-phase functions of the watch are correctly programmed.
BRIEF DESCRIPTION OF THE DRAWINGS
With the above and other objects and advantages in view, the present invention will become more clearly understood in connection with the detailed description of a preferred embodiment, when considered with the accompanying drawings, of which:
FIG. 1 is a view of the drive of an automatic calendar and moon-phase display;
FIG. 2 is a view of the dial of the watch of FIG. 1;
FIG. 3 is a partial view of the watch drive of FIG. 1 showing a crown and correction gears;
FIG. 4 is a detailed fragmentary view of the mechanism of FIG. 1 showing the year display; and
FIG. 5 is a side sectional view of the mechanism of FIG. 4.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIGS. 1-5, 1 is an hour pipe of the motion work. By a drive (not shown) a lever 5 which is swingable around a shaft 4 is moved back and forth once a day by the watch movement.
A feeler arm 6 of the lever 5 has its free end resting radially from the outside against the circumferential periphery of a turnably mounted month step disk 7.
The month step disk 7 has on its circumferential periphery 20 notches and elevations each, they representing the 48 months of a leap-year period. By means of these elevations and depressions, the feeler arm 6 and the lever 5 can swing a greater or lesser distance towards a shaft of rotation 8 of the month step disk 7. The elevations 9 represent months having 31 days and the depressions 10, which are of smaller depth represent months of 30 days; the depressions 11 of greatest depth in each case represent February with 28 days and the depression 12 represents February of a leap year, having 29 days.
By the daily swinging movement of the lever 5, a date wheel 13 mounted turnably on the shaft 4 is turned in clockwise direction by means of a shift pawl 14. The shift pawl 14 engages in a tooth gap on the periphery of the date wheel 13, provided on its periphery with 31 radial sawtooth teeth. In order to prevent the date wheel 13 from turning further by itself, a detent lock 16 engages under spring action into a tooth gap.
One tooth 15 of the 31 teeth of the date wheel 13 extends further outward radially than the other teeth. At the end of each month, a gearwheel 17 having 48 teeth which is turnable on the shaft 8 and firmly connected to the month step disk 7 can be turned by one tooth in counterclockwise direction by said tooth 15. The gearwheel 17 is also secured against turning further by itself by a detent lock 18, which can engage under spring action into a tooth gap.
On the lever 5 there is turnably mounted an additional pawl 19 the free end of which rests under spring action against a spirally shaped eccentric cam 20. This eccentric cam 20 is firmly connected to the date wheel 13 and is turnable around the shaft 4.
The radially outer end of the spiral of the cam 20 which increases in radius in counterclockwise direction forms a stop 21 against which the tip of the free end of the additional pawl 19 can come to rest.
While due to the swinging of the lever 5 with the feeler arm 6 resting on an elevation 9 further movement of the date wheel 13 by the shift pawl 14 takes place by only one tooth, the somewhat larger path of swing of the lever 5 in the case of the depressions 10 on the last day of the month leads first to a turning of the date wheel 13 by one tooth by the additional pawl 19 and then to a turning by another tooth by means of the shift pawl 14.
The depressions 11 lead to a further shifting by three teeth and the depressions 12 by two teeth as a result of the additional pawl 19 before the shift pawl 14 advances further by one additional tooth.
As a result of this, the gearwheel 17 of the month disk 7 is always turned further correctly by the tooth 15 for the change of the month.
A turnably mounted month wheel 22 having 12 teeth also meshes with the gearwheel 17. A month display (not shown) is driven by the month wheel 22 (pointer on scale 57 in FIG. 2).
A radially protruding shift finger 24 is rigidly connected to the month wheel 22 and is turnable around the axis 23 thereof. This finger engages like a single tooth into a two-part intermediate wheel 25. The two parts of the intermediate wheel 25 which are arranged coaxially to and firmly connected to each other have the same pitch diameter and the same pitch.
The one part is developed completely with teeth--namely ten teeth--while 9 teeth are removed on the other part so that only a single tooth is present. The intermediate wheel 25 is advanced by the shift finger 24 by one tooth once a year.
Two identical gearwheels each having ten teeth mesh with the intermediate wheel 25. Said gearwheels are turnable coaxially alongside of each other but independently of each other around an axis.
The one gearwheel meshes with the part of the intermediate gear 25 which has ten teeth and forms a year wheel while the other gearwheel meshes with the part of the intermediate wheel 25 having one tooth and forms a decade wheel 26. In this way the year wheel is moved once a year by one tooth and the decade wheel 26 is moved once every ten years by one tooth.
The year wheel is firmly connected to a coaxial year display ring 27 and the decade wheel 26 to a decade display ring 28 which surrounds the year display ring 27, both the year display ring 27 and the decade display ring 28 bearing numbers from 1 to 9 printed thereon. The decade wheel 26 and the year wheel are secured against turning further by themselves by means of detent locks 29.
Radially protruding from the decade display ring 28 there is a shift projection 30 which can engage in recesses 31 in a century slide 33 which is guided slidably tangential to the decade display ring 28 in a guide groove 32. In this connection, the recesses 31 in the lengthwise direction of the century slide 33 are so arranged one behind the other that after each decade revolution of the decade display ring 28 the century slide 33 is moved further by an amount equal to one recess.
Since one century number is printed on the century slide 33 for each spacing, the complete year is indicated by the radially adjacent digits of the century slide 33, the decade display ring 28 and the year display ring 27, the year being visible to an observer through a window 34 in the dial 35.
The recesses 31, separated by arms 36, extend continuously across the century slide 33. On the side opposite the decade display ring 28, a detent device engages on the century slide 33, it securing the latter in its position after each displacement.
This detent device consists of a disk 37 which is of a larger diameter than a recess 31 and is guided transversely to the century slide 33 in a guide, the disk being urged by a spring 38 in each case partially into the recess 31.
The lever 5 has a radially protruding part which forms a swing lever 40 on which there is developed a slot 39 into which a pin 41 extends. The pin 41 is swingable on the free end of a lever arm of a double-armed shift lever 42 which is swingable about an axis. The free end of the other lever arm of the shift lever 42, upon the daily swinging motion of the latter, turns a 7-tooth day-of-the-week wheel 44 further by one tooth division. The shift lever 42 is brought out of engagement with the day-of-the-week wheel 44 by a spring 43.
The day-of-the-week wheel 44 which is connected with a day-of-the-week display (pointer on scale 58, FIG. 2) is secured against turning by itself by a detent lock 45 which engages under spring action in a tooth gap.
A moon-phase wheel 46 is firmly connected coaxially to the day-of-the-week wheel 44 and meshes with a moon-phase intermediate wheel 47. The moon-phase intermediate wheel 47 in its turn, is firmly connected coaxially to a step-down wheel 48 which meshes with a display drive wheel 49. A moon disk 50 is coaxially connected to the display drive wheel 49, two moons 51 being arranged diagonally opposite each other on the moon disk.
The transmission ratio from day-of-the-week wheel 44 to display drive wheel 49 is 8.4375:1. Thus the display drive wheel 49 is turned once every 59.0625 days.
Since the moon disk 50 is provided with two moons 51, one moon period of the display lasts for 29.53125 days. As compared with the actual moon period of 29.53059 days, this is a deviation of only 0.00066 days per moon period, which means a difference of one day in 122 years.
The high degree of accuracy of the moon-phase display together with the complete automatic display of the calendar dates including the year number has the advantage that none of the displays ever has to be adjusted individually. The entire calendar is permanently programmed up to Mar. 1, 2100. Only then is a slight correction by a watchmaker necessary.
Due to the fixed programming and the correction by means of the crown no correction buttons are necessary, which on the one hand simplifies the operation of the watch and makes rapid correction of all displays possible. On the other hand, this development permits a water-tight development of the watch in simple manner.
The small number of parts as a result of the elimination of the individual correction devices contributes to the production of watches of smaller size and in particular of smaller structural height.
As shown in FIG. 2, the dial 35 of the watch, which is moved over by an hour hand 52, a minute hand 53 and a second hand 54, also bears the calendar and moon-phase displays. For this purpose, a window 55 is provided for the moon-phase display, a scale with pointer for the date display 56, a scale with pointer for the month display 57, a scale and a pointer for the day-of-the-week display 58, and the window opening 34 for the year display. | A watch having a crown for setting the motion work and having a device, which can be driven by the hour wheel of the movement of the watch, for the automatic display of the months and the days of the month in accordance with the Gregorian calendar. In this connection, the display of the day of the month can be driven by a date wheel 13 and the display of the month by a month wheel 22 of the device. A year wheel of a year display and a decade wheel 26 of a decade display and possibly a century drive of a century display form together with the wheelwork of the month display and the day of the month display a closed coupling-less calendar wheelwork train whose date wheel 13 can be set by a correction device. | 6 |
FIELD OF THE INVENTION
This invention relates generally to the field of ventilation and more particularly to ventilation of residential and commercial living spaces. Fresh air is needed for the comfort and health of building occupants. Most particularly this invention relates to air to air heat exchangers of the type which may be used to transfer heat and energy from an exhaust air stream being expelled from a building into a fresh air stream being drawn into the building to replace the stale air being exhausted from the building.
BACKGROUND OF THE INVENTION
Ventilation of building's occupied by humans is required. Such ventilation is required to provide fresh oxygen to the occupants of the building and to remove stale air with high concentrations of CO 2 for health and comfort reasons. Modern construction and building codes have imposed certain requirements on building ventilation systems. In particular modern construction focuses on heavily insulated and air tight buildings to reduce overall energy consumption. Making the building substantially airtight limits the amount of energy loss through drafts and the like.
On the other hand, modern building codes require a sufficient turnover of air within a dwelling in order to provide sufficient fresh air and oxygen for the occupants to be healthy and comfortable. Certain technology and equipment have been developed to meet with these competing demands. In particular, specialized ventilation units have been developed to provide a source of fresh air while at the same time limiting the amount of energy lost through the exhaust airstream.
Such devices are called heat recovery or energy recovery ventilation units and may be referred to in northern climates as HRVs. In southern climates they are referred to as energy recovery ventilation devices or ERVs. Essentially, the only difference between these two units is that an HRV captures heat energy from the exhaust airstream, whereas an ERV reduces a cooling load imposed by the fresh air stream.
Typically, these devices comprise a body containing an air to air heat exchanger. The exhaust airstream is passed through one side of the heat exchanger while the fresh air stream is passed through the other side of the heat exchanger. In this way the airstreams are allowed to exchange energy by means of a counter current heat exchange, without the airstreams being in direct contact or being allowed to mix with one another. Thus the quality of the fresh air is preserved.
Again typically, HRV and ERV devices include small fans to drive the air through the heat exchanger. Ideally the flow of fresh air into the building should be equally matched by the flow of stale air being exhausted out of the building. Although the fans can be calibrated in a factory setting to a predetermined flow rate, site-specific installation parameters can affect the aerodynamic head for the inflow and outflow lines and thus volumetric performance of the fans.
As a result there is understood to be a need to balance the airflow streams manually for each ERV/HRV installation for example through the use of manually adjustable dampers that restrict the airflow through the conduits leading to the fans. This balancing is accomplished by means of a skilled technician using small airflow measurement devices called pitot tubes, which may be temporarily installed on the respective airstreams to measure and calibrate the incoming and outgoing airflows. Then the airflow through an individual fan can be site adjusted by a technician by adjusting dampers until the visual inspection of the pitot tubes reveals a balanced airflow across the ERV/HRV for that specific location at that specific time.
Unfortunately, this airflow balancing adjustment requires considerable time from the technician and there is no easy way for a building occupant to be able to tell if it is been done correctly, or indeed, if at all. In some cases this balancing step may be skipped by the installer to save money. In other cases changes to the airflow system or in air pressure can affect the balancing and so what might have been balanced at one point can get out of balance. Further there is a tendency for the fan characteristics to change over time, due to changes in the lubrication and wear on the mechanical parts, or even an accidental change to the baffle position during routine maintenance or the like of the unit. In most cases the units will include removable filters which require periodic cleaning meaning that the unit is opened and the sensitive elements, such as the baffles, are exposed. None of these potential unbalancing changes can be accurately detected without a return of the technician and a recalibration of the system by means of the pitot tube measurements. Therefore there is a need for an improved way of balancing the air flows through ERVs and HRVs.
Examples exist in the prior art that attempt to improve airflow balancing in these types of ventilation units. For example, U.S. Pat. No. 7,458,228, is directed to some of these issues. However in this device a single motor is used to drive two fans. Adjustment of the airflow is accomplished by means of movable dampers which restrict the air flow by closing one or the other the air flow pathway to a certain extent. This patent teaches that balancing is achieved by determining the first static pressure difference in the fresh air path by using first and second static pressure sampling locations and then determining a second static pressure difference in the exhaust air path using third and fourth static pressure sampling locations comparing the predetermined exhaust air flow value corresponding to the first static pressure difference with a predetermined exhaust air flow value corresponding to that second static pressure difference to determine if a predetermined fresh air and exhaust air flow values are at least substantially equal. Again, this invention requires the use and installation of pitot tubes, and manual adjustment of fan dampers. Further, this system cannot adjust to changes in the airflows over time, without some intervention of a skilled technician.
Other examples of prior disclosures which address the issue of balancing air flows include U.S. Pat. Nos. 6,289,974; 7,007,740; 7,458,228; 7,656,942; 7,795,827; and U.S. Publication Application Nos., 2001/0030036A1; and 2002/0017107 A17. While interesting, none of these prior devices overcome the issue of requiring a manual measurement and then manual adjustment of for example movable dampers for the airflow to be balanced across the ventilation units. Thus, none of these prior disclosures overcome the issue of requiring a re-attendance of a skilled technician to deal with any changes that might occur to the airflows over time.
SUMMARY OF THE INVENTION
What is desired is a simple and easy to use HRV and/or ERV unit that can reliably maintain a balanced airflow between the fresh air and the exhaust air without requiring manual measurement, visual inspection of gauges or pitot tubes, manual adjustments of dampers or the like, and most preferably does not require the services of a skilled and expensive technician for each and every installation. Such a device should provide a balanced airflow under all conditions regardless of site specific aerodynamic issues and should be able to maintain such a balanced airflow in light of changed conditions either by reasons of a change to the site-specific ventilation ducting configuration, which can change the aerodynamic head, changes in air pressure, changes in fan motor characteristics due to mechanical wear or for any other reason. As well such a device should preferably provide to the occupants a reliable indication that the air flows through the device are both appropriate for the occupants' air-quality concerns and that inflows and outflows are balanced. It is further desirable for the device to render the air flows through the device adjustable to suit varying occupancy levels. For example, it is desirable to be able to reduce the airflow when a dwelling is unoccupied and there is less need for fresh air to conserve energy. At the same time a minimum airflow may be required to for example control humidity or the like.
The present invention addresses the foregoing issues through the use of a ventilation device with automatic air flow rebalancing. According to the present invention air flow sensors can be used which produce a signal proportional to a volume of air flowing past the sensor. These signals can be generated for each of the fresh air inflow and exhaust air outflow across the heat exchanger. By comparing the two signals the present invention enables a controller to monitor and adjust the individual fan speeds to achieve a dynamic and if desired relatively continuous balancing of the air flows.
The invention comprehends using air flow diffusers, in the vicinity of the sensors, to assist in developing a laminar air flow stream past the sensors. Laminar air flow is more reliably measurable than is turbulent air flow. The invention also comprehends using identically sized cross-sectional flow areas in the vicinity of the inflow and outflow sensors, to permit the sensors readings to be easily equated, although using different areas with an appropriate area calibration factor is also comprehended, if less preferred
Therefore according to a first aspect of the present invention there is provided a heat and energy recovery ventilation unit for a building, said building having an inside and an outside, said unit comprising:
A main body having a fresh air inlet and an indoor air outlet on one side and a fresh air outlet and an indoor air inlet on the other side and having an air to air heat exchanger within said main body and connected to each of said inlets and outlets to define respective air flow passageways for each of said indoor air and said fresh air, said heat exchanger permitting heat and energy exchange between said indoor air and said fresh air;
A first variable speed blower for causing said indoor air to pass through said heat exchanger to said outside;
A second variable speed blower for causing said fresh air to pass through said heat exchanger to said inside;
At least one electronic air flow sensor to measure at least one of said indoor air flow and said fresh air flow, said air flow sensor producing a data signal related to said measured air flow; and
A controller for receiving said data signal, said controller using said data signal to control at least one of said variable speed blowers to provide a balanced fresh air inflow and indoor air outflow through said heat recovery ventilation unit.
According to another aspect of the invention there is provided a method of operating a heat and energy recovery ventilation unit comprising the steps of:
a. Using a first airflow sensor to indicate an air flow through said unit in a first direction; b. Using a second airflow sensor to indicate an airflow through said unit in a second direction; c. Communicating said indicated air flows to a controller, d. Comparing said indicated air flows and determining if a difference exists between the indicated air flows and e. Sending motor control signals to at least one blower motor to change the speed of the blower to reduce said determined difference.
BRIEF DESCRIPTION OF THE DRAWINGS
Reference will now be made by way of example only to preferred embodiments of the present invention with reference to the attached figures in which:
FIG. 1 shows a ventilation device according to the present invention installed in the building with ducting connecting the device to both the outside fresh air source and an inside exhaust air source;
FIG. 2 shows a close-up of the ventilation device of FIG. 1 from above with a cover removed;
FIG. 3 shows a side view of a diffuser according to the present invention;
FIG. 4 shows a remote control wall unit with display according to the present invention;
FIG. 5 shows a view of the unit showing a tilted core housing and associated drain;
FIG. 6 shows a schematic layout according to the present invention;
FIG. 7A shows a side cutaway view of an embodiment of a wall box exhaust according to the present invention;
FIG. 7B shows a side cutaway view of an embodiment of a wall box intake according to the present invention;
FIG. 8A shows a front view of a timer switch according to the present invention; and
FIG. 8B shows a side view of the timer switch of FIG. 8A .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows a heat energy recovery ventilation unit 10 installed in the building 12 . In the present specification the term building means any structure with living quarters that requires fresh air turn over. Thus the term building comprehends single or multiple family dwellings such houses, duplexes, apartments in high rise buildings, condominium units, row houses and any other enclosed living or occupation space that requires an inflow of fresh air and an exhaust of stale air to meet the needs of living breathing occupants.
The unit 10 may be installed in a basement 14 , for example, and includes ducting leading up to and away from the unit 10 . The unit 10 is sized and shaped to be installed in either a vertical orientation or a horizontal orientation. Good results have been achieved with an overall size of about 27¾ inches in width, about 21 inches in depth and about 9 inches in height, and having a total weight of between 50 and 60 pounds, most preferably about 55 pounds.
The ducting 16 begins with inflow air registers 18 located in rooms 20 and 22 and includes ducting 23 which directs stale air towards the unit 10 . The ducting 24 carries fresh air from the unit 10 and distributes it into rooms 26 , 28 , 30 and 32 for example through fresh air registers 27 , 29 , 31 , and 33 . It will be understood by those skilled in the art that the configuration of the ducting 23 , 24 can be easily altered without departing from the scope of this invention. All that is required is to provide a flow path within the building 12 to supply the amount of fresh air that is stipulated in the local building code and to distribute the fresh air into the building in an acceptable way while also providing a flow path within the building 12 to collect and remove stale air.
Leading away from the unit 10 towards an exterior wall 34 is further ducting 36 and 38 . The ducting 38 carries fresh air from the outside 40 to the unit 10 . The ducting 36 carries stale or exhaust air from the unit 10 to an outside vent, which may be in the form of wall boxes 42 to permit the stale air to be vented to the outside 40 . It will be appreciated by those skilled in the art that many forms of outside register or vent can be used including a double vent with double grille, a double vent with side exhaust/intake, and two single vents by way of example, all of which are comprehended by the present invention. Most preferably the wall box 42 is provided with at least one flapper valve 43 (see FIGS. 7A and 7B ), to cover the inlet opening when it is not in use. Further, the flapper valve 43 is preferably biased to a closed position, and releasably retained in the closed position such as by a weak magnet or magnetic clasp. In this way, when not in use, the ventilation opening will be closed to prevent bugs, animals and the like from gaining access, and also to preserve energy. The magnetic clasp can be sized and shaped to open for example, under the influence of the air pressure when the fan in the unit is being operated. The present invention further comprehends that flapper valves can be provided over both the air outflow and air inflow openings.
Similar to a conventional HRV/ERV the present invention allows heat exchange to occur through a heat exchanger core between air exiting the building and air entering the building. In this way the at least some of the energy contained within the air inside the building can be recovered and effectively transferred to the incoming air stream. A number of materials can be used to form the core depending upon the application but good results have been achieved with cores made from aluminum and plastic. For an ERV an enthalpy core is also provided. As with conventional HRVs and ERVs the present invention uses a core consisting of a series of passageways through the core where the fresh and stale air pass past one another separated by a thin heat transfer barrier such as aluminum. This permits the air streams to exchange energy, in a counter current fashion, without permitting direct contact or mixing of the air streams to occur.
FIG. 2 shows a view of the unit 10 from above. For ease of illustration a cover has been removed to show the internal components. The cover, when in place seals the unit 10 and establishes separation between the inflow air stream and the outflow air stream. The core is shown at 50 within the primary plenum 52 in the unit 10 . A secondary plenum 54 is also shown. Stale air passes through inlet 56 into the core 50 . Once through the core 50 it is passed to an exhaust outlet 58 . Fresh air enters the unit 10 through fresh air inlet 60 , and passes through the core 50 . Fresh air is exhausted from the unit 10 through fresh air outlet 62 . In the preferred embodiment of the present invention two separate variable speed blowers are provided, one at 64 for the fresh air flow through the unit 10 and the other at 66 for the exhaust air flow through the unit 10 . Good results have been achieved with high efficiency, energy saving, permanently lubricated PSC motors which are thermally protected for continuous operation.
Also shown in FIG. 2 is a defrost damper 70 , controlled by an actuator arm 72 which is in turn attached to a solenoid 74 . Most preferable the defrost damper is automated and comes on in the event the air temperature reaches −5 degrees C. The solenoid 74 is controlled by a controller 76 which is housed in an electrical box 78 . The functions of the controller 76 are described in more detail below. Also shown are hinges 80 , and a backdraft damper 82 .
FIG. 2 shows the location of airflow diffusers 84 , and 86 which are intended to transform the turbulent airflow produced by the blowers into a more regular or laminar form of air flow. Better results have been achieved with the present invention when the air flow sensors are measuring the air flow across the diffusers than without the diffusers. The diffusers encourage laminar air flow, which can be more reliably measured than can turbulent airflow. According to the present invention air flow sensors 88 ( FIG. 3 ) are positioned in the diffusers 84 , 86 to measure the air flow passing through the unit in both inflow and outflow directions. Although the present invention comprehends having only one airflow sensor 88 the most preferred form of the invention is to include an airflow sensor 88 within each of the fresh air and the stale air streams, so the airflows can be dynamically balanced through electronic fan control.
The preferred form of airflow sensors 88 are ones which produce an electronic signal that is proportional to or can be correlated to the volume of air flow flowing past the sensor. Although different types of sensors maybe used the preferred sensor is one which is quite sensitive to small temperature changes, and thus can be used to measure air friction, which in turn is an indication of the airflow rate. As will be understood by those skilled in the art, this type of electronic sensor needs to be calibrated to deliver reasonable results. The present invention comprehends other forms of air flow sensors, provided they produce an electronic signal that is proportional to the air flow past the sensor.
Ideally the cross sectional area of the inflow air stream where it is measured will be the same as the cross sectional area of the outflow air stream where it is measured to ensure that the sensor outputs are directly comparable. The present invention comprehends that the areas could be different, but then the air flows would have to be calibrated and a calibration factor would need to be applied to the sensor readings before they could be directly compared. Therefore, for ease of operation positioning the sensors in air flows of identical cross sectional areas makes the operation of the device easier.
In the most preferred embodiment of the present invention the electronic signals produced by the two sensors are provided to the controller on a continuous basis. As will be appreciated by those skilled in the art various sample rates can be used to transmit the air flow data to the controller. A preferred range of sample rates is between once per second and once per millisecond, although other rates are also comprehended by the present invention. When the signals are received by the controller the controller makes a comparison to determine if the signals representing the in air flow and the exhaust air flow are the same or different. In the event that a difference is detected the controller sends a motor control signal to each of the blowers to try to reduce the difference. In order to avoid uncontrolled oscillations in motor speeds a dampening algorithm is used. In this way the present invention provides for a motor control system that is continually seeking to reduce the difference between the air inflow rate and the air exhaust rate.
In the most preferred form of the invention when the air flow rates are sufficiently close then the controller does not send out a motor control signal and does not adjust the speed of the blowers. Although different sensitivities can be used keeping the measured air flow rates within about 5% of each other has been found to provide adequate results.
FIG. 3 shows a view of a diffuser of FIG. 2 . This shows the diffuser 84 with the air flow sensor mounted to one of the ribs 90 . Air flowing through said diffuser therefore impinges on the electronic air flow sensor whereby an electronic signal can be created which is generally proportional to the volume of air flowing past the sensor. This signal is then sent to the controller. As will be understood by those skilled in the art the air flow sensor is operatively connected to the controller, either directly by wire or by a wireless connection as is known in the art.
FIG. 4 shows a remote wall unit 98 that can be used to control the operation of the unit. The wall unit includes a display 100 for the purpose of displaying to the user the state of operation of the unit. A variety of settings are possible, including, an adjustable air flow rate with for example four low speeds rates of between about 45 to 95 CFM and four high speed rates of about between 95 to 125 CFM being preset into the controller. These rates are appropriate for a unit to service the fresh air needs of a living space having a floor area of about 2000 square feet. Other flow rates and sizes of units may be appropriate for larger living spaces.
Preferably the wall unit 98 includes push buttons 102 to permit a user to control the unit 10 . The display 100 can show what mode of operation the unit 10 is in including off, normal, high, recirculating, or energy saving modes. The display also preferably includes a humidity and error display and permits humidity settings of up to 80% relative humidity. Ideally two defrost modes are also provided, one in which the air is recirculating and the other in which the air is not recirculating. There may be multiple controls operatively connected to a single unit 10 and it is preferred that they be wired directly to the unit 10 to eliminate the need for batteries in the wall unit. Another mode of operation can be manual air balancing instead of automatic air balancing, but automatic air balancing will be used most often. The manual air balancing setting can be used to check on the calibration of the system, and the present invention provides for preformed pitot tube insertion openings 200 ( FIG. 6 ) strategically position in the cover plate to permit the balancing of the unit to be manually checked from time to time.
According to the present invention the unit 10 has power ratings of 115V/1/60 Hz, 1.10 Amp. Also the preferred standby current is about 7 W.
FIG. 5 shows the bottom panel 110 of the unit 10 (when the unit is installed horizontally). This bottom panel includes a sloped impression 112 that is pressed into the panel, for the purpose of allowing the unit to sit level, even though the core is set at a slight angle relative to horizontal. Many different angles can be used but good results are achieved with an angle of between 1 degree and 10 degrees, most preferably about 2 degrees. All that is required is to provide enough of an angle to the core to ensure that any condensation which condenses on the core is encouraged to drain out of the core and then out of a drain. A drainage tube can be provided to direct the condensation to a house or floor drain in a known manner. It will now be appreciated that the sloped impression 112 provides for an automatically draining core which is simple and easy to fabricate and reliable in terms of establishing good drainage of the core.
FIG. 6 shows a plan view of a schematic of the present invention. As shown, the dampers 84 , 86 are placed on opposite sides of the main plenum 52 , each damper includes an associated air flow sensor 88 . The blower motors 64 and 66 are shown, to force the air through the core (not shown). A humidity sensor 210 is also shown along with a temperature sensor 214 . As well a safety switch 216 is also provided to cause the unit to shut off in the event the lid is removed. The temperature sensor 214 , and the humidity sensor 210 are used to help control the unit 10 and the readings may also be displayed in the display 100 of the wall unit 98 .
FIG. 7A shows a side view of an embodiment of a wall box exhaust 42 A and FIG. 7B shows a side view of an embodiment of a wall box intake 42 B. Each of the wall boxes 42 A and 42 B include a magnetic flapper valve 43 A and 43 B, respectively. Each of the wall boxes 42 A and 42 B include a baffle 120 which has a neoprene backdraft damper 122 . Each baffle 120 is biased towards a corresponding magnet 124 . Airflow direction is shown by arrows in each of FIGS. 7A and 7B . As shown in FIG. 7A , airflow travels out of the exhaust wall box 42 A. As shown in FIG. 7B , airflow travels into the intake wall box 42 B. The baffle 120 is biased against the direction of airflow to ensure that the ventilation openings are closed when not in use.
FIGS. 8A and 8B show an electronic timer switch 126 . The timer switch 126 allows the user to activate the HRV or ERV units on high speed for periods of time, such as 20, 40 or 60 minutes. The timer switch 126 can be activated by the user pressing the button 130 . LEDs 132 are shown on the side of the timer switch 126 . All 3 LEDs 132 will blink to indicate error if any failure is detected on the HRV or ERV.
The operation of the present invention can now be understood. Once energized, the controller will send a control signal to the fresh air motor to provide a certain preset flow rate, for example, a low flow of 55 CFM. This will cause the fresh air blower to start to draw fresh air through the heat exchange core. At the same time, a motor control signal will be sent to the exhaust air flow blower, to cause it to operate at almost the same speed. However, although approximately equal control signals can be sent, there is no guarantee that the actual air flows will be the same due to variations in aerodynamic head and the like. At this point any magnetized dampers on the outside vent or boxes will have been opened by the air pressure caused by the blowers.
The next step is for the air flow sensors to begin sampling the air flow flowing past them through the dampers. At this stage the sensors are going to produce an electronic signal which is generally proportional to the air flow past each sensor. As noted above generally laminar air flow provides more reliable air flow measurements and laminar air flow can be encouraged by using diffusers as shown. Further by ensuring that the cross sectional area of the two air flows is about the same, the sensor readings can be reliably compared.
The next step is to communicate the electronic signal which is proportionate to the air flow, so the two signals, from inbound fresh air and outbound stale air can be compared. The comparison can be made in any convenient way including simply summing the electrical values of the signals, or translating the signals into some form of value and then comparing the values. Once the comparison is made, an adjustment is made to one or both of the motor speeds to reduce any difference detected. A statistical sampling algorithm can be used to smooth out the readings, such as taking an average reading from a number of readings taken over a predetermined time frame. Further the algorithm can take into account that the values are to approach the desired value such as by changing the speed by less the amount required so as to allow the fans to approach the same speed without constant overshooting.
Also, the present invention comprehends that a threshold value can be used to decide that the air flows are close enough that no further adjustment is required. Most preferably there would be no adjustment required of the air flows are within eight percent or lower at each other and ideally being within about five percent is desired. Now the system of the present invention is going to continuously dynamically balance the air flows even as certain environmental factors, such as air pressure, changes. In this way the present invention provides a reliable balanced air flow for the unit as a whole. Even if the air flow rate is changed, for example is increased to 95 CFM the sensors will again measure the difference between inflow and outflow air speeds and engage in continuous dynamic balancing by means of individual blower motor control, but simply with the different higher air air flow rate used as the target rate for the set point. As will be understood by those skilled in art the preferred form of the invention uses identically sized inflow and outflow cross-sectional areas where sensors are located. Identical areas allow the signals to be directly compared. The present invention comprehends using different sized areas, but in that case a flow area calibration factor would need to be used before comparing the signals.
While the foregoing description includes detailed aspects of one or more preferred embodiments it will be understood by those skilled in the art that many modifications and variations of the invention are possible without departing from the scope of the appended claims. Some of these have been discussed above and others will be apparent to those skilled in the art. For example, while the preferred position for the blowers is as shown in the drawings, the blowers could be placed on the opposite side of the unit and still function in generally the same manner. | A heat and energy recovery ventilation unit for a building, having an inside and an outside. The unit including a main body having a fresh air inlet and an indoor air outlet on one side and a fresh air outlet and an indoor air inlet on the other side and having an air to air heat exchanger within the main body and connected to each of said inlets and outlets to define respective air flow passageways for each of said indoor air and said fresh air, the heat exchanger permitting heat and energy exchange between said indoor air and said fresh air. Also included is a first variable speed blower and a second variable speed blower and at least one electronic air flow sensor to measure at least one of the air flows the air flow sensor producing at least one electronic signal related to the sensed air flow. Also included is a controller for receiving the data signal, the controller using the data signal to control at least one of the variable speed blowers to provide a balanced fresh air inflow and indoor air outflow through the ventilation unit. A method of operating the unit is also disclosed. | 5 |
FIELD OF THE INVENTION
[0001] The present invention relates to the field of customization of clothes, accessories and other articles.
BACKGROUND OF THE INVENTION
[0002] People like to express their individuality and often do so through the clothes that they wear and the accessories that they select. They show this individuality both when wearing the clothes and/or accessories and when sharing images of or participating in discussions about them on-line. However, there is an inherent challenge in trying to express one's individuality through mass produced goods. When companies produce and market new articles of clothing or accessories or new styles, the first purchasers and users may stand out, but as those articles become popular, by definition they are no longer expressions of individuality because a large number of people will wear and use them.
[0003] One solution that the apparel and accessories industries have found is to offer articles that can be customized by the user. For example, common gifts for young children and tweens are jewelry making kits and key chain making kits. For older persons, also sold in the marketplace are fabric pens and tools for adding jewels or other decorations to clothing, typically denim. Unfortunately, many of these and similar tools are not sufficiently user friendly, particularly for children.
[0004] Thus, to date the desire for consumers to find new ways to customize their apparel, accessories, and other articles of personal property remains unsatisfied. The present invention addresses this need by providing new, efficient, and user friendly tools, kits and methods for personalizing articles of personal property.
SUMMARY
[0005] Various embodiments of the present invention provide one or more of tools, kits and methods for customizing articles, including but not limited to apparel, accessories and other goods. A person may use these embodiments to introduce the appearance of a shape to an article by removing color or material that corresponds to the shape. Through the use of the inventions described herein, one can effectively, efficiently and enjoyably customize articles.
[0006] According to a first embodiment, the present invention provides a kit for customizing an article of personal property comprising: (a) a rubbing template, wherein the rubbing template has a front surface and a back surface, wherein the front surface defines a shape and the back surface has a surface area; (b) a rubbing tool, wherein the rubbing tool comprises an abrasive surface; and (c) a mounting sheet, wherein the mounting sheet comprises a first surface and a second surface, wherein the first surface comprises an adhesive material and the first surface has an area that is larger than the surface area of the back surface of the rubbing template.
[0007] According to a second embodiment, the present invention provides a method for customizing an article comprising: (a) affixing a rubbing template to a mounting sheet to form an affixed rubbing template, wherein the rubbing template has a front surface and a back surface, wherein the front surface defines a shape and the back surface has a surface area and wherein the mounting sheet comprises a first surface and a second surface, wherein the first surface comprises an adhesive material and the first surface has an area that is larger than the surface area of the back surface of the rubbing template; (b) placing the affixed rubbing template adjacent to an inside surface of an article at a transfer location; and (c) rubbing an outside surface of the article at a location that corresponds to the transfer location.
[0008] Through the use of the various components of the present invention, one may efficiently and effectively transfer shapes to articles, including but not limited to apparel and accessories. The various components of the kits and the tools recited for use in the methods described herein may be used together to provide an enjoyable way for children and adults to personalize their articles through the introduction of the appearance of shapes such as designs, slogans and letters.
[0009] These and other tools, kits, methods, features, and advantages of the present invention will be apparent to those skilled in the art from the following detailed description of the embodiments and the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] The tools, kits and methods disclosed herein and the following detailed description of certain embodiments thereof may be understood by reference to the following figures. Elements in the figures are presented for illustrative purposes, and they are not necessarily drawn to scale.
[0011] FIG. 1 is a representation of the front and back of a pair of jeans that have been customized.
[0012] FIG. 2 is a representation of two rubbing templates.
[0013] FIG. 3 is a representation of a rubbing template affixed to a mounting sheet.
[0014] FIG. 4 is a representation of a rubbing template situated under a layer of a pair of jeans.
[0015] FIG. 5 is a representation of person using a rubbing tool in order to create a rub design.
[0016] FIG. 6 is a representation of how the fabric, a rubbing template, and a mounting sheet may be oriented with a peel off adhesive in place to protect the mounting sheet prior to its use at a desired location.
DETAILED DESCRIPTION
[0017] The present invention will now be described in detail by describing various illustrative, non-limiting embodiments thereof with reference to the accompanying drawings. The invention may, however, be embodied in many different forms and should not be construed as being limited to the illustrative embodiments set forth herein. Rather, the embodiments are provided so that this disclosure will be thorough and will fully convey the concept of the invention to those skilled in the art.
[0018] According to a first embodiment, the present invention provides a kit for customizing articles. An article is “customized” when a user introduces his or her style through one or more designs, words, slogans, letters, symbols or representations of real or imaginary objects or other shapes. The term customized is used interchangeably with the term “personalized.” A “kit” refers to a combination of elements that are stored, sold or shipped together. They may, for example, exist in a box at a point of sale in a brick and mortar or online environment.
[0019] The kit comprises a rubbing template, a rubbing tool and a mounting sheet. Optionally, the kit may further contain one or both of a rubbings collector and an article of personal property. The components may be used to transfer a shape to the article efficiently and effectively. By transferring the shape, a shape that is the same size as that of a shape on the rubbing template may be caused to appear on the article of personal property; however, no physical part of the rubbing template becomes permanently affixed to or part of the article. Thus, the step of transferring is in effect a means by which to copy the shape through rubbing and displacement of coloring that was previously at a location on the article. What has been transferred and appears on the article may also be referred to as a “rub design.” Each of the aforementioned components is described below.
[0020] Rubbing Template
[0021] The rubbing template is a physical item that has a front surface that defines a shape of interest. The shape is what is to be transferred to the article. In some embodiments, only one surface of the rubbing template defines a shape to be transferred. In other embodiments, two, three, four, five, six, or more surfaces of the rubbing templates define different shapes that can be transferred at different locations of the same article or at location on one or more other articles.
[0022] In some embodiments, there is only one surface that defines a shape to be transferred, and that surface may be referred to as a front surface. In some embodiments, the front surface may be flat and it may form the outline of the shape and none of the interior of the shape; or the outline of the shape and some but not all of the interior of the shape; or the outline and the complete interior of the shape. In one embodiment, the front surface forms a relief. In some embodiments, the front surface is flat and all of the edges or some of the edges (e.g., only the edges that form the exterior of the shape when the shape to be transferred contains less than the complete interior as defined by the outline) of the front surface are beveled. Through the use of beveled edges, one can reduce the likelihood of tearing of any article of personal property or fabric to which a shape is to be transferred.
[0023] When the front surface defines only the outline of the shape, there may be recesses in the rubbing template between the outline so that when the shape is transferred, the article displays only an outline of that shape. In these embodiments, the rear surface may be solid. Alternatively, when the shape is to form an outline, the interior between the outline over the entire height of the shape may have an absence of material, which renders the rubbing template similar to a cookie cutter with a thick wall. As persons of ordinary skill in the art will recognize, in these cases, the front surface forms the perimeter of the shape. As a person of ordinary skill in the art will also recognize, these gaps, regardless of whether they extend all of the way through the rubbing template will correspond to areas on the article in which color or material is not removed. In some embodiments, the outline is a uniform thickness and, e.g., 2 mm to 10 mm or 3 mm to 8 mm.
[0024] When the front surface defines the outline of the shape and only a portion of the interior of the shape, there may be recesses so that when the shape is transferred, the article displays an outline of that shape and certain features that are not along the perimeter of the shape. This allows for more complex designs to be used. For example, select features of an animal or plant or flower may form part of the front surface or designs within shapes such as stars, hearts and rainbows may be formed by the presence of lines that appear in the interior of the shape. By way of non-limiting examples, the features and lines may have a thick of 2 to 10 mm or 4 to 6 mm.
[0025] On the rubbing template the side that contains the front surface may have depressions between the elements of the first surface so that the back surface remains solid, or the gaps between the front surface may extend through to the back surface. As a person of ordinary skill in the art will recognize, these gaps, regardless of whether they extend all of the way through the rubbing template will correspond to areas on the article in which color or material is not removed.
[0026] In any case in which there are depressions, the distance from the back surface of the rubbing template, which is the surface that is opposite of the front surface may be a first distance and the depressions may be a uniform second distance from the back surface or each depression may be a second distance from the back surface that is not uniform. Alternatively, when the shape is to form an outline, the interior between the outline over the height of the shape is hollow. Thus, in these cases, the front surface forms the perimeter of the shape and the back surface is configured in the same manner.
[0027] When the front surface defines the outline and the complete interior of the shape, a solid shape will appear on the article after transfer and the face on which the first surface is located is a uniform distance from the rear surface.
[0028] The term “shape” includes but is not limited to a symbol, a pattern of symbols, a letter, a group of letters, a word, a phrase, a number, a representation of an animal, a representation of a person, a representation of a flower, a representation of a tree, a representation or a motor vehicle, a logo or a combination thereof. Further, when a shape is used, one may repeat the transferring process with that shape or alternating with other shapes or a non-regularly alternating plurality of shapes to create a pattern of shapes.
[0029] Each of the front surface and the rear surface has a surface area. The surface area of the front surface may be smaller than, larger than or the same size as that of the rear surface. In some embodiments, the walls of the rubbing template are all perpendicular to the front surface and the rear surface.
[0030] The rubbing template may be made of any material that is sufficiently sturdy that the acts of rubbing and affixing as described in this specification will not destroy its integrity. Further, the material is preferably sufficiently sturdy that it allows for effective transfer of a shape and reuse of the rubbing template. By way of non-limiting examples, the rubbing template may comprise, consist essentially of or consist of rubber, plastic, wood, a laminate material, one or more metals, one or more metal oxides, or a metal alloy, or combinations thereof. In one embodiment, the rubbing template comprises, consists essentially of or consists of rubber and a laminate material and the first surface is rubber and the second surface is the laminate material. When the material is rubber, preferably it is sufficiently sturdy, that rubbing as described herein will not distort its shape.
[0031] In some embodiments, none of the surfaces of the rubbing template are adhesive. In other embodiments, the front surface comprises or is associated with a tacky material that allows for reversible adhesion to another surface. When a tacky material is present, preferably it is the selected so that it permits reversible association with the article at a desired location.
[0032] In some embodiments, the rubbing template may, for example, be from 2 cm to 30 cm or from 5 cm to 20 cm long; from 2 cm to 30 cm or from 5 cm to 20 cm wide; and from 1 cm to 5 cm or from 2 cm to 4 cm high.
[0033] In some embodiments, the rubbing template also comprises a loop. The loop may be made of the same material or different material as that of which the rubbing template is made, e.g., plastic, rubber, metal, a metal oxide or combinations thereof. Alternatively, it may comprise, consist of or consist essentially of a different material such as an elastic rubber that is more flexible than the material of the rubbing template. The loop is preferably situated so that it does not interfere with either the process of the transferring of the shape or the process of causing the subbing template to affix to the mounting sheet. For example, it may be located on a side of the rubbing template. This loop may be used to hang the rubbing template on a hook or through a clip. In some embodiments the diameter of the loop is 0.5 to 5 cm or 1 to 4 cm.
[0034] Rubbing Tool
[0035] The rubbing tool is designed to rub or scratch off color containing elements of the article. This is accomplished at the locations on the article that are overlain at the highest points on the rubbing template i.e., the front surface. When the article is pulled taut over the rubbing template, those points will have the greatest tension and will either not bend or give in response to being rubbed, or they will do so less than the areas at which there is less tension. Consequently, in these areas in which the highest tension is formed, the rubbing tool will permit removal of color containing elements of the article. By contrast, in other areas, the material of the article will move, fold or crease in response to rubbing, and the rubbing tool will cause no or de minims amounts of the color containing elements to be removed.
[0036] In some embodiments, the rubbing tool comprises an abrasive surface. The abrasive surface may, for example, be made of a combination of an elastomeric material and abrasive particles. The abrasive particles may be embedded in and/or disposed upon the surface of the elastomeric material so that a sufficient number of abrasive particles are capable of contacting and abrading the fabric. Examples of elastomers include but are not limited to nitrile, rubber, urethanes such as polyurethane, acrylics, epoxies, polyvinyl chlorides and butadiene rubber. The abrasive particles are preferably rigid and/or granular. Many different types of abrasive particles may be used alone or in combination with one another, including aluminum oxide, silicon carbide, alumina zirconia, diamond, ceria, cubic beron nitride, ganat, ground ceramic particles, ground plastics (i.e., polyvinyl chloride (PVC)), gromid glos and quartz.
[0037] The abrasive surface may be located on fewer than all sides of the rubbing tool, e.g., on only one side, which may be referred to as a rubbing face. By way of a non-limiting example, the rubbing tool may be an emery board.
[0038] In some embodiments, in addition to an abrasive surface, there may also be a buffing surface. The buffing surface may, for example, also be located on the rubbing face. When both the abrasive surface and the buffing surface are located on the rubbing face, they may, for example, be located on opposite portions of the rubbing face so that a user is able to use exclusively the abrasive surface or the buffing surface at any one time and to switch between them he or she may rotate the device, e.g., 180 degrees. The abrasive surface is designed to permit scratching away of color containing material, whereas the buffing material is designed to slide away the material and to give the appearance of a complete removal.
[0039] By way of further example, the rubbing tool may be in the form of a flexible foam block such as a block made from polyurethane that has an abrasive coating. The foam block may be molded or cut into a shape and of a size that renders it suitable for holding by a user in her or his hand. Thus, it may have gripping material, and additionally or alternatively indentations that correspond to places for a user's fingers. Alternatively, in some embodiments it may be rectangular or substantially a 3-D rectangle.
[0040] In some embodiments, the rubbing tool may, for example, be approximately 8 cm to 30 cm long, 5 cm to 10 cm side and 1 cm to 4 cm high.
[0041] Mounting Sheet
[0042] The mounting sheet holds the rubbing template in place. Thus, it is configured to be placed under the material to which the shape of the rubbing template is to be transferred. The mounting sheet may be rigid or flexible or semi-flexible. Preferably when nothing is affixed to the mounting sheet it is flat or substantially flat. In some embodiments, it may be in the form of flexible foam that has a surface with adhesive properties or has been treated with a material to render that surface adhesive. The adhesive property of the mounting sheet allows for the mounting sheet to maintain contact with the article of personal property to which the shape will be transferred during the transferring process, including but not limited to during the rubbing step. Thus, it facilitates locking in place of the shape relative to the article of personal property when the shape is mounted on the mounting sheet because the shape is affixed to the mounting sheet and the mounting sheet is affixed to the article of personal property. The ability to cause the mounting sheet to retain its position, and thus the shape to retain its position, relative to the article of personal property will allow users to create greater contrast in their designs.
[0043] The mounting sheet may be defined by its first surface and its second surface. The first surface comprises an adhesive material. Within the definition of comprising an adhesive material is the situation in which it is coated with the adhesive material. When not in use, the mounting sheet may have a protective coating or film that rests on the first surface. This protective coating or film may, for example, comprise, consist essentially of or consist of plastic that is capable of being removed from the mounting sheet and leaving the adhesive material capable of adhering to other materials.
[0044] Preferably, the mounting sheet is designed so that the protective coating or film may be reused on the same mounting sheet to protect the adhesive material from either or both of becoming permanently affixed to another surface and drying out. This additional sheet may be in the form of a peel off adhesive. Regardless of whether there is a peel off adhesive or other protection sheet, the mounting sheet may be designed such that its adhesive is reusable. The advantage of a peel off adhesive that may be reusable is that it prolongs the life of the mounting sheet.
[0045] On the side of the mounting sheet that is opposite to the first surface is a second surface. In some embodiments, the second surface comprises or is coated with a material that is not adhesive. By way of a non-limiting example, the second side comprises, consists essentially of or consists of rubber and/or a laminate material. In these embodiments, the second side is non-adhesive and although friction may hold it in place with another surface, no adhesive material is present to cause adhesion.
[0046] Preferably, the first surface of the mounting sheet has an area that is larger than the surface area of the back surface and the front surface of the rubbing template. Furthermore, preferably the surface area of the first surface of the mounting sheet is larger than the combined surface areas of the back surface and all of the side surfaces of the rubbing template. In some embodiments, the first surface of the mounting sheet has an area of adhesive material that is at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, or at least 60% larger than the surface area of the back surface of the rubbing template.
[0047] By way of a non-limiting example, in some embodiments, the mounting sheet is a regular shape such as a circle, ellipse, oval, triangle square, rectangle with adjacent sides having unequal lengths, or other polygon. In other embodiments, the mounting surface is an irregular shape. For example, it may be circle with a radius of 4 cm to 15 cm or 8 cm to 12 cm. In other non-limiting examples, it may be a square with sides from 5 cm to 30 cm or 10 cm to 20 cm or a rectangle with a length from 5 to 10 cm and a width from 8 to 30 cm. In some embodiments, the mounting sheet has a thickness of 2 mm to 30 mm or 5 mm to 25 mm or 10 mm to 15 mm.
[0048] For illustrative purposes, one mounting sheet is described above as being used with a single rubbing template. However, persons of ordinary skill in the art will recognize that provided that the mounting sheet is sufficiently larger relative to the size of a plurality of rubbing templates, a single mounting sheet could be used with a plurality of rubbing templates, e.g., at least 2, at least 3, at least 4 or at least 5. In these cases, optionally, the rubbing templates contain mating members that allow them to be held is place relative to each other, e.g., a male member on one side and a female member on the other side, wherein these sides are neither the front surface nor the back surface. Further, one could use a plurality of mounting sheets each with one or more rubbing templates in a desired orientation and location relative to one another. In these embodiments, the mounting sheets may be the same or different sizes.
[0049] Rubbings Collector
[0050] In some embodiments, the present invention comprises a rubbings collector. The rubbings collector is a device that is constructed to collect the rubbings i.e., the material of the article that has been removed through abrasion, thereby leaving the shape. The rubbings collector may have an adhesive surface similar to that of a lint brush. Additionally or alternatively, it may have a magnet, which would be of use should the material that is abraded contain metal.
[0051] The rubbings collector may be a separate instrument or it may be configured to be reversibly affixed to the rubbing tool. In some embodiments, the rubbings collector has an adhesive surface that is capable of reversibly adhering to the rubbing tool and the adhesive surface is wider than the rubbing tool.
[0052] Additionally or alternatively, in some embodiments, the rubbings collector may have a cut out or be otherwise configured with a region that forms a trough in which at least part of the rubbing tool may rest. The side of the rubbings collector that abuts the rubbing tool may be affixed to the rubbings tool through one or more of clips, snaps, hook and latches e.g., VELCROX®, and an adhesive surface. As persons of ordinary skill in the art will recognize, in each of the aforementioned systems other than the use of an adhesive surface, two elements are used and one must be on the rubbings collector and the other reciprocal element on the rubbing tool. Preferably, the two devices are capable of being reversibly affixed to each other. Thus, each of the rubbing tool and the rubbings collector may be reused after being separated from each other, regardless of whether they are re-associated with each other.
[0053] As noted above, the rubbing tool may have an abrasive surface. In various embodiments, preferably, this is not the side that abuts the rubbings collector when the rubbings collector is used.
[0054] When the rubbing tool sits within the trough preferably, the rubbings collector is wider than the rubbings tool. For example, it may be 1 to 5 cm wider than the rubbing tool on each side of the rubbing tool. By being wider than the rubbing tool, the rubbings collector can collect rubbings after each movement of the rubbing tool from side to side. In other dimensions, the rubbings collector may be shorter or longer than the length of the rubbing tool and e.g., 0.5 cm to 5 cm thick.
[0055] In some embodiments the rubbings collector is configured with a hand-grip or a handle. When there is a handgrip, it may, for example, reside on the back of the trough. When there is a handle, it may, for example, extend from the back side of the trough.
[0056] Article of Personal Property
[0057] The article of personal property is the article to which the shape will be transferred. Preferably, it is capable of retaining a rub design and it may, for example, be a fabric. Prior to use of the present invention, the fabric may have a coloring at a location at which the shape is to be formed. After using the present invention, the coloring in that region of the fabric will have been removed and the shape will be defined by a negative, i.e., an absence of color. The rub design may be created when the fabric is either in the form of an article, for example, a consumer product, or it may be in the form of a sheet or swatch that is to be incorporated into the article.
[0058] Fabrics that are capable of retaining a rub design and methods for making those fabrics are described in WO 2014/035817, Ring Dyed Polymer Treated Materials, published Mar. 6, 2014; the entire disclosure of this reference is incorporated by reference as if set forth in its entirety and examples of information that describes types of fabrics as discussed in that disclosure appear in the following paragraphs.
[0059] Fabrics that may be used to retain a rub design include but are not limited to materials that have been formed from one or both of ring dyed yarn and surface dyed yarn. These materials may be prepared with a dye binding composition that includes a polymer and/or additives that are engineered to provide a minimum or maximum degree of migration to position the composition within or on a fiber surface depending on molecular weight and monomer selection. The polymer is generally applied in an aqueous medium. The polymer can be formulated from a number of monomers in the urethane, guanidine, azetidinium, and vinyl halogen families to form polymer emulsions. The solids added on to the textile substrate can range from 0.5% to 50% or 2.0% to 12.0%). Preferably, the polymer has good film forming properties, is durable to laundering conditions, has the ability to incorporate materials that can provide targeted dyestuff attraction and durability, and/or is capable of fixing the dye in its matrix.
[0060] In some embodiments, the dye binding composition comprises a urethane based polymer with a molecular weight ranging from 1,000 to 400,000 g/mole or from 2,000 to 200,000 g/mole. The urethane based polymer may be designed to attract and hold selective dyes. In some embodiments, additional materials may be added. The urethane based polymer, in some embodiments, comprises a polyurethane dispersion.
[0061] For dyeing with selective dyes, materials that can attract targeted dyes within the polymeric matrix may be incorporated into the dye binding composition. In some embodiments, the dye binding composition comprises cellulose esters including cellulose acetate, cellulose propionate, cellulose butyrate, and combinations thereof. In other embodiments, the dye binding composition comprises the polymer and the cellulose ester.
[0062] In some embodiments, the dye binding composition is applied to fibers, yarns, fabrics, and garments in concentrations ranging from 0.5%> to 50%> solids; however, with greater percent solids come greater expense and greater stiffness. In one embodiment, the percent solids range to be applied to the fibers, yarns, fabrics, or garments is between 2.0 and 12.0% or between 3.0 and 10.0%. Preferably, the dye binding composition, including the percentage of solids in the composition, is specifically engineered to produce a dye binding composition that causes the polymer and/or selective dye to migrate to the surface for use in producing ring dyed yarns and/or surface dyed fabrics.
[0063] Yarns and fabrics can be constructed from any of a host of textile fiber, particularly natural fibers including cotton, wool, silk, hemp, flax, or synthetic fibers including polyesters, rayon, acetate, acrylics, nylons (aromatic and aliphatic), modacrylics, spandex, olefins inclusive of super high molecular weight polyethylene, polyethylene, polypropylene, etc., or combinations of two or more of these fibers. In some embodiments, the yarn contains fiber comprised of 100% cotton. In other embodiments, the yarns comprise cotton fibers blended with non-cotton fibers. The blend of fibers, in some embodiments, is at least 50% cotton fibers.
[0064] In the case of applying the chemical to yarn, yarns may be coated and the polymer of the dye binding composition dried such that the yarns are not broken from being stuck together after drying. The dye binding composition can be applied to scoured yarn, scoured & bleached yarn, or yarn in its raw state. Each condition provides a different appearance with the raw yarn providing the greatest ring dyed characteristic. Bath concentrations are also different under each condition because of the absorbency of the yarn for the polymer/water mixture; however, targeted solids addition range from 2.0% to 12.0% depending upon the size of the yarn being treated.
[0065] Examples of articles of personal property that may be used in connection with various embodiments of the present invention include but are not limited to apparel for dancers, such as, tee shirts, sweatshirts, pants, leggings, shorts and jackets; athletic such as, namely, shirts, pants, jackets, footwear, hats and caps, athletic uniforms; athletic footwear; athletic tops and bottoms for running, exercising, sports activities, sports activities and yoga, exercising, sports activities and yoga; baseball caps and hats; bath slippers; bathing suits; bathrobes; beach footwear; belts; boots; bottoms; bow ties; boxer briefs; briefs; coats; compression garments for athletic or other non-medical use, namely, running, exercising, sports activities and yoga; denim jackets; dresses; ear muffs; footwear; gloves; graphic T-shirts; hats; headwear; hosiery; jackets; jeans; loungewear; mittens; neckwear; pajamas; pants; rainwear; scarves; shoes; shorts; skirts; slippers; sneakers; socks; sports caps and hats; sports jackets; sports jerseys; sports pants; sports shirts; sports vests; sweat bands; sweatshirts; swimwear; tee shirts; tops; underwear; yoga pants; yoga shirts, backpacks; bags for carrying babies' accessories; all-purpose sport bags; athletic bags; backpack straps; bags for sports; beach bags; belt bags and hip bags; book bags; briefcases and attaché cases; bum bags; canvas shopping bags; carry-all bags; carry-on bags; carrying cases; clutch bags; cosmetic bags; cosmetic carrying cases; diaper bags; drawstring bags; duffle bags; fanny packs; fashion handbags; garment bags for travel; sport trolley bags; gym bags; handbags; hiking bags; jewelry pouches; knapsacks; luggage; make-up bags; messenger bags; military duffle bags, garment bags for travel, tote bags, shoulder bags and backpacks; pouches; purses; roll bags; school bags; school book bags; shaving bags; shoulder bags; sports bags; suit bags; toiletry bags; tote bags; travel bags; umbrellas; wallets; decorative ribbons; elastic ribbons; hair accessories, claw clips; hair sticks; jaw clips; nap clips; twisters; scrunchies; hair ribbons; ribbons; and bath mats; carpets and rugs; door mats; floor mats; and wallpaper.
[0066] Methods for Customizing Articles
[0067] Various embodiments of the present invention are directed to a method for customizing an article. The method begins with affixing a rubbing template to a mounting sheet to form an affixed rubbing template. The affixing may be to an adhesive surface of the mounting sheet. The template and the mounting sheet may be defined as elsewhere in this specification.
[0068] Next, one places the affixed rubbing template to an inside surface of an article at a transfer location. Because the mounting sheet is larger than the rubbing template, a portion of the adhesive surface of the mounting sheet that is not affixed to the rubbing surface may be affixed to the article. Finally, one rubs an outside surface of the article at a location that corresponds to the transfer location.
[0069] The rubbing may be performed with a rubbing tool and the rubbing tool may comprise an abrasive surface. By using the abrasive surface, one may displace color material form the article. In some embodiments, the rubbing tool further comprises a buffing surface, act the act of rubbings comprises: (i) rubbing with the abrasive surface; and (ii) rubbing with the buffing surface.
[0070] In some embodiments, the rubbing tool is associated with a rubbings collector. The rubbings collector has an adhesive surface that is capable of reversibly adhering to the rubbing tool and the adhesive surface of the rubbings collector is wider than the rubbing tool. When using the rubbings collector, the method further comprises collecting displaced rubbings through adhesion of the displaced rubbings to the adhesive surface.
[0071] In some embodiments, the fabric is denim or a denim blend. The denim may be treated on its surface with ink. The fabric may be any color or colors, or combination of colors, e.g., one or more of red, orange, yellow, green, blue, indigo and violet or combinations thereof. After abrasion of a color, e.g., blue in blue jeans, one may see an absence of dye color, e.g., white.
[0072] Various embodiments of the present invention may be further illustrated by reference to the accompanying figures. FIG. 1 is a representation of the front and back of a pair of jeans 100 that has been customized. The front side of the jeans 110 shows various designs 130 that have been rubbed out of the jeans. The rear side of the jeans 120 also shows various designs 140 that have been rubbed out of the jeans.
[0073] FIG. 2 is a representation of a set of rubbing templates. By way of a non-limiting example, shown are two-dimensional representations of a peace sign 210 and a star 280 . The star is an example of a solid shape, whereas the peace sign is an example of a partially solid shape, i.e., a shape in which there would be gaps or color showing between what has been removed after transfer through the abrasion described in this specification.
[0074] FIG. 3 is a representation of a rubbing template in the form of a star 380 affixed to a mounting sheet 330 . As with FIG. 2 , for illustrative purposes, the representation is shown in two dimensions.
[0075] FIG. 4 is a representation of a rubbing template 480 situated under a layer of a pair of jeans 410 . For illustrative purposes, the dotted lines are used to define the boundary of the star in order to represent that the shape is under the front side of the jeans.
[0076] FIG. 5 is a representation of person 570 using a rubbing tool 550 in order to create a rub design 585 on a pair of jeans 510 . The underside of the rubbings tool contains the abrasive surface.
[0077] FIG. 6 is a representation of how the fabric 620 , a rubbing template 640 , and a mounting sheet 680 may be oriented with a peel off adhesive 662 in place to protect the mounting sheet prior to its use at a desired location. By leaving the protective sheet in place until actual use of the adhesive surface of the mounting sheet, one can try out different positions of the rubbing template relative to the article before transferring a shape.
[0078] Various aspects of the present invention have been described for use in connection with one or more embodiments. However, unless explicitly stated or otherwise apparent from context, each feature described above in any one embodiment may be used in connection with any and all embodiments. | Kits and methods are provided for customization of articles by abrasion of materials that capable of retaining rub designs. The articles may, for example, be apparel such as jeans, and through the use of the components of the present invention one may transfer shapes, such symbols, letter, numbers, representations of animals, representations of persons, representation of flowers, representation of trees, representations of motor vehicles, logos or a combination thereof. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to packet processing.
2. Related Art
In a computer network for transmitting information, messages are received by each router (or switch) at an input interface and retransmitted at an output interface, so as to forward those messages onward to their respective destinations. Each router performs a lookup operation for each message it encounters, in which the router determines from the message to which output interface the message should be forwarded.
One problem in the known art is that the lookup operation can be relatively complex, and can use a relatively large amount of processor resources. For example, the lookup operation can be complicated by concurrently determining one or more of the following:
which output interface is the closest, within a defined network topology, to the specified destination; whether the message is unicast or multicast, and in the latter case, from which input interface the message was received; whether the message is authorized to be forwarded by this router from its specified source, and whether the message is authorized to be forwarded by this router to its specified destination; whether the message should be forwarded to a selected output interface for quality of service considerations, security considerations, or other administrative considerations; whether the message should be counted, measured, or otherwise accounted for, concurrently with forwarding.
Known responses to this problem include (1) to provide greater processing capability, so as to make up for the processor load on the router, (2) to provide only some of these concurrent services, or to provide them only a reduced functionality. While these responses achieve the goal of routing messages in a forwarding network, they have the disadvantage that added services introduce additional load on the router processor and slow down the router.
Accordingly, it would be advantageous to provide a method and system for packet processing that is not subject to drawbacks of the known art.
SUMMARY OF THE INVENTION
The invention provides a method and system for packet processing, in which a router (or switch) is capable of processing incoming packets very quickly, thus performing level 2, 3, and 4 routing and switching, and substantial additional services, in real time. A system includes a packet processing engine (PPE), having elements for receiving packets, distinguishing header and payload information for those packets, outsourcing router decision-making to additional hardware resources (herein a “fast forwarding engine,” or FFE), and ultimately forwarding those packets in response to out-sourced decisions.
In a first aspect of the invention, the PPE is time-synchronized to the FFE, so that the PPE can send and the FFE can receive packet routing information for decision-making at each one of a sequence of constant-duration time quanta. Similarly, the PPE can receive and the FFE can send packet routing information at each one of a sequence of similar time quanta. In addition to information about where to forward a packet, packet routing information possibly also includes additional information such as packet treatment in response to access control, class of service or quality of service, accounting, and other administrative or managerial criteria.
In a second aspect of the invention, the PPE and the FFE each have separate hardware resources allocated to their functions; these separate hardware resources can include pin count, on chip memory, and transfer bandwidth to off-chip memory. This allows the PPE and the FFE to each perform their functions in parallel without substantial contention for operating resources.
In a third aspect of the invention, multiple PPE and FFE pairs can be incorporated into a scaleable parallel system, operating in parallel to route (or switch) packets among a plurality of input and output interfaces.
In a preferred embodiment, the PPE includes separate treatment of packet header information and payload information, so the amount of information exchanged between the PPE and the FFE, and the amount of actual data movement performed by the PPE, can be relatively minimized. When determining the packet header information, the PPE can also parse the data packet (particularly what is conventionally called the packet header) and extract fields needed by the FFE to perform it's forwarding, ACL and QoS decisions. In this way, the PPE reduces the amount of data that it needs to transmit to the FFE, thereby reducing the number of pins required by both the PPE and the FFE to implement this communication.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a block diagram of a system for packet processing and packet forwarding.
FIG. 2 shows a process flow diagram of a method of using a packet processing element as in FIG. 1 .
FIG. 3 shows a block diagram of a system for parallel packet processing and packet forwarding.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In the following description, a preferred embodiment of the invention is described with regard to preferred process steps and data structures. Those skilled in the art would recognize after perusal of this application that embodiments of the invention can be implemented using circuits adapted to particular process steps and data structures described herein, and that implementation of the process steps and data structures described herein would not require undue experimentation or further invention.
System Elements
FIG. 1 shows a block diagram of a system for packet processing and packet forwarding.
A router 100 includes a set of input interfaces 111 , a set of output interfaces 112 , a packet processing engine (PPE) 120 , a PPE memory 130 , and a fast forwarding engine (FFE) 140 . The router 100 is coupled to one or more communication networks 160 . In one embodiment, PPE 120 comprises a single monolithic semiconductor circuit. In one embodiment, FFE 140 comprises single monolithic semiconductor circuit. In one embodiment, PPE, 120 and FFE 140 are together integrated in a single monolithic semiconductor circuit.
The router 100 is disposed for routing (or switching) a sequence of packets 170 . Each packet 170 includes packet header information 171 and packet payload information 172 . Each packet 170 ultimately has packet forwarding information 173 (not shown) decided for it, which is used for routing the packet 170 . Each packet 170 might also have a packet index 174 (not shown) for reference purposes.
Packet Processing Engine
The PPE 120 is disposed to perform the following operations:
The PPE 120 receives input packets 170 at the input interfaces 111 .
The input interfaces 111 are coupled to at least one communication network 160 .
The PPE 120 distinguishes packet header information 171 from packet payload information 172 .
In a preferred embodiment, input packets 170 and output packets 170 are modified using known packet modification protocols, for which there are known parsing rules. The PPE 120 uses these known parsing rules to distinguish packet header information 171 from packet payload information 172 . The PPE 120 extracts the packet header information and then stores that packet in the PPE memory 130 .
The PPE 120 records packet header information 171 and packet payload information 172 in the PPE memory 130 .
In a preferred embodiment, the PPE 120 uses memory access bandwidth to reference the PPE memory 130 for recording and retrieving packet header information 171 and packet payload information 172 using the PPE memory 130 . This allows the PPE 120 to refer to packets by a packet index 174 .
The PPE 120 forwards packet header information 171 to the FFE 140 .
In a preferred embodiment, the PPE 120 is ready to forward packet header information 171 to the FFE 140 each two clock cycles. Each clock cycle is preferably 6–7 nanoseconds. It may occur, for any individual incoming packet 170 , that the PPE 120 takes much longer than two clock cycles to distinguish packet header information 171 and packet payload information 172 . However, the PPE 120 should have at least one new set of packet header information 171 for the FFE 140 at least that often.
Similarly, in a preferred embodiment, the FFE 140 is ready to receive packet header information 171 from PPE 120 each two clock cycles. It may occur, for any individual incoming packet 170 , that the FFE 140 takes much longer than two clock cycles to decide associated packet forwarding information 173 . However, the FFE 140 should be ready to receive one new set of packet header information 171 from PPE 120 at least that often.
The PPE 120 receives packet forwarding information 173 for associated packet header information 171 from the FFE 140 .
In a preferred embodiment, the PPE 120 uses the packet index 174 to reference both packet header information 171 and associated packet payload information 172 in the PPE memory 130 .
The PPE 120 modifies the packet to generate an output packet 170 .
In a preferred embodiment, the PPE 120 performs a rewrite operation on the packet 170 . Rewrite operations include adjusting a TTL (time-to-live) IP field, determining a new CRC, rewriting the MAC-level addresses, and possibly other modifications of the fields. Rewrite operations, and rewrite rules, are known in the art of Internet packet forwarding.
The PPE 120 sends output packets 170 from the output interfaces 112 .
Similar to the input interfaces 111 , the output interfaces 112 are also coupled to at least one communication network 160 , preferably the same communication network 160 as the input interfaces 111 .
Fast Forwarding Engine
The FFE 140 includes a packet information input port 141 , a packet forwarding information output port 142 , and is coupled to assistance devices for assisting in making packet forwarding decisions.
The FFE 140 is coupled to a set of routing information memories 143 (including a spanning tree memory and a multicast expansion table), a forwarding content addressable memory (CAM) 144 and a forwarding memory 145 , an input access CAM 146 and an output access CAM 147 , a CPU 148 , and a net-flow routing engine 150 .
The FFE 140 is disposed to perform the following operations:
The FFE 140 receives packet header information 171 . The FFE 140 , with the assistance of the assistance devices, determines packet forwarding information 173 in response to packet header information 171 .
In a preferred embodiment, the FFE 140 forwards the packet header information 171 to the forwarding CAM 144 , which performs a lookup in its CAM entries to determine packet forwarding information 173 associated with the packet header information 171 . Indices responsive to the lookup by the forwarding CAM 144 are recorded in the forwarding memory 145 .
The FFE 140 accesses the forwarding CAM 144 to record new forwarding information rules as they become available, such as changes to the perceived network topology, access control, and other administrative or managerial rules. The FFE 140 accesses the forwarding memory 145 to retrieve the packet forwarding information 173 as it is determined.
In a preferred embodiment, the forwarding CAM 144 includes a set of ternary CAM entries. Each ternary CAM entry includes a set of bits which can match to logical 0, to logical 1, or to either (that is, a “don't care” bit). Each ternary CAM entry is thus capable of being matched against the packet header information 171 to determine an index in the forwarding memory 145 of a set of packet forwarding information 173 .
In a preferred embodiment, this additional information is responsive to the IP source address, IP source port, IP destination address, IP destination port, protocol type for the packet 170 , and whether the packet 170 is unicast or multicast.
In a preferred embodiment, the FFE 140 forwards an identifier for the input interface 111 at which the packet 170 was received to the input access CAM 146 , to determine if access is permitted for the packet 170 at that input interface 111 .
Similarly, after determining an output interface for the packet 170 , the FFE 140 forwards an identifier for the output interface 112 to which the packet 170 is to be sent to the output access CAM 147 , to determine if access is permitted for the packet 170 at that output interface 112 .
In a preferred embodiment, the packet forwarding information 173 includes how to forward the packet 170 (that is, to which output interface), as well as some or all of the following additional information:
(1) what access control rules (that is, what ACL) to apply to the packet 170 ; (2) what class of service (CoS) and quality of service (QoS) rules to apply to the packet 170 ; (3) what accounting and statistics to keep regarding the packet 170 or the net flow that the packet 170 is part of; (4) what other administrative or managerial rules or restrictions to apply to the packet 170 .
In a preferred embodiment, this additional information (and other additional services with regard to the packet 170 ) can be introduced without substantially adding to processing load on the FFE 140 , as the forwarding CAM 144 and the forwarding memory 145 provide pattern matching against the packet header information 171 .
The network flow routing engine 150 provides network flow packet forwarding information 173 to the FFE 140 , if that network flow packet forwarding information 173 is available.
In a preferred embodiment, if the packet 170 can be routed using network flow information, the network-flow routing engine 150 independently determines net-workflow packet forwarding information 173 in response to the network flow associated with the packet header information 171 . If the network-flow routing engine 150 is able to determine that network flow packet forwarding information 173 , the FFE 140 uses the network flow packet forwarding information 173 in place of packet forwarding information 173 it might otherwise determine for itself.
Method of Operation
FIG. 2 shows a block diagram of a packet processing element in a system as in FIG. 1 .
A method 200 includes a set of flow points and a set of steps. The system 100 performs the method 200 . Although the method 200 is described serially, the steps of the method 200 can be performed by separate elements in conjunction or in parallel, whether asynchronously, in a pipelined manner, or otherwise. There is no particular requirement that the method 200 be performed in the same order in which this description lists the steps, except where so indicated.
At a flow point 210 , the PPE 120 is ready to receive input packets 170 at the input interfaces 111 .
At a step 211 , the PPE 120 receives an input packet 170 at one of the input interfaces 111 .
At a step 212 , the PPE 120 parses the packet 170 to distinguish a packet header from a remainder of the packet, and to determine those portions of the packet header that are relevant to packet routing. This allows the PPE 120 to distinguish packet header information 171 from packet payload information 172 . The packet 170 is not affected by this parsing. The entire packet 170 remains stored in the PPE memory 130 as one unit.
For example, in a preferred embodiment, the PPE 120 determines the IP source address, IP source port, IP destination address, IP destination port, protocol type for the packet 170 , and whether the packet 170 is unicast or multicast. In a preferred embodiment, these values are treated as packet header information 171 .
At a step 213 , the PPE 120 forwards packet header information 171 for the packet 170 to the FFE 140 . As part of this step, the FFE 140 receives packet header information 171 for the packet 170 from the PPE 120 .
At a step 214 , the FFE 140 sends packet forwarding information 173 for the packet 170 to the PPE 120 . As part of this step, the PPE 120 receives packet forwarding information 173 for the packet 170 from the FFE 140 .
At a step 215 , the PPE 120 associates the packet forwarding information 173 received from the FFE 140 with the packet 170 , using the packet index 174 .
At a step 216 , the PPE 120 rewrites the packet 170 using the packet forwarding information 173 and a set of rewrite rules for the packet 170 . As noted above, rewrite operations include adjusting a hop count for the packet, determining a new CRC, and possibly other protocol reformatting operations.
At a step 217 , the PPE 120 sends the packets 170 to the output interface 112 indicated by the packet forwarding information 173 .
After a flow point 218 , the PPE 120 has sent the packet 170 to a designated output interface 112 .
Parallel System
FIG. 3 shows a block diagram of a system for parallel packet processing and packet forwarding.
A system 300 for parallel packet processing and packet forwarding includes a plurality of interfaces 110 , a plurality of routing pairs 320 , and a cross-bar switch 330 .
Each plurality of interfaces 110 includes a set of input interfaces 111 and a set of output interfaces 112 . Packets 170 can be received at the input interfaces 111 and can be sent using the output interfaces 112 .
Each routing pair 320 includes a matched PPE 120 and FFE 140 , and associated memories and assistance devices, as described with reference to FIG. 1 .
The cross-bar switch 330 is coupled to outputs from each PPE 120 in each matched routing pair 320 .
When a packet 170 is received at a particular interface 110 (and thus at a particular input interface 111 therein), they are coupled to the routing pair 320 associated with that particular interface 110 .
When a packet 170 is received at a particular routing pair 320 , it is received by the PPE 120 in that particular matched routing pair 320 . The PPE 120 and the FFE 140 in that particular routing pair 320 cooperate to route (or switch) and otherwise process the packet 170 as described with regard to FIG. 1 and FIG. 2 .
When a packet 170 is output from a routing pair 320 , the PPE 120 forwards the packet 170 to the crossbar switch 330 with instructions indicating a particular destination interface 110 . The crossbar switch 330 provides flow control between different routing pairs 320 so that multiple routing pairs 320 do not simultaneously send packets 170 to the same output interface 112 and overrun buffering therein.
When a packet 170 arrives at the cross-bar switch 330 , the cross-bar switch 330 forwards that packet 170 to its destination interface 110 , at which it is output from its destination output interface 112 .
ALTERNATIVE EMBODIMENTS
Although preferred embodiments are disclosed herein, many variations are possible which remain within the concept, scope, and spirit of the invention, and these variations would become clear to those skilled in the art after perusal of this application. | The invention provides a method and system for packet processing, in which a router (or switch) is capable of quickly processing incoming packets, thus performing level 2, 3, and 4 routing and additional services, in real time. A system includes a packet processing engine (PPE), having elements for receiving packets, distinguishing header and payload information for those packets, outsourcing router decision-making to additional hardware resources such as a fast forwarding engine (FFE), and forwarding those packets. The PPE is synchronized to the FFE, so that the PPE can send and the FFE can receive packets at each one of a sequence of constant-duration time quanta. Similarly, the PPE can receive and the FFE can send packet routing information at each one of a sequence of similar time quanta. The PPE and the FFE have separate hardware so that their functions can be performed in parallel without contention for operating resources. | 7 |
[0001] This application is a continuation application of co-pending U.S. patent application Ser. No. 11/360,797, filed Feb. 22, 2006, which is a continuation application of co-pending U.S. patent application Ser. No. 10/177,715, filed Jun. 20, 2002, now issued as U.S. Pat. No. 7,013,314, which is a continuation of co-pending U.S. patent application Ser. No. 09/213,199, filed Dec. 17, 1998, now issued as U.S. Pat. No. 6,434,574.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates generally to computer operating systems and more particularly to storing and retrieving filenames in computer memory.
[0004] 2. Description of the Background Art
[0005] The storing and retrieving of filenames in computer memory is extremely important to all computer users. When a computer user saves a file and filename into computer memory, it is important that the filename remain uniquely identifiable regardless of any other filenames or text encodings saved in the memory. If a filename is not uniquely identifiable, then a computer may be unable to retrieve the named file. Further, if the memory containing the filename is moved to a different computer then that filename must remain identifiable if the named file is to be retrievable.
[0006] Conventionally, a filename identity is represented by a string of bytes (“encoding”) stored in computer memory. A conventional Roman character based computer system will interpret the encoding to represent Roman characters in the American Standard Code for Information Interchange (ASCII) character set, even if the encoding actually represents Japanese characters. For example, a Japanese computer user may save a file with a Japanese filename onto a removable memory device, such as a floppy disk. The Japanese filename encoding is interpreted by a conventional Japanese character based computer system to be Japanese characters. However, if the Japanese user then inserts the removable memory device into a conventional Roman character based computer system, the Roman computer system will assume the Japanese encoding actually represents a Roman character filename rather than a Japanese character filename.
[0007] A problem with the conventional Roman character based computer system is that because it assumes that a filename is in Roman characters, it may equate two non-Roman character filenames as being identical. This is because a Roman computer system treats uppercase and lowercase letters in a filename as equivalent. Therefore, a Roman computer system would assume that the filenames “Example.txt” and “example.txt” (and their associated files) are the same even though they are represented by different strings of bytes, possibly leading to the assumption that two non-Roman filenames, which vary only by case, are identical. If a Roman computer system misinterprets a non-Roman filename, the system may mistakenly open the wrong file or may refuse to create a new file since it believes that that filename is already in use.
[0008] FIG. 1 is a diagram of Japanese characters in which characters within any given column appear identical to a conventional Roman character based computer system. For example, characters 104 , 106 , 108 and 110 in column 102 appear identical to a prior art Roman computer system because it treats all filenames as if they were written in the Roman alphabet. Therefore, if two Japanese filenames differed by just one character, such as characters 104 and 106 , a prior art Roman computer system would actually consider them to be identical. Similar problems occur with other text encodings but the problem is most acute in Japanese and Chinese text encodings since in these languages each character is a word and therefore filenames are shorter and more likely to vary by just one character.
[0009] A Roman character based prior art system can only store filenames in Roman text encodings as partially represented by ASCII text encoding table 200 of FIG. 2 . Each Roman character has its own encoding. For instance, character 202 , the letter “A”, is stored as 7-bit encoding 204 . However, because ASCII only allows 7 bit encodings, which means that ASCII can encode only 128 characters, basic ASCII encoding table 200 contains no encodings for Japanese or any other language that uses non-Roman characters. Japanese and other east-asian languages can easily have several thousand characters that need to be encoded. Therefore, a prior art Roman character based computer system cannot always accurately store or retrieve some east-asian filenames or other non-Roman filenames.
[0010] Therefore, an improved system and method are needed to store and retrieve filenames and files in a computer system.
SUMMARY OF THE INVENTION
[0011] The present invention provides a system and method for accurately storing and retrieving filenames in computer memory by converting filenames into Unicode text encoding. The Unicode Standard, like the ASCII text encoding standard and others, encodes each character as a numerical value. However, instead of encoding simply in ASCII, Unicode text encoding encodes all the characters used in the world's major written languages, including Greek, Arabic, Tamil, Thai, Japanese, Korean and many others.
[0012] The invention stores a filename into computer memory by first determining a default text encoding based upon which it converts the filename into Unicode text encoding. If the conversion is successful, the invention stores the Unicode text-encoded filename into computer memory and sets a bit that corresponds to the default text encoding in an Encoding Bitmap located in computer memory.
[0013] If the conversion based on the default text encoding is unsuccessful, the invention tries using Roman text encoding to convert the filename into Unicode text encoding. Once the conversion is complete, the invention stores the filename into computer memory and sets the bit that corresponds to Roman text encoding in the encoding bitmap. The invention assumes that any sequence of bytes can be converted to Unicode using Roman text encoding, which assigns a meaning to every possible byte sequence. If conversion using the default encoding fails, conversion using Roman text encoding will definitely succeed, even if it produces the wrong Unicode characters.
[0014] To retrieve a filename, the invention first converts the retrieval request into Unicode text encoding based on the default text encoding of the system. The invention then searches the computer memory for a matching Unicode text encoded filename. If the search is successful, the search result is returned. If the search is not successful, the invention determines if Roman text encoding is the default text encoding. If Roman text encoding is not the default text encoding, the invention uses Roman text encoding to convert the retrieval request into Unicode text encoding and then searches the computer memory for a matching Unicode filename. If the search is successful, a search result is returned.
[0015] If the search is not successful, or if Roman text encoding is the default text encoding, the invention next retrieves a list of all text encodings previously used in the system as specified in an Encoding Bitmap located in the computer memory of the system. The invention then converts the retrieval request into Unicode text encoding based on each text encoding specified in the encoding bitmap and uses each conversion to search the computer memory for a match. If a match is found, the invention returns the search result.
[0016] Finally, if the search is still not successful the invention converts the retrieval request into Unicode text encoding based on any other text encodings installed in the computer memory that have yet to be tried. The invention then uses each conversion in searching the computer memory for a matching Unicode filename. If the search is successful, the invention returns the search result. If the search is not successful, the invention returns an error message.
[0017] Accordingly, the present invention not only more accurately and efficiently stores and retrieves filenames in computer memory but also allows multiple encodings to be used in computer memory over time.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a diagram of Japanese characters in columns that appear identical when storing or retrieving a filename using a prior art system;
[0019] FIG. 2 is a diagram of ASCII text encodings used by a prior art system;
[0020] FIG. 3 is a block diagram of a computer system suitable for use with the present invention;
[0021] FIG. 4 is a block diagram of the preferred allocation of the memory shown in FIG. 3 ;
[0022] FIG. 5 is a block diagram of the preferred embodiment of the Unicode Table in the memory shown in FIG. 4 ;
[0023] FIG. 6 is a block diagram of the preferred embodiment of the Encoding Bitmap in the memory shown in FIG. 4 ;
[0024] FIG. 7 is a flowchart of preferred method steps for storing a filename into computer memory according to the present invention; and
[0025] FIGS. 8 a and 8 b are a flowchart of preferred method steps for retrieving a filename from computer memory according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0026] The present invention relates to an improvement in storing filenames in, and retrieving them from, computer memory.
[0027] FIG. 3 is a block diagram of a computer system suitable for use with the invention. Computer system 300 preferably includes a Central Processing Unit (CPU) 304 , a monitor 306 , a keyboard 308 , memory 310 , and an input and output (I/O) interface 312 , all connected by a system bus 302 . Memory 310 may comprise a hard disk drive, random access memory (RAM) or any other appropriate memory configuration.
[0028] FIG. 4 is a block diagram of the preferred allocation of memory 310 , which stores a Unicode table 402 that contains 16 bit encodings for most modern written languages as discussed further in conjunction with FIG. 5 . Memory 310 also stores a File Manager 404 which manages document 406 and other documents with their respective filenames that are stored in memory 310 , as discussed further in conjunction with FIG. 7 , FIG. 8 a and FIG. 8 b . Memory 310 also stores text encodings 408 for various languages such as Roman, Greek and Japanese, and an encoding bitmap 410 which lists all previously used text encodings, as discussed further in conjunction with FIG. 6 .
[0029] FIG. 5 is a diagram of the preferred embodiment of the Unicode Table 402 , which contains bit encodings for most of the world's modern written languages. Unicode, published as The Unicode Standard, Worldwide Character Encoding, is now the standard for representing text. Unicode uses a 16-bit coding scheme that allows for 65,536 distinct characters—more than enough to include all languages in use today. Currently, Unicode text encoding covers 38,887 different characters. For example, the Roman character “A” 502 is represented by bit encoding 504 . The Greek character “α” 506 is represented by bit encoding 508 . The Chinese character for sky (“tian” in Mandarin Chinese and “tin” in Cantonese) 510 is represented by bit encoding 512 . Most modern written languages can be encoded using Unicode text encoding. However, some relatively obscure languages in current use, such as Cherokee and Mongolian, cannot be encoded using Unicode text encoding. Accordingly, almost any filename can be accurately represented in its native language using Unicode text encoding instead of having to be converted, possibly inaccurately, to Roman characters.
[0030] FIG. 6 is a diagram of the preferred embodiment of the FIG. 4 Encoding Bitmap 410 , which contain a list of all text encodings previously used in system 300 . Whenever a given text encoding is used in system 300 , file manager 404 sets a relevant field in encoding bitmap 410 . For instance, if field 602 represents Hebrew and Hebrew has not been used in system 300 , field 602 contains a 0. If field 604 represents Arabic and Arabic has been used in system 300 , field 604 contains a 1.
[0031] FIG. 7 is a flowchart of steps in a preferred method 700 for file manager 404 to store a filename into computer memory 310 according to the invention. In step 703 , file manager 404 receives a “save” request, which contains filename information for document 406 . Alternatively, the “save” request can be a request to change a filename. In step 704 , file manager 404 creates a file and/or saves document 406 in memory 310 . If the save request in step 703 was a change filename request, step 704 can be skipped. The contents of the document 406 can also be saved in memory 310 after completion of the method 700 .
[0032] In step 706 , file manager 404 determines a default text encoding of system 300 , which in this case is a text encoding used to view filenames on monitor 306 . In step 708 , file manager 404 uses the default text encoding determined in step 706 to convert the filename to a Unicode name.
[0033] Step 710 determines whether the step 708 conversion using the default text encoding was successful. If the step 708 conversion was not successful, then in step 712 file manager 404 uses Roman text encoding to convert the user-entered filename to Unicode text encoding. Note that step 712 cannot fail. Even if the filename was not actually written in Roman characters, method 700 will still convert the user-entered filename to Unicode using Roman encoding. This is because all possible byte sequences yield valid Roman characters that can be converted into Unicode. The filename will not be in the intended characters, but the filename will be individually distinguishable.
[0034] Once the step 712 conversion is complete, or if the step 708 conversion was successful, then in step 714 file manager 404 saves the Unicode name to memory 310 . In step 716 , file manager 404 sets a bit in encoding bitmap 410 that corresponds to the type of text encoding used to convert the user-entered filename. In step 718 method 700 ends.
[0035] FIGS. 8 a and 8 b are a flowchart of steps in a preferred method 800 for file manager 404 to retrieve a filename from computer memory according to the invention. In step 804 file manager 404 receives a search request which was. generated when a system 300 user attempted to open document 406 , or any other document, stored in memory 310 . The search request contains a user-entered filename. In step 805 file manager 404 converts the user-entered filename to Unicode text encoding based on the default text encoding of system 300 . As discussed in conjunction with FIG. 7 , the default text encoding in this example is the text encoding used to view filenames on monitor 306 . If the step 805 conversion was not successful, then file manager 404 proceeds to step 816 as discussed below. If the conversion was successful, then in step 807 file manager 404 searches memory 310 for the converted filename. If file manager 404 locates a matching filename, file manager 404 returns the search result and retrieves the file having the matching filename in step 812 and method 800 ends in step 814 .
[0036] If the step 807 search did not locate a matching filename, or if the step 805 conversion was not successful, then in step 816 file manager 404 determines if Roman text encoding is the default text encoding of system 300 . If Roman text encoding is not the default text encoding, then in step 817 file manager 404 converts the user-entered filename to Unicode text encoding using Roman text encoding. In step 819 , file manager 404 searches memory 310 for the converted filename. If it finds a matching filename, then in step 822 file manager 404 returns a search result and retrieves the file having the matching filename, and method 800 ends in step 824 .
[0037] If the step 819 search did not locate a matching filename, or if in step 816 file manager 404 determined that Roman text encoding is the default text encoding of system 300 , then in step 826 file manager 404 retrieves a list of text encodings from encoding bitmap 410 .
[0038] Next, in step 827 , file manager 404 converts the user-entered filename into Unicode text encoding using a text encoding from the list retrieved in step 826 from encoding bitmap 410 . File manager 404 converts the filename into Unicode using only text encodings not already used in steps 805 and 817 . However, in practice system 300 will probably only have installed one or two text encodings—usually Roman and a local text encoding such as Japanese. The local text encoding is normally set as the default text encoding that is tried in step 805 . Therefore, method 800 generally is successful at either step 808 or step 820 and does not reach step 826 .
[0039] If the step 827 conversion is not successful, then File Manager 404 proceeds to step 834 . If the step 827 conversion is successful, then in step 829 file manager 404 uses the converted user-entered filename to search memory 310 for a matching Unicode filename. If in step 830 the search is successful, then in step 832 file manager 404 returns a search result and retrieves the file having the matching filename, and in step 833 method 800 ends. If in step 830 the search was unsuccessful, or if the step 827 conversion was unsuccessful, then in step 834 file manager 404 determines if there are other text encodings listed in encoding bitmap 410 that have not been tried. If there are some text encodings that have not yet been tried, then file manager 404 returns to step 827 .
[0040] If in step 834 all text encodings listed in encoding bitmap 410 have been tried, then file manager 404 proceeds to step 835 and tries to convert the user-entered filename into Unicode text encoding based on any other text encodings installed in system 300 . As in step 827 , file manager 404 tries conversions to Unicode text encoding using only previously untried text encodings. if the step 835 conversion is unsuccessful, then File Manager 404 proceeds to step 844 . Otherwise, in step 837 , file manager 404 searches memory 310 for a matching Unicode filename. If the search is successful, then in step 840 file manager 404 returns a search result and retrieves the file having the matching filename, and in step 842 method 800 ends. If the search is unsuccessful, but in step 844 not all text encodings have been tried, then file manager 404 returns to step 835 and tries to convert the user-entered filename to Unicode text encoding using another text encoding. If in step 844 all the text encodings installed in system 300 have been tried, then in step 846 file manager 404 returns an error result and in step 848 the method 800 halts.
[0041] The invention has been explained with reference to a preferred embodiment. Other embodiments will be apparent to those skilled in the art in light of this disclosure. For example, the invention may readily be implemented using configurations other than those described in the preferred embodiment. Additionally, the invention may effectively be used in conjunction with systems other than the one described as the preferred embodiment. Therefore, these and other variations upon the preferred embodiments are intended to be covered by the appended claims. | The invention receives a request to store a file having a filename written in a first text encoding, converts the filename into a Unicode filename and stores the Unicode filename and the file into memory. The invention then sets a flag, associated with the memory, indicating that a first text encoding has been used. To retrieve a Unicode filename, the invention receives a request to locate a Unicode filename from memory. Next, the invention uses a predetermined text encoding to convert the filename into Unicode. The invention then searches for the Unicode filename in the memory. If the Unicode filename is not found, the invention uses a next text encoding from the set of text encodings which have been used, to repeat the conversion and searches the memory until the Unicode filename is identified. Lastly, the Unicode file is retrieved. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a semiconductor device provided with multi-level interconnects and a manufacturing method thereof.
[0003] In particular, the invention relates to a semiconductor integrated circuit device having multi-level interconnects with low parasitic capacitance and operated at high speed of several hundreds of MHz or more and a manufacturing method thereof.
[0004] 2. Description of Related Art
[0005] In a semiconductor integrated circuit device operated at high speed of several hundreds of MHz or more, signal propagation delay due to parasitic capacitance in multi-level interconnects is significant.
[0006] [0006]FIG. 1 is a schematical plan view of multi-level interconnects. Reference numeral 1 denotes a semiconductor substrate, 4 a lower level interconnect, 14 a via, and 24 a higher level interconnect. Normally, adjacent level interconnects are laid out in directions crossing perpendicularly to each other. This means that the area to face each other is small between higher level and lower level interconnects. As a result, parasitic capacitance between adjacent interconnects in a level is generally larger than that between interconnects in different levels, and exert more influence on signal propagation delay. Accordingly, attempts have been made to reduce parasitic capacitance between the adjacent interconnects in a level by replacing the insulating film material (silicon oxide film (specific dielectric constant: k˜4) and silicon nitride film (k˜7)) between adjacent interconnects in a level with insulating film material with lower dielectric constant.
[0007] Methylsiloxane type film is one of the low dielectric constant film (k˜about 3 or lower). This is a film having Si—CH 3 bond and Si—O—Si bond as main components. In addition, Si—H bond or Si—C—Si bond may be contained. There are the following methods to form the film: spin-coating and chemical vapor deposition (CVD). In the spin-coating, oligomer solution containing methylsiloxane (spin-on glass (SOG)) is deposited by spin-coating, and then is cured. In the CVD, a gas containing Si—CH 3 bond reacts with oxidizing gas in a CVD chamber. The advantageous feature of methylsiloxane type film is that it has high heat-resistant property and is stable in heat treatment (up to 450° C.) in the manufacturing process of multi-level interconnects.
[0008] However, when high-pressure oxygen plasma treatment is performed on methysiloxane type film, the film is deteriorated due to oxygen radicals in the plasma and absorbs moisture, and the quality of the film such as electrical characteristics is deteriorated. For this reason, conventional type patterning method cannot be used, in which a resist mask is removed by high-pressure oxygen plasma treatment after transferring the pattern.
[0009] A first method to solve this problem is disclosed in Japanese Patent Application 151102/1988, which describes the use of low-pressure oxygen plasma to remove the resist. According to this method, deterioration of the quality of methylsiloxane type film is suppressed. This is because oxygen ions in the low-pressure oxygen plasma modify the surface of the methylsiloxane type film to fine silicon oxide, and this surface layer protects inner part of the film from oxygen radicals.
[0010] There is a second method to prevent deterioration of the quality when the resist is removed, and this is disclosed in JP-A-87502/1999. It is a method to transfer resist pattern to hard mask, and after removing the resist in advance, the methylsiloxane type film is etched using the hard mask.
[0011] [0011]FIG. 2 to FIG. 4 each represents a cross-sectional view showing of a manufacturing process to explain the second method. On a methylsiloxane type film 6 , a hard mask material 8 such as silicon nitride is deposited. A silicon oxide film 27 , and further, a resist 9 are formed on it, and the resist is patterned by lithography (FIG. 2). After etching the silicon oxide film 27 using the resist mask 9 , the resist 9 is removed (FIG. 3). In this case, the methylsiloxane type film 6 is covered with the hard mask material 8 , and it is not exposed to oxygen plasma, and hence, it is not deteriorated. After transferring the pattern to the hard mask 8 , the silicon oxide film 27 is removed. Then, using the hard mask 8 , the methylsiloxane type film 6 is patterned (FIG. 4).
[0012] According to the first method as described above, it is not possible to form a hole pattern or a trench pattern with high aspect ratio (depth over diameter or depth over trench width). When the aspect ratio increases, the number of ions impinging on the pattern side-wall surface is decreased. As a result, surface passivation layer is not formed on the methylsiloxane type film and its quality is deteriorated. In practical application, this method is effective only in the case where the aspect ratio <3.
[0013] When the methylsiloxane type film is fabricated by the second method as described above, shoulder portion of the hard mask 8 collapses diagonally as shown in FIG. 4 (faceting). In case low resistance copper wire is used as the lower level interconnect 4 , an etching stopper 5 on the surface of the interconnect must be etched (FIG. 5). As the etching stopper 5 , silicon nitride film, silicon carbide film, etc. are used. Under the etching condition to etch the etching stopper 5 , both the hard mask 8 and the methylsiloxane type film 6 are etched at the similar rate as the etching stopper 5 . As a result, faceting of the hard mask 8 occurs more remarkably (FIG. 6). When there is a portion where the hard mask 8 completely disappears, faceting occurs on the methylsiloxane type film 6 underneath. Further, the faceting is expanded in argon sputter-etching, which is performed as pre-treatment (cleaning) of the next metal deposition (FIG. 7).
[0014] The first problem caused by the faceting is that sputtered dielectrics 98 are deposited on pattern bottom in case of argon sputter-etching, and this results in via-connection failure. The faceting prior to the sputter-etching increases the amount of the sputtered dielectrics, so increases the via-connection failure.
[0015] The second problem caused by the faceting is that buried metals 14 in the pattern are not completely separated from each other, and this causes short-circuit failure (FIG. 8).
SUMMARY OF THE INVENTION
[0016] It is an object of the present invention to provide a semiconductor device and a manufacturing method thereof, by which it is possible to form a trench or a hole with high aspect ratio on a methylsiloxane type film with low dielectric constant without causing via-connection failure and short circuit failure due to faceting even when lower level interconnects are covered with etching stopper.
[0017] According to an aspect of the method for manufacturing a semiconductor device of the present invention, inter-level dielectrics for forming holes for vias or trenches for interconnects are fabricated as layered films of a methylsiloxane type film and a different insulating film formed on the film, and the layered films are processed using a hard mask. As a result, hole pattern or trench pattern is transferred to the hard mask using a resist, and the resist is then removed. In this case, deterioration of the quality of the methylsiloxane type film can be prevented because the methylsiloxane type film is covered with the insulating film.
[0018] Also, when a hole or a trench is formed on the layered films, it is possible to prevent transfer of the faceting of the hard mask to the methylsiloxane type film because the insulating film is formed between the methylsiloxane type film and the hard mask. Thus, the first and the second problems as described above can be overcome. By setting the etching rate of the insulating film to ⅓ or less of that of the hard mask, the insulating film acts as a hard mask for the methylsiloxane type film, and the higher effects can be obtained. As an example of the material for the insulating film, it is effective to use silicon oxide film because it can suppress the increase of parasitic capacitance between the interconnects.
[0019] Further, in case the dual damascene process in which holes for vias or trenches for interconnects are formed at the same time, layered films of methylsiloxane type film, a different insulating film and a hard mask are deposited on the similar layered films, and then the hole and the trench are formed at the same time. In this case, the insulating film prevents quality deterioration caused by removal of the resist on the methylsiloxane type film under the insulating film, and also the transfer of the faceting of the hard mask to the methylsiloxane type film can be prevented. In case of the dual damascene process in which trench pattern is transferred to the higher level hard mask and hole pattern is transferred to the lower level hard mask, the resist used for patterning of the lower level hard mask is removed by low-pressure oxygen plasma treatment, and quality deterioration of the methylsiloxane type film formed on the lower level hard mask can be suppressed.
[0020] In case the etching stopper is formed on the lowermost layer of the inter-level dielectrics, the hard mask on the exposed portion is removed at the same time when the hole is formed on the etching stopper. As a result, it is possible to reduce parasitic capacitance between the multi-level interconnects.
[0021] According to an aspect of a semiconductor device of the present invention, inter-level dielectrics with dual damascene interconnects formed on it are made as layered films comprising a first methylsiloxane type film, a first insulating film, a hard mask, a second methylsiloxane type film, and a second insulating film in this order from below, and the manufacturing method as described above can be applied. The decrease of production yield caused by via-connection failure or short-circuit failure of multi-level interconnects can be prevented, and a semiconductor integrated circuit device to be operated at high speed of several hundreds of MHz or more can be manufactured at lower cost.
[0022] Other and further objects, features and advantages of the invention will appear more fully from the following description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] A preferred form of the present invention illustrated in the accompanying drawings in which:
[0024] [0024]FIG. 1 is a schematical plan view of conventional type multi-level interconnects;
[0025] [0025]FIG. 2 is a cross-sectional view showing a process for manufacturing conventional type multi-level interconnects;
[0026] [0026]FIG. 3 is a cross-sectional view showing a process for manufacturing conventional type multi-level interconnects;
[0027] [0027]FIG. 4 is a cross-sectional view showing a process for manufacturing conventional type multi-level interconnects;
[0028] [0028]FIG. 5 is a cross-sectional view showing a manufacturing process to explain problems in the conventional example;
[0029] [0029]FIG. 6 is a cross-sectional view showing a manufacturing process to explain problems in the conventional example;
[0030] [0030]FIG. 7 is a cross-sectional view showing a manufacturing process to explain problems in the conventional example;
[0031] [0031]FIG. 8 is a cross-sectional view showing a manufacturing process to explain problems in the conventional example;
[0032] [0032]FIG. 9 is a cross-sectional view of a manufacturing process of a first embodiment of the present invention;
[0033] [0033]FIG. 10 is a cross-sectional view of a manufacturing process of a first embodiment of the present invention;
[0034] [0034]FIG. 11 is a cross-sectional view of a manufacturing process of a first embodiment of the present invention;
[0035] [0035]FIG. 12 is a cross-sectional view of a manufacturing process of a first embodiment of the present invention;
[0036] [0036]FIG. 13 is a cross-sectional view of a manufacturing process of a first embodiment of the present invention;
[0037] [0037]FIG. 14 is a plan view showing a process for manufacturing the first embodiment of the present invention;
[0038] [0038]FIG. 15 is a cross-sectional view of a process for manufacturing the first embodiment of the present invention;
[0039] [0039]FIG. 16 is a cross-sectional view of a process for manufacturing the first embodiment of the present invention;
[0040] [0040]FIG. 17 is a cross-sectional view of a process for manufacturing the first embodiment of the present invention;
[0041] [0041]FIG. 18 is a plan view of a process for manufacturing the first embodiment of the present invention;
[0042] [0042]FIG. 19 is a cross-sectional view of a process for manufacturing the first embodiment of the present invention;
[0043] [0043]FIG. 20 is a plan view of a process for manufacturing the first embodiment of the present invention;
[0044] [0044]FIG. 21 is a diagram showing relationship between sputter-etched thickness before deposition of vias and interconnects and via-connection yield of vias;
[0045] [0045]FIG. 22 is a cross-sectional view of a process for manufacturing a second embodiment of the present invention;
[0046] [0046]FIG. 23 is a cross-sectional view of a process for manufacturing the second embodiment of the present invention;
[0047] [0047]FIG. 24 is a cross-sectional view of a process for manufacturing the second embodiment of the present invention;
[0048] [0048]FIG. 25 is a cross-sectional view of a process for manufacturing the second embodiment of the present invention;
[0049] [0049]FIG. 26 is a cross-sectional view of a process for manufacturing the second embodiment of the present invention;
[0050] [0050]FIG. 27 is a cross-sectional view of a process for manufacturing the second embodiment of the present invention;
[0051] [0051]FIG. 28 is a cross-sectional view of a process for manufacturing a third embodiment of the present invention;
[0052] [0052]FIG. 29 is a cross-sectional view of a process for manufacturing the third embodiment of the present invention;
[0053] [0053]FIG. 30 is a plan view of a process for manufacturing the third embodiment of the present invention;
[0054] [0054]FIG. 31 is a cross-sectional view of a process for manufacturing the third embodiment of the present invention;
[0055] [0055]FIG. 32 is a plan view of a process for manufacturing the third embodiment of the present invention;
[0056] [0056]FIG. 33 is a cross-sectional view of a process for manufacturing the third embodiment of the present invention;
[0057] [0057]FIG. 34 is a cross-sectional view of a process for manufacturing the third embodiment of the present invention;
[0058] [0058]FIG. 35 is a cross-sectional view of a process for manufacturing the third embodiment of the present invention; and
[0059] [0059]FIG. 36 is a cross-sectional view of a process for manufacturing the third embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
EXAMPLE 1
[0060] [0060]FIG. 9 to FIG. 20 each represents a cross-sectional view or a plan view of a process for manufacturing a first embodiment of a semiconductor device of the present invention, in which single damascene process is applied for forming multi-level interconnects.
[0061] As shown in FIG. 9, a first inter-level dielectric film 2 is formed on a silicon substrate 1 where a device component is fabricated. Then, a contact hole is opened, and titanium nitride is buried by CVD method. By chemical-mechanical polishing, the metal outside the hole is removed, and a contact plug 3 is formed. In the figure, a MOS transistor is shown as a device component.
[0062] Next, as shown in FIG. 10, a second inter-layer dielectric 12 is formed, and a trench for a first level interconnect is fabricated. Sputter-etching is performed for the time as long as a 20-nm-thick blanket silicon oxide film is removed. Titanium nitride and copper are thinly formed by sputtering. Further, copper plating is performed to bury the trench with layered films of a barrier metal film 4 a comprising titanium nitride and a copper film 4 b . Further, by chemical-mechanical polishing, titanium nitride and copper outside the trench were removed, and first-level interconnects 4 a and 4 b were formed. A plan view of the process in this stage is shown in FIG. 11. Here, FIG. 10 is a cross-sectional view along the line A-B in FIG. 11. The relationship between this cross-sectional view and the top view is the same in the description given below.
[0063] Next, as shown in FIG. 12, a silicon nitride film was formed in thickness of 50 nm by plasma CVD method as an etching stopper 5 of the first level interconnect. Then, 300-nm-thick organic SOG film was coated as a methylsiloxane type film 6 , and this was cured in nitrogen ambient at 425° C. Further, by plasma CVD method, a silicon oxide film 7 was formed in thickness of 100 nm, and a silicon nitride film 8 was formed in thickness of 100 nm as a hard mask 8 .
[0064] Next, as shown in FIG. 13, reactive ion etching was performed using a resist 9 as mask, and via pattern was transferred from the resist 9 to the hard mask 8 . In this etching process, it is necessary to stop the etching at the silicon oxide film 7 without exposing the lower level organic SOG film as shown in the plan view of FIG. 14. There is no need to stop the etching exactly at the upper surface of the silicon oxide film 7 as shown in FIG. 13, and there is no problem even when the silicon oxide film is etched to some extent.
[0065] Then, as shown in FIG. 15, the resist 9 was removed by ICP type asher, and reactive ion etching was performed using the silicon nitride film 8 as hard mask, and etching was performed on the silicon oxide film 7 and the organic SOG film 6 . In this etching process, etching selectivity or selection ratio of the silicon oxide and the organic SOG film to the silicon nitride was 10 . By this etching process, film thickness of the hard mask was turned to 60 nm.
[0066] Next, as shown in FIG. 16, the space inside the hole was cleaned using wet solution, and the etching stopper 5 was removed by etching, and upper surface of the first level interconnects 4 a and 4 b were exposed. In this case, almost the entire hard mask on upper portion of the pattern disappeared. When the upper surfaces of the first level interconnects 4 a and 4 b were exposed, the hard mask 8 may remain. However, it is preferable to remove it in the etching process by over-etching in order to reduce parasitic capacitance between interconnects.
[0067] Further, as shown in FIG. 17, sputter-etching was performed for the time as long as a 20-nm-thick blanket silicon oxide film is removed, and titanium nitride and copper were thinly formed by sputtering. Then, by copper plating, layered films of the barrier metal film 4 a comprising titanium nitride and the copper film 4 b was buried in the hole. Further, by chemical-mechanical polishing, titanium nitride and copper were removed, and vias 14 a and 14 b were formed. A plan view of the process in this stage is shown in FIG. 18.
[0068] Then, as shown in FIG. 19, the procedure of FIG. 12 to FIG. 18 was repeated, and second level interconnects 24 a and 24 b were formed. Reference numeral 15 denotes a silicon nitride film as an etching stopper, 16 is an organic SOG film as methylsiloxane type film, 17 a silicon oxide film, 24 a titanium nitride used as barrier metal film, and 24 b a copper layer. A plan view of the process in this stage is shown in FIG. 20. This process is different from the process shown in FIG. 12 to FIG. 18 in that film thickness of the organic SOG film 16 is as thin as 200 nm and that hole pattern of vias is changed to trench pattern of the second level interconnects.
[0069] In the semiconductor device of Example 1 as formed above, yield of the multilevel interconnects was evaluated. As a result, via connection yield of 0.25 μm diameter vias and insulation yield of 0.25 μm spacing interconnects were both 95% or more, and no decrease of yield due to faceting was observed.
[0070] Further, the process from FIG. 12 to FIG. 20 of Example 1 was repeated, and 3-level interconnects were formed, and capacitance between adjacent wires of the second level interconnects was measured. Effective dielectric constant between the adjacent wires thus obtained was 3.3.
[0071] In the above Example, silicon nitride film was used as hard mask, but this may contain Si—H bond in addition to the main component. Also, the film may replace silicon carbide film or may contain Si—H bond or Si—CH 3 bond in addition to the main component of silicon carbide film.
[0072] In the above Example, the organic SOG film was used as methylsiloxane film, while Si—H bond or Si—C—Si bond may be contained in addition to the main components of Si—CH 3 bond and Si—O—Si bond. Also, the film may be formed by CVD method instead of coating method. Or, oligomer solution mixed with organic polymer may be coated in advance, and organic polymer may be decomposed and removed by curing, and low density organic SOG thus prepared may be used.
[0073] The materials of the hard mask and methylsiloxane film are the same in the examples as described below.
[0074] The effect of sputter-etching length is shown in FIG. 21. Here, the samples were the same as that shown above except for the length of sputter-etching. The sputter-etching length is represented by the sputter-etched thickness, which is the decrease in thickness when the sputter-etching for the same length is applied to a blanket silicon-oxide film.
EXAMPLE 2
[0075] [0075]FIG. 22 to FIG. 27 each represents a cross-sectional view or a plan view of a manufacturing process of a semiconductor device in Example 2 of the present invention where dual damascene process is applied for formation of multi-level interconnects. In this Example, the process from FIG. 9 to FIG. 14 is the same as in Example 1.
[0076] After the process of FIG. 13, the resist 9 was removed as shown in FIG. 22. A second organic SOG film was coated as a methylsiloxane film 16 in thickness of 200 nm, and this was cured under nitrogen ambient at 425° C. Further, a second silicon oxide film 17 was formed in thickness of 100 nm by plasma CVD method, and a silicon nitride film was formed in thickness of 150 nm as a second hard mask 18 .
[0077] Next, as shown in FIG. 23, reactive ion etching was performed using a second resist 19 as mask, and the second level interconnect pattern was transferred to the second hard mask 18 . In this etching process, it is necessary to stop the etching in the second silicon oxide film 17 without exposing lower level second organic SOG film 16 as shown in the plan view of FIG. 24. There is no need to stop the etching exactly on the upper surface of the second silicon oxide film 17 as shown in FIG. 23. The second silicon oxide film may be etched if the second organic SOG film 16 is not exposed.
[0078] Next, as shown in FIG. 25, the resist 19 was removed by ICP type asher, and reactive ion etching was performed using the second silicon nitride film 18 and the first silicon nitride film 8 as hard masks, and etching was performed on the first silicon oxide film 7 and the second silicon oxide film 17 as well as the first organic SOG film 6 and the second organic SOG film 16 . In this etching process, etching selectivity of the silicon oxide and the organic SOG to silicon nitride was 10 . By this etching process, film thickness of the exposed portion of each of the first hard mask 8 and the second hard mask 18 was turned to 60 nm. As a result, via holes were formed in the layered film of the first organic SOG film 6 and the first silicon oxide film 7 . Also, a trench for the second level interconnect was formed in the layered film of the second organic SOG film 16 and the second silicon oxide film 17 .
[0079] Next, as shown in FIG. 26, the spaces in the hole and the trench were cleaned using wet solution, and etching was performed on the etching stopper 5 . In this case, exposed portions of the first hard mask 8 and the second hard mask 18 almost completely disappeared. The hard masks 8 and 18 on the exposed portions may remain after the etching stopper 5 on the upper surface of the first level interconnects 4 a and 4 b is completely removed. However, it is preferable to completely remove them by over-etching because parasitic capacitance between interconnects can be reduced.
[0080] Further, as shown in FIG. 27, sputter-etching was performed for 20 nm as measured using blanket silicon oxide film, and titanium nitride and copper were thinly formed by sputtering. Then, by copper plating, layered films of a barrier metal film 34 a comprising titanium nitride and a copper film 34 b were buried in the hole and the trench. Further, by chemical-mechanical polishing, titanium nitride and copper outside the hole and the trench were removed. Consequently, vias 34 a and 34 b , and interconnects 34 a and 34 b were fabricated in the layered films.
[0081] On the multi-level interconnects of the Example 2 thus prepared, the yield was evaluated. As a result, via connection yield of 0.25 μm diameter vias and insulation yield of 0.25 μm spacing interconnects were both 95% or more, and no decrease of yield due to faceting was observed.
[0082] Further, by repeating the process from FIG. 12 to FIG. 14 of Example 1 and the process from FIG. 22 to FIG. 27 of Example 2, 3-level interconnects were formed, and capacitance between adjacent interconnects of the second level interconnects was measured. Effective dielectric constant of the adjacent wires thus obtained was 3.6. The increase of effective dielectric constant compared with Example 1 is attributed to the fact that the silicon nitride film 8 for the first hard mask of 100 nm in thickness remains in the inter-level dielectrics.
EXAMPLE 3
[0083] [0083]FIG. 28 to FIG. 36 each represents a cross-sectional view or a plan view of a manufacturing process of a semiconductor device in Example 3 of the present invention where dual damascene process is applied for formation of multi-level interconnects. In this example, the processes from FIG. 9 to FIG. 12 are the same as in Example 1.
[0084] After the process of FIG. 12, as shown in FIG. 28, a second organic SOG film 16 was coated in thickness of 200 nm as a methylsiloxane film 16 , and this was cured in nitrogen ambient at 425° C. Further, by plasma CVD method, a second silicon oxide film 17 was formed in thickness of 100 nm, and a silicon nitride film was formed in thickness of 100 nm as a second hard mask 18 .
[0085] Next, as shown in FIG. 29, reactive ion etching was performed using a first resist 19 as mask, and the pattern of the second level interconnects was transferred to the second hard mask 18 . In this etching process, it is necessary to stop the etching in the second silicon oxide film 17 without exposing the second organic SOG film 16 as shown in the plan view of FIG. 30. There is no need to stop the etching exactly on the upper surface of the second silicon oxide film 17 as shown in FIG. 29. The second silicon oxide film 17 may be removed to some extent if the second organic SOG film 16 is not exposed.
[0086] Next, as shown in FIG. 31, the first resist 19 was removed by ICP type asher, and the second resist 9 was formed and patterned using lithography. Then, via hole pattern was transferred to the second silicon oxide film 17 and the second organic SOG film 16 . In this etching process, it is necessary to etch the first hard mask completely. There is no need to stop the etching exactly on the upper surface of the first silicon oxide film 7 in FIG. 31, and the first silicon oxide film 7 and the first organic SOG film 6 may be etched to some extent.
[0087] Next, as shown in FIG. 33, low-pressure reactive ion etching was performed using oxygen at the pressure of 10 mTorr, and the second resist 9 was removed. Under this condition, aspect ratio of the hole formed in the second organic SOG film 16 and the second silicon oxide film 17 was 3 or less in a hole pattern of 0.25 μm in diameter. By removing the second resist 9 at low pressure, the quality deterioration did not occur in the second organic SOG film 16 .
[0088] Further, as shown in FIG. 34, reactive ion etching was performed using the second silicon nitride film 18 and the first silicon nitride film 8 as hard mask, and etching was performed on the first silicon oxide film 7 and the second silicon oxide film 17 as well as the first organic SOG film 6 and the second organic SOG film 16 . In this etching process, etching selectivity of the silicon oxide film and the organic SOG to silicon nitride was 10 . By this etching process, film thickness of the exposed portions of the first hard mask 8 and the second hard mask 18 was turned to 60 nm. As a result, via-holes were formed in the layered films of the first organic SOG film 6 and the first silicon oxide film 7 . Also, trench was formed in the layered films of the second organic SOG film 16 and the second silicon oxide film 17 .
[0089] Next, as shown in FIG. 35, the surface of the holes and the trenches were cleaned using wet solution, and etching was performed on the etching stopper 5 . In this case, exposed portions of the first hard mask 8 and the second hard mask 18 disappeared almost completely. If upper surfaces of the first level interconnects 4 a and 4 b are exposed, there is no problem even when the hard masks 8 and 18 of the exposed portions may remain. However, if it is completely removed, it is possible to reduce parasitic capacitance between the interconnects.
[0090] Further, as shown in FIG. 36, sputter-etching was performed for the time as long as a 20-nm-thick blanket silicon oxide film is removed, and titanium nitride and copper were formed thinly by sputtering. Then, by copper plating, layered films of a barrier metal film 34 a comprising titanium nitride and a copper film 34 b were buried in the hole and the trench. Further, by chemical-mechanical polishing, titanium nitride outside the hole and the trench were removed. Consequently, vias 34 a and 34 b , and interconnects 34 a and 34 b were fabricated in the layered films.
[0091] On the multi-level interconnects of Example 3 thus prepared, the yield was evaluated. As a result, via connection yield of 0.25 μm diameter vias and insulation yield of 0.25 μm spacing interconnects were both 95% or more, and no decrease of yield due to faceting was observed.
[0092] In the above examples, description has been given on the case where titanium nitride was used as barrier metal film, while the invention is not limited to these examples, and film of nitride of refractory metal such as tantalum nitride, tungsten nitride, etc. may be used.
[0093] According to the present invention, it is possible to prevent via-connection failure and short failure in multi-level interconnects.
[0094] The foregoing invention has been described in terms of preferred embodiments. However, those skilled, in the art will recognize that many variations of such embodiments exist. Such variations are intended to be within the scope of the present invention and the appended claims. | To provide a method for manufacturing a semiconductor device, by which it is possible to form a trench or a hole with high aspect ratio on a methylsiloxane type film with low dielectric constant with causing neither via-connection failure nor short-circuit failure even when lower level interconnect is covered with etching stopper. The method comprises the processes of forming a layered film with a silicon oxide film on upper layer of a methylsiloxane type film and forming the layered film using a hard mask. When the etching stopper is etched, the silicon oxide film acts as a hard mask for the methylsiloxane type film, and transfer of faceting to the methylsiloxane type film is prevented. Thus, parasitic capacitance of multi-level interconnect can be reduced without causing via-connection failure and short failure. | 7 |
[0001] This invention relates to a novel assay to screen for anti-malarial drugs using plasmodial heat shock protein 90 as target.
PRIOR ART
[0002] Hsp90 is an abundant protein in eukaryotes comprising of 1-2% of total cellular proteins. It is indispensable for viability of yeast (1). In addition, Hsp90 is also shown to be essential for growth and development in fruit flies (2) and plants (3). Hsp90 in concert with Hsp70 and other co-chaperones, aids in the folding of certain subset of newly synthesized proteins and helps them to attain their mature, functional conformation. It associates with a variety of substrates in the eukaryotic cytosol like transcription factors (steroid receptors, aryl hydrocarbon receptor, heat shock factor, mutant p53, etc.), kinases (pp60 v-src , Raf-1, eIF-2α kinase, etc.), cytoskeletal proteins (actin and tubulin), telomerase, and proteosomes, thus participating in several important cellular functions like regulation of gene expression, signal transduction, cell proliferation and protein degradation (4, 5).
[0003] This multi-functional protein has also been shown to take part in protein targeting by associating with different co-chaperones. For instance, it utilizes the co-chaperone p50 cdc37 to transport kinases to plasma membrane and it uses FKBPs and p23 to translocate steroid receptors from cytosol to nucleus.
[0004] Hsp90, in combination with Hsp70 and Hop (Hsp70-Hsp90 organizing protein) forms multi-chaperone machinery in the eukaryotic cytosol (6). This pre-formed complex forms a part of “foldosome”, which helps in the folding and assembly of client proteins. During stress, it prevents misfolding and non-specific aggregation of proteins. It is also involved in the folding of tumor suppressor protein, p53.
[0005] Hsp90 is found in elevated levels in several tumor cell lines. In tumor cells, Hsp90 stabilizes oncogenic protein kinases, mutated p53, etc. and thus takes part in tumor cell proliferation (7). Inhibiting Hsp90 function in tumor cells would therefore cause reversion to normal phenotype.
[0006] Ansamycin antibiotics, Geldanamycin (GA) and Herbimycin A (HA) were isolated from the fungus, Streptomyces hygroscopicus . The ansa ring of GA and HA resembles the adenine base of ATP and benzoquinone moiety is analogous to the ribose and phosphate group of ATP. Hence they compete with ATP in binding to ATP-binding domain of Hsp90 (8). GA is known to interfere with Hsp90 function by associating with ATP-binding pocket. When cell extracts were passed through GA-immoblized column, Hsp90 was the only protein from cell lysates that specifically bound to the column (9,10).
[0007] During its asexual life cycle in human erythrocytes, the malarial parasite progresses through three growth phases (11). The early form following invasion, called the ring stage, is the phase of establishment in the erythrocyte. Trophozoite stage is the metabolically most active, biosynthetic phase while the schizont stage represents the phase of nuclear division before release of merozoites from the erythrocyte. Heat shock proteins of the class Hsp60, Hsp70 and Hsp90 are known to be expressed by the parasite during the intra-erythrocytic stages in the vertebrate host (12,13,14). While these heat shock proteins share significant homologies with their mammalian counterparts, there is very limited information available about their functional roles in parasite development.
[0008] Hsp90 of Plasmodium falciparum (PfHsp90) is encoded by a single copy gene located in chromosome 7. The gene has a single intron of 800 bp and the encoded protein product has 745 amino acids with a molecular weight of 86 kDa (15). PfHsp90 sequence is highly conserved across various species. It shows 59% identity and 69% similarity to mammalian Hsp90. Very limited information is available regarding the functional role of PfHsp90 (16,17).
OBJECTIVE OF INVENTION
[0009] While it was well known that plasmodial Heat shock proteins of the class Hsp60, Hsp70 and Hsp90 are known to be expressed by the parasite during the intra-erythrocytic stages in the vertebrate host and that these heat shock proteins share significant homologies with their mammalian counterparts, there is very limited information available about their functional roles in parasite development. The objective of the invention was to determine whether these heat shock proteins are functionally important in the growth of parasites in vivo and in vitro using HSP90 as a model and develop suitable screening assays that will be useful to test chemical library of compounds and select novel anti-malarial agents.
SUMMARY OF INVENTION
[0010] The sequence alignment of Plasmodium falciparum HSP90 with human HSP90 (a and β) and its homologue Grp94 show that N-terminal domain of PfHsp90 shares 69% identity with human Hsp90. Sequence comparison with human Hsp90 reveals that this domain has an ATP/Geldanamycin binding site. The GXXGXG motif in this domain essential for ATP-binding is present in PfHsp90 also. The residues, which make contact with GA in mammalian Hsp90, are also conserved in PfHsp90. Both Geldanamycin and Herbimycin A kill the malarial parasite at the stage of early trophozoite development thereby showing that compounds binding to the geldanamycin binding site can be potential anti-malarial agents. It has been shown in in vitro assays that geldanamycin binds to Plasmodium falciparum HSP90 and such binding can be quantified using suitable immunochemical or radiochemical or non-radioactive assays. It has therefore been possible to describe in the assays wherein any suitably immobilized compound can be tested for the potential to bind to Plasmodium HSP90; the specific anti-malarial effect of a compound that binds to Plasmodium HSP90 can then be tested using known methods. Such assays can be further developed into high throughput assays using the currently known technologies enabling screening of compound libraries as exemplified by the BIAcore assay.
DETAILED DESCRIPTION OF THE INVENTION
[0011] A prototype assay is described below:
[0012] 1.0: Covalent immobilization of the test compound on suitable matrices such as Sepharose or BIAcore CM5 sensor chips by known methods.
[0013] 2.0: Preparation of Saponin-freed Plasmodial trophozoite lysate. P. falciparum infected erythrocytes in the trophozoite stage were treated with a final concentration of 0.075% saponin in PBS (10 mM sodium phosphate (pH 7.4), 137 mM NaCl, 2.7 mM KCl.) and centrifuged at 4,500 rpm for 4 min. Parasites are in the pellet fraction and are then washed twice in PBS and lysed in TNESV buffer (50 mM Tris-HCl, (pH 7.5), 1% NP40, 2 mM EDTA, 100 mM NaCl, 1 mM orthovanadate).
[0014] 3.0: Reacting the trophozoite lysate with the covalently immobilized test compound.
[0015] 4.0: Detection of the compound bound Plasmodium falciparum 90 kDa heat shock protein. This can be performed either by western blotting using polyclonal antibodies to PfHsp90 or by use of radiolabeled trophozoite protein extracts and subsequent detection by phosphorimager analysis as described for analysis of GA binding in examples 3.1 to 3.4. All compounds showing more than 10% of total binding to PfHsp90 were used for further screening.
[0016] Known Covalent Immobilization methods are:
[0017] 1. Photochemical coupling.
[0018] 2. Covalent immobilization of biomolecules using beads coated with carboxyl groups (e.g., LiquiChip Carboxy Beads, Qiagen) using carbodiimide chemistry. In this process, beads are washed and incubated with an activator (typically EDC/NHS), washed again, the capture molecule is added and incubated, and the beads washed again.
[0019] 3. Using immobilized PCR primers
[0020] 4. Spatially controlled covalent immobilization of Biomolecules on silicon surfaces.
[0021] In addition, a non-radioactive assay for screening test compound and related compounds using SPR analysis with a BIAcore 2000™ (Amersham Biosciences) biosensor system may also be used based on technical details provided for GA binding in example 3.4. Briefly, test compound is covalently immobilized on the research CM5 sensor chips at a concentration of 20 mM in 8% DMSO using the amine coupling kit (1-ethyl-3-(dimethylaminopropyl) carbodiimide), (N-hydroxysuccinimide) provided by the manufacturer. For compounds of unknown structure, derivatization is done with biotin using photobiotin acetate (22) followed by BIAcore analysis using the BIAcore SA chip that carries a streptavidin surface. All measurements are carried out with TNESV buffer (50 mM Tris-HCl, (pH 7.5), 1% NP40, 2 mM EDTA, 100 mM NaCl, 1 mM orthovanadate). The surface regenerated by a 50 s pulse of 0.5% SDS flowing at 10 μL/min. For binding analysis, saponin released trophozoites of P. falciparum are lysed in an equal volume of TNESV buffer and the lysate is clarified by centrifugation at 20,000 g for 20 min. Binding is evaluated by passing the parasite lysate at a flow rate of 1 μL/min in TNESV buffer and measuring the change in refractive index as was done for GA binding in example 3.4.
[0022] Compounds thus selected by any of these assays or a combination thereof can then be further tested using known assays described in examples 2.1 and 2.2 and the novel flow cytometry assay as described in example 3.5 to select for the desired anti-malarial effect.
EXAMPLES
Example 1.0
Geldanamycin Binding Site in Pf HSP90
[0023] Sequence alignment of Human Hsp90 (α and β and its homolog Grp94 with PfHsp90 indicates that several domains are evolutionarily conserved suggesting functional similarity among Hsp90 proteins of different organisms. PfHsp90 possesses a charged acidic domain in the central region, which is absent in human Hsp90. N-terminal domain of PfHsp90 shares 69% identity with human Hsp90. Sequence comparison with human Hsp90 reveals that this domain has an ATP/Geldanamycin binding site. The GXXGXG motif in this domain essential for ATP-binding is present in PfHsp90 also. The residues, which make contact with GA in mammalian Hsp90, are also conserved in PfHsp90.
[0024] Crystal structure of N-terminal Hsp90-GA complex has already been solved (PDB ID: 1YET) (18). High degree of similarity between the ATP-binding domains of mammalian Hsp90 and PfHsp90 enabled us to model the ATP-binding domain of PfHsp90 using mammalian Hsp90 as a template. N-terminal sequence of PfHsp90 (1-177 amino acids) was submitted to SWISS-MODEL program to obtain the 3-D structure using the crystal structure of N-terminal Human Hsp90 (PDB code: 1YET) as a template. This model was superimposed over the structure of human Hsp90-GA complex using STAMP (Structure Alignment of Multiple Protein) program as shown in FIG. 1 a of the accompanying drawings. PfHsp90 is shown in blue line while yellow line denotes mammalian Hsp90. GA is represented in yellow colour in the centre of the structure.
[0025] FIG. 1 b shows a magnified view of the GA-binding region and the contact making residues, namely Lys 58, Asp 93, Gly 97, Lys 112, Phe 138 and Gly 183 were indicated. Sequence and structure comparison suggests that GA could possibly interact with PfHsp90 also.
Example 2.0
Effect of Ansamycin Antibiotics on Plasmodial Parasite
[0000] 2.1: Growth Inhibitory Effect of GA:
[0026] In order to check if GA could inhibit Plasmodium falciparum growth in vitro, we prepared highly synchronous ring-infected parasites using 5% sorbitol. These ring-staged parasites were suspended in RPMI to make 5% hematocrit. 200 μl cell suspension was treated with DMSO or with GA in DMSO at various concentrations (0.5, 1, 5 and 10 μM for 24 h. Smears were taken at the end of treatment, Giemsa-stained and viewed under microscope. While the DMSO treated rings progressed to trophozoite stage at the end of 24 hrs, GA-treated parasites persisted in the ring stage even after 24 hrs. The degree of inhibition in stage progression increased with increasing concentration of GA. Maximal growth inhibition was found at 5 μM concentration. The same experiment was performed with early-trophozoites and schizonts also. When GA was added in the trophozoite stage, 100% growth inhibition was observed at a GA concentration of 10 μM. This correlates with elevated expression of Pfhsp90 in the trophozoite stage compared to ring stage. When schizont-staged parasites were treated with GA, it did not affect the release of merozoites and their subsequent reinvasion of erythrocytes.
[0000] 2.2: Anti-Malarial Effect of GA and HA
[0027] To show the effects of GA on overall parasitemia, ring-infected erythrocytes were either treated with DMSO or with 5 μM GA for 48 hrs (culture was replenished with medium and GA every 24 hrs) and parasitemia was calculated by giemsa staining. While the mock-treated parasites multiplied at the end of 48 hrs, parasitemia was reduced to 50 percent in GA treated cultures by 48 hrs. When cultures were similarly treated with various concentrations of HA (0.5, 1, 5 and 10 μM), maximal reduction in parasitemia was observed at 10 μM concentration.
[0028] Examples 2.1 and 2.2 clearly demonstrate that ansamycin antibiotics affect overall parasitemia at the stage of the formation of trophozoites.
Example 3.0
In vitro Assay to Test the Effect of Geldanamycin for Binding to PfHsp90 and Parasite Growth Inhibition
[0000] 3.1: Solid-Phase GA Binding Assay:
[0029] Geldanamycin was immobilized on sepharose beads (9). GA was first modified by adding 1,6-hexanediamine as a linker for coupling to the activated ester beads. 1,6-hexanediamine was added to GA (10 mM in CHCl 3 ) to yield 10-fold molar excess and allowed to react at room temperature for 2 h in the dark to yield 17-hexamethylenediamine-17-demethoxy-geldanamycin. The reaction solution was extracted with water to remove the unreacted 1,6-hexanediamine. The products were then dried under nitrogen, redissolved in DMSO, and reacted with NHS-activated Sepharose 4 fast flow beads (Amersham Biosciences) for 2 h in the dark at room temperature. The resulting beads were washed twice in ice-cold TNESV buffer (50 mM Tris-HCl, (pH 7.5), 1% NP40, 2 mM EDTA, 100 mM NaCl, 1 mM orthovanadate) and rocked overnight at 4° C. GA beads were then blocked with 1% BSA for 1 h. For control beads, the resin was treated in the same way, but without adding 17-hexamethylenediamine-17-demethoxy-geldanamycin.
[0000] 3.2: Immunoblot analysis of PfHSP90 and GA binding:
[0030] P. falciparum cultures were treated with saponin at a concentration of 0.075% to release the trophozoites. Saponin released trophozoites of P. falciparum were lysed in TNESV buffer (50 mM Tris-HCl, pH 7.5), 1% NP-40, 2 mM EDTA, 100 mM NaCl, 1 mM orthovanadate) containing protease inhibitors. Clarified lysate was incubated with either with GA coupled beads or control beads and incubated overnight at 4° C. Beads were washed four times with TNESV buffer, solubilized in Laemmli buffer and analyzed on SDS-PAGE (7.5% resolving gel with 3% stacker gel) (19). Proteins were transferred to nitrocellulose membrane and the membrane was blocked in 1% milk powder in TBST (20 mM Tris, 136 mM NaCl, 0.05% Tween-20, pH 7.2) for 1 h. The membrane was then washed thrice with TBST for 10 min each. The membrane was then probed with rabbit polyclonal antibody to PfHsp90. After 3 washes with TBST for 10 min each, the membrane was probed with anti-rabbit IgG conjugated to ALP (alkaline phosphatase). The membrane was developed using BCIP (5-bromo, 3-chloro, indolyl phosphate)/NBT (nitroblue tetrazolium) as substrate. Under these conditions, we could clearly see binding of PfHsp90 to the GA-coupled beads. Control beads did not show any binding to PfHsp90.
[0000] 3.3: Analysis of PfHSP90 and GA binding by metabolic labeling of proteins:
[0031] P. falciparum infected erythrocytes in the trophozoite stage were labeled with [ 35 S]-cys and [ 35 S]-met. Following lysis with 0.075% saponin, parasites were lysed in TNESV buffer containing protease inhibitors. Lysate was incubated with either with GA coupled beads or control beads and tumbled overnight at 4° C. Beads were washed four times with TNESV buffer and solubilized in 2D lysis buffer. The sample in 2D lysis buffer was loaded onto 7 cm×1.5 mm IEF tube gels pre-focused at 250 V for 30 mins. Following this, the tube gels were electrophoresed at 500 V for 4 hours. After the run was over, the tube gels were incubated in 1 ml of equilibration buffer (125 mM Tris (pH 6.8), 4.9 mM DTT, 10% glycerol, and 2% SDS, pH 6.8) for 9 minutes. The tube gels were laid horizontally on top of 7.5% SDS-polyacrylamide gels and sealed with 1% agarose in SDS-PAGE running buffer (50 mM Tris, 380 mM glycine, and 0.1% SDS). SDS-PAGE was carried out at 110 V for one hour and 10 minutes. The spots were visualized using fluorography (20). Earlier work from the lab has unequivocally established the position of PfHsp90 (pI=4.94, M w =86 kDa) on 2D-PAGE (21). Based on this, the protein bound to GA coupled beads was identified as PfHsp90. Control beads did not show any binding to PfHsp90.
[0000] 3.4 Analysis of PfHSP90 and GA binding by Surface Plasmon Resonance Spectroscopy:
[0032] To test the feasibility of a non-radioactive assay for screening GA and related compounds, we used SPR analysis with a BIAcore 2000™ (Amersham Biosciences) biosensor system. Geldanamycin was covalently immobilized on the research CM5 sensor chips at a concentration of 20 mM in 8% DMSO using the amine coupling kit (1-ethyl-3-(dimethylaminopropyl) carbodiimide, N-hydroxysuccinimide) provided by the manufacturer. Nearly 700 resonance units (RU) of GA were immobilized under these conditions. The unreacted moieties on the surface were blocked with 1M ethanolamine. All measurements were carried out with TNESV buffer. The surface was regenerated by a 50-s pulse of 0.5% SDS flowing at 10 μL/min.
[0033] For binding analysis, saponin released trophozoites of P. falciparum were lysed in an equal volume of TNESV buffer and the lysate was clarified by centrifugation at 20,000 g for 20 min. Binding was evaluated by passing the parasite lysate at a flow rate of 1 μL/min in TNESV buffer and measuring the change in refractive index as response units. Upon passing the parasite lysate over the GA coupled chip, significant binding (response of 900 RU) was observed. In order to make sure that the binding was due to PfHsp90, parasite lysate was mixed with antiserum to PfHsp90 and then passed over the GA coupled chip. In this instance, binding was completely abolished, indicating that PfHsp90 from the parasite lysate was specifically binding to GA coupled in the chip.
[0000] 3.5: Analysis of the Inhibition of P. falciparum Growth by GA Using Flow Cytometry
[0034] In order to confirm P. falciparum inhibition by GA and related compounds, we developed an assay involving flow cytometry. Briefly, parasites were purified on 75% percoll thrice in order to obtained a pure parasite population free of uninfected RBCs. 30 μL of such a suspension was added to 600 μL of the staining solution (6 mg/L of acridine orange in 10 mM Tricine and 120 mM NaH 2 PO 4 at pH 9). The suspension of stained cells was injected into a flow cytometer (BD (Becton Dickinson) FACScan) equipped with an argon ion laser set at 488 nm at a power output of 15 mW. Green fluorescence (GF) was detected at 560 nm. Side scatter (SSC) was detected simultaneously with GF. At most, 10,000 cells were assessed and plotted in a two-dimensional scattergram of SSC (linear scale) against GF (logarithmic scale) in less than 60 seconds. The parasite area was defined in a two dimensional scattergram of SSC vs. GF. The ring and trophozoite forms were clearly defined by analysis of scattergrams for parasites at various times after synchronization. The validity of the assay was confirmed by treating highly synchronous ring stage parasites with 10 μM GA for 24 h. DMSO treated parasites were used as control. GA treated parasites displayed a scattergram corresponding to rings while the scattergram of the DMSO treated control corresponded to that of trophozoites. The data clearly demonstrates that GA and related compounds can be effective as anti-malarials.
[0035] Based on the assays described in example 3 of this specification, it is feasible for one skilled in the art to develop similar assays and to test for the binding of test compounds to Pfhsp90 (using solid phase coupling to sepharose beads and BIACORE chips) as well as for inhibition of the growth of P. falciparum (using the flow cytometry assay).
REFERENCES
[0000]
1. Borkovich K. A., Farrelly F. W., Finkelstein D. B., Taulien J. and Lindquist S. (1989) Hsp82 is an essential protein that is required in higher concentrations for growth of cells at higher temperature. Mol. Cell Biol. 9, 3919-3930.
2. Rutherford S. L. and Lindquist S. (1998) Hsp90 as a capacitor for morphological evolution. Nature 396, 336-342.
3. Queitsch C., Sangster T. A. and Lindquist S. (2002) Hsp90 as a capacitor for phenotypic variation. Nature 417, 618-624.
4. Csermely P., Schnaider T., Soti C., Prohaszka Z. and Nardai G. (1998) The 90-kDa molecular chaperone family: structure, function, and clinical applications. A comprehensive review. Pharmacol. Ther. 79, 129-168.
5. Buchberger A. and Bakau B. (1997) Guidebook to Molecular Chaperones and protein - folding catalysts . Oxford University Press, Oxford, UK, pp. 147.
6. Murphy P. J. M., Kanelakis K. C., Galigniana M. D., Morishima Y and Pratt W. B. (2001) Stoichiometry, abundance and functional significance of the hsp90/hsp70-based multiprotein chaperone machinery in reticulocyte lysate. J. Biol. Chem. 276, 30092-30098.
7. Blagosklonny M V. (2002) Hsp90-associated oncoproteins: multiple targets of geldanamycin and its analogs. Leukemia 16, 455-462.
8. Grenert J. P., Sullivan W. P., Fadden P., Haystead T. A. J., Clark J., Mimnaugh E., Krutzsch H., Ochel H. J., Schulte T. W., Sausville E., Neckers L. M. and Toft D. O. (1997) The Amino-terminal domain of heat shock protein 90 (hsp90) that binds geldanamycin is an ATP/ADP switch domain that regulates hsp90 conformation. J. Biol. Chem. 272,23843-23850.
9. Whitesell L., Mimnaugh E. G., Costa B., Myers C. E. and Neckers L. M. (1994) Inhibition of heat shock protein Hsp90-pp60 v-src heteroprotein complex formation by benzaquinone ansamycins: Essential role for stress proteins in oncogenic transformation. Proc. Natl. Acad. Sci. USA 91, 8324-8328.
10. Schneider C., Lorenzino L., Nimmesgem E., Ouerfelli O., Danishefsky S., Rosen N. and Hartl U. F. (1996) Pharmacologic shifting of a balance between protein refolding and degradation mediated by Hsp90 . Proc. Natl. Acad. Sci. USA 93, 14536-14541.
11. Bannister L. H., Hopkins J. M., Fowler R. E., Krishna S. and Mitchell G. H. (2000) A brief illustrated guide to the ultrastructure of Plasmodium falciparum asexual blood stages. Parasitology Today 6,427433.
12. Das A., Syin C., Fujioka H., Zheng H., Goldman N., Aikawa M. and Kumar N. (1997) Molecular characterization and ultrastructural localization of Plasmodium falciparum Hsp60 . Mol. Biochem Parasitol. 88, 95-104.
13. Kumar N., Koski G., Harada M., Aikawa M. and Zheng H. (1991) Induction and localization of Plasmodium falciparum stress proteins related to the heat shock protein 70 family. Mol. Biochem. Parasitol. 48, 47-58.
14. Jendoubi M., Dubois P. and Silva L. P. (1985) Characterization of one polypeptide antigen potentially related to protective immunity against the blood infection by Plasmodium falciparum in the squirrel monkey. J. Immunol. 134,1941-1945.
15. Bonnefoy S., Attal G., Langsley G., Tekaia F. and Puijalon O. M. (1994) Molecular characterization of the heat shock protein 90 gene of the human malarial parasite Plasmodium falciparum. Mol. Biochem. Parasitol. 67,157-170.
16. Banumathy G, Singh V, Pavithra S R, Tatu U. (2003) Heat shock protein 90 function is essential for Plasmodium falciparum growth in human erythrocytes. J. Biol. Chem. 278, 18336-45.
17. Kumar R, Musiyenko A, Barik S. (2003) The heat shock protein 90 of Plasmodium falciparum and anti-malarial activity of its inhibitor, geldanamycin. Malar J. 2, 30-41.
18. Stebbins C. E., Russo A. A., Schneider C., Rosen N., Hartl F. U. and Pavletich N. P. (1997) Crystal structure of an Hsp90-geldanamycin complex: Targeting of a protein chaperone by an antitumor agent. Cell 89, 239-250.
19. Laemmli U. K. (1970) Cleavage of structural proteins during the assembly of the head of bacteriophage T4 . Nature 227, 680-685.
20. O'Farrell P. H. (1975) High resolution two dimensional gel electrophoresis of proteins. J. Biol. Chem. 250, 4007-4021.
21. Banumathy G, Singh V, Tatu U. (2002) Host chaperones are recruited in membrane-bound complexes by Plasmodium falciparum. J. Biol. Chem. 277, 3902-12.
22. McInnes J. (1990) Preparation and uses of photobiotin. Meth. Enzymol. 184, 588-600. | Malarial parasite Plasmodium falciparum is responsible for the most severe form of malaria in humans, causing about 2 million deaths every year. Lack of effective vaccines and emergence of drug-resistant strains necessitate the need of novel drug targets to treat the disease. The present invention describes a novel assay method of identifying candidate compounds as anti-malarials based on the property of binding to plasmodial parasite 90 kDa heat shock protein. | 8 |
BACKGROUND OF THE INVENTION
The present invention provides novel compositions of matter. This invention further provides novel processes for preparing these compositions of matter. The present invention provides novel (11R)-11-deoxy-11-alkyl-6-oxo-PG type compounds. The 6-oxo-PGE-type compounds from which the compounds of this invention are derived are known in the art and are structural and pharmacological analogs of the prostaglandins.
The prostaglandins are a family of 20 carbon atom fatty acids, being structural derivatives of prostanoic acid, which exhibit useful activity in a wide variety of biological systems. Accordingly, such prostaglandins represent useful pharmacological agents in the treatment and prevention of a wide variety of disease conditions. The term "PG-type compounds" is used to describe structural analogs of the prostaglandins. For a fuller discussion of the prostaglandins, see Bergstrom, et al., Pharmacol. Rev. 20: 1 (1968) and references cited therein.
Similarly, the 6-oxo-PGE type compounds from which the compounds of the present invention are derived exhibit useful activity in a wide variety of biological systems. They also represent useful pharmacological agents in the treatment and prevention of a wide variety of disease conditions.
All of the compounds of the present invention are useful for curing and preventing duodenal ulcers and for preventing or treating gastrointestinal cell damage caused by the use of other pharmacological agents. The compounds of the present invention may also exhibit one or more other useful pharmacological properties. Thus, they may be useful for lowering blood pressure; for inhibiting gastric secretion; for decreasing blood platelet adhesion; for inhibiting blood platelet aggregation and thrombosis formation induced by various physical and chemical stimuli; for the treatment of asthma; for the control of fertility and procreation; and for the treatment of vascular disease states.
PRIOR ART
The known 6-oxo-PGE type compounds are disclosed in U.S. Pat. Nos. 4,215,142; 4,205,178; 4,124,601; 4,251,466; 4,171,447; 4,255,355; 4,246,197; and 4,223,157 and European patent application No. 19069. 6-oxo PGE analogs are also disclosed in copending application No. 070,226. 11-Deoxy-11-alkyl prostaglandins are disclosed in U.S. Pat. Nos. 4,036,871; 4,052,446; 4,187,381; 4,190,587; 4,211,724; and 4,237,060.
SUMMARY OF THE INVENTION
The present invention provides a compound of the formula I, or an enantiomer or a racemic mixture of enantiomers thereof;
wherein M 1 is:
(1) --(CH 2 ) d --C(R 3 ) 2 --;
(2) --CH 2 --O--CH 2 --Y 1 --;
(3) cis-CH 2 --CH═CH--; or
(4) trans-CH 2 --CH═CH--;
wherein N 1 is
(1) --COOR 4 ;
(2) --CH 2 OR 8 ;
(3) --CH 2 NR 5 R 6 ;
(4) --CO--NR 5 R 6 ;
(5) --CN;
(6) --COR 1 ; or
(7) --COCH 2 OH;
wherein E 1 is
(1) trans--(CH═CH--;
(2) cis-CH═CH--;
(3) --C.tbd.C--; or
(4) --CH 2 --CH 2 --;
wherein Q 1 is
(1) α-OR 8 :β-R 7 ;
(2) α-R 17 :β-OR 8 ;
(3) oxo; or
(4) α-H:β-H;
wherein L 1 is
(1) α-R 9 :β-R 10 ;
(2) α-R 10 :β-R 9 ;
(3) α-OR 8 :β-R 7 ; or
(4) α-R 7 :β-OR 8 ;
wherein R 1 is (C 1 -C 4 )alkyl;
wherein R 2 is
(1) --O--(PhX);
(2) --C p H 2 .sbsb.p --(PhX);
(3) --C m H 2 .sbsb.m --(DZ);
(4) --C p H 2 .sbsb.p +1;
(5) --CH 2 --CH 2 --CH═C(CH 3 ) 2 ;
(6) --C a H 2 .sbsb.a --O--C b H 2 .sbsb.b +1;
(7) --O--(T); or
(8) --C p H 2 .sbsb.p --(Py);
wherein (PhX) is phenyl substituted by zero to 3 of the following:
(1) (C 1 -C 4 )alkyl;
(2) chloro;
(3) fluoro;
(4) bromo;
(5) nitro;
(6) trifluoromethyl; or
(7) OR 8 ;
wherein DZ is a (C 3 -C 6 ) cycloaliphatic substituted by zero to 3 of the following:
(1) (C 1 -C 4 )alkyl;
(2) chloro;
(3) fluoro;
(4) bromo;
(5) nitro;
(6) trifluoromethyl; or
(7) OR 8 ;
wherein T is 3-thienyl;
wherein Py is 2, 3, or 4-pyridinyl;
wherein R 3 is
(1) hydrogen;
(2) fluoro; or
(3) methyl;
wherein R 4 is
(1) hydrogen;
(2) (C 1 -C 12 )alkyl;
(3) (C 3 -C 10 )cycloalkyl;
(4) (C 7 -C 12 )aralkyl;
(5) phenyl;
(6) phenyl, mono-, di-, or trisubstituted by chloro or alkyl of from one to 3 carbon atoms, or
(7) a pharmacologically acceptable cation, or
(8) phenyl para-substituted by
(a) --NHCO--R 25 ;
(b) --O--CO--R 26 ;
(c) --O--CO--R 24 ;
(d) --O--CO--(p-Ph)--R 27 ; or
(e) --CH═N--NH--CO--NH 2 ;
wherein R 24 is phenyl or acetamidophenyl; R 25 is methyl, phenyl, acetamidophenyl, benzamidophenyl, or amino, R 26 is methyl, amino or methoxy; R 27 is hydrogen or acetamido; and (p-Ph) is 1,4-phenylene; wherein R 5 and R 6 are the same or different and are
(1) hydrogen;
(2) (C 1 -C 4 )alkyl;
(3) (C 6 -C 12 )aryl; or
(4) (C 7 -C 14 )aralkyl;
wherein R 7 is
(1) hydrogen; or
(2) C 1 -C 4 alkyl;
wherein each occurrence of R 8 is the same or different and is
(1) hydrogen;
(2) (C 1 -C 4 )alkyl; or
(3) --COR 13 ;
wherein R 9 and R 10 are the same or different and are
(1) hydrogen;
(2) (C 1 -C 4 )alkyl; or
(3) fluoro;
wherein R 13 is
(1) hydrogen;
(2) (C 1 -C 12 )alkyl;
(3) (C 3 -C 10 )cycloalkyl;
(4) (C 7 -C 12 )aralkyl;
(5) phenyl; or
(6) substituted phenyl;
wherein R 17 is (C 1 -C 4 )alkyl;
wherein Y 1 is
(1) a valence bond; or
(2) --(CH 2 ) r --;
wherein d is an integer from 0-5;
wherein p is an integer from 0-8;
wherein m is an integer from 0-3;
wherein q is an integer from 3-6;
wherein a is an integer from 0-2;
wherein b is an integer from 1-5; and
wherein r is an integer from 1-2.
Examples of phenyl esters substituted in the para position (i.e., N 1 is --COOR 4 , R 4 is p-substituted phenyl) include p-acetamidophenyl ester, p-benzamidophenyl ester, p-(p-acetamidobenzamido)phenyl ester, p-(p-benzamidobenzamido)phenyl ester, p-amidocarbonylamidophenyl ester, p-acetylphenyl ester, p-benzylphenyl ester, p-amidocarbonylphenyl ester, p-methoxycarbonylphenyl ester, p-benzoyloxyphenyl ester, p-(p-acetamidobenzoyloxy)phenyl ester and p-hydroxybenzaldehyde semicarbazone ester.
The carbon atom content of various hydrocarbon-containing moieties is indicated by a prefix designation the minimum and maximum number of carbon atoms in the moiety, i.e., the prefix (C i -C j ) indicates a moiety of the integer "i" to the integer "j" carbon atoms, inclusive. Thus (C 1 -C 3 )alkyl refers to alkyl of one to 3 carbon atoms, inclusive, or methyl, ethyl, propyl, and isopropyl.
Examples of alkyl of one to 12 carbon atoms, inclusive, are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and isomeric forms thereof.
Examples of cycloalkyl of 3 to 10 carbon atoms, inclusive, which includes alkyl-substituted cycloalkyl, are cyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl, 2,3-diethylcyclopropyl, 2-butylcyclopropyl, cyclobutyl, 2-methylcyclobutyl, 3-propylcyclobutyl, 2,3,4-triethylcyclobutyl, cyclopentyl, 2,2-dimethylcyclopentyl, 2-pentylcyclopentyl, 3-tert-butylcyclopentyl, cyclohexyl, 4-tert-butylcyclohexyl, 3-isopropylcyclohexyl, 2,2-dimethylcyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
Examples of aralkyl of 7 to 12 carbon atoms, inclusive, are benzyl, 2-phenethyl, 1-phenylethyl, 2-phenylpropyl, 4-phenylbutyl, 3-phenylbutyl, 2-(1-naphthylethyl), and 1-(2-naphthylmethyl).
Examples of phenyl substituted by one to 3 chloro or alkyl of one to 4 carbon atoms, inclusive, are p-chlorophenyl, m-chlorophenyl, 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, p-tolyl, m-tolyl, o-tolyl, p-ethylphenyl, p-tert-butylphenyl, 2,5-dimethylphenyl, 4-chloro-2-methylphenyl, and 2,4-dichloro-3-methylphenyl.
Examples of substituted benzyl, phenylethyl, or phenylpropyl are (o-, m-, or p-)tolyl, (o-, m-, or p-)ethylphenyl, 2-ethyl-(o-, m-, or p-)tolyl, 4-ethyl-o-tolyl, 5-ethyl-m-tolyl, (o-, m-, or p-)propylphenyl, 2-propyl-(o-, m-, or p-)tolyl, 4-isopropyl-2,6-xylyl, 3-propyl-4-ethylphenyl, (2,3,4-, 2,3,5-, 2,3,6-, or 2,4,5-)trimethylphenyl, (o-, m-, or p-)fluorophenyl, 2-fluoro-(o-, m-, or p-)tolyl, 4-fluoro-2,5-xylyl, (2,4-, 2,5-, 2,6-, 3,4-, or 3,5-)difluorophenyl, (o-, m-, or p-)chlorophenyl, 2-chloro-p-tolyl, (3-,4-,5- or 6-)chloro-o-tolyl, 4-chloro-2-propylphenyl, 2-isopropyl-4-chlorophenyl, 4-chloro-3,5-xylyl, (2,3-, 2,4-, 2,5-, 2,6- or 3,5-)dichlorophenyl, 4-chloro-3-fluorophenyl, (3- or 4-)chloro-2-fluorophenyl, (o-, m-, or p-)trifluoromethylphenyl, (o-, m-, p-)ethoxyphenyl, (4- or 5-)chloro-2-methoxyphenyl, and 2,4-dichloro-(5- or 6-)methylphenyl.
With regard to the divalent substituents described above (e.g., L 1 and M 1 ), these divalent radicals are defined as α-R i :β-R j , wherein R i represents the substituent of the divalent moiety in the alpha configuration with respect to the plane of the ring and R j represents the substituent of the divalent moiety in the beta configuration with respect to the plane of the ring. Accordingly, when M 1 is defined as α-OH:β-H, the hydroxy of the M 1 moiety is in the alpha configuration, and the hydrogen substituent is in the beta configuration.
The prostaglandin analogs of the present invention are useful in mammals, including humans and certain useful animals, e.g., dogs and pigs, to reduce or avoid gastrointestinal ulcer formation, and accelerate the healing of such ulcers already present in the gastrointestinal tract. For this purpose, these compounds are injected or infused intravenously, subcutaneously, or intramuscularly in an infusion dose range about 0.1 μg to about 500 μg/kg of body weight per minute, or in a total daily dose by injection or infusion in the range about 0.1 to about 20 mg/kg of body weight per day, the exact dose depending on the age, weight, and condition of the patient or animal, and on the frequency and route of administration.
These compounds are also useful in reducing the undesirable gastrointestinal effects resulting from systemic administration of anti-inflammatory prostaglandin synthetase inhibitors, and are used for the purpose of concomitant administration of the prostaglandin and the anti-inflammatory prostaglandin synthetase inhibitor. See Partridge et al., U.S. Pat. No. 3,781,429, for a disclosure that the ulcerogenic effect induced by certain non-steroidal anti-inflammatory agents in rats is inhibited by concomitant oral administration of certain prostaglandins of the E and A series, including PGE 1 , PGE 2 , PGE 3 , 13,14-dihydro-PGE 1 , and the corresponding 11-deoxy-PGE and PGA compounds. The compounds of the present invention are useful, for example, in reducing the undesirable gastrointestinal effects resulting from systemic administration of indomethacin, phenylbutazone, and aspirin. These are substances specifically mentioned in Partridge et al., as non-steroidal, anti-inflammatory agents. These are also known to be prostaglandin synthetase inhibitors.
The prostaglandin analog is administered along with the anti-inflammatory prostaglandin synthetase inhibitor either by the same route of administration or by a different route. For example, if the anti-inflammatory substance is being administered orally, the prostaglandin is also administered orally, or alternatively, is administered rectally in the form of a suppository or, in the case of women, vaginally in the form of a suppository or a vaginal device for slow release, for example as described in U.S. Pat. No. 3,545,439. Alternatively, if the anti-inflammatory substance is being administered rectally, the prostaglandin is also administered rectally, or, alternatively, orally or, in the case of women, vaginally. It is especially convenient when the administration route is to be the same for both anti-inflammatory substance and prostaglandin, to combine both into a single dosage form.
The dosage regimen for the prostaglandin in accord with this treatment will depend upon a variety of factors, including the type, age, weight, sex, and medical condition of the mammal, the nature and dosage regimen of the anti-inflammatory synthetase inhibitor being administered to the mammal, the sensitivity of the particular individual mammal to the particular synthetase inhibitor with regard to gastrointestinal effects, and the particular prostaglandin to be administered. For example, not every human in need of an anti-inflammatory substance experienced the same adverse gastrointestinal effects when taking the substance. The gastrointestinal effects will frequently vary substantially in kind and degree. But it is within the skill of the attending physician or veterinarian to determine that administration of the anti-inflammatory substance is causing undesirable gastrointestinal effects in the human or animal subject and to prescribe an effective amount of prostaglandin to reduce and then substantially to eliminate those undesirable effects.
As an example of the potency of these compounds for the protection of the gastrointestinal tract, in a standard laboratory test (11R)-6-oxo-11-deoxy-11,16,16-trimethyl PGE 1 (Example 2 below) exhibits an ED 50 of 80 μg/kg (when administered orally) in protecting against ethanol induced gastric lesions in the rat.
The compounds of the present invention may also exhibit one or more other useful pharmacological properties as described above. The use of compounds having such utilities are described for example, in U.S. Pat. No. 4,205,178.
As an example of the other useful properties exhibited by one or more of the compounds of this invention, (11R)-6-oxo-11-deoxy-11,16,16-trimethyl PGE 1 (Example 2 below) is 100 times as potent as PGF 2 α in monkey uterine stimulating activity, greater than 32 but less than 100 percent as potent as PGF 2 α in increasing rat blood pressure in a standard laboratory test, and is an effective antifertility agent in hamsters at between 30 and 1000 μg/animal.
When N 1 is --COOR 4 , the novel compounds are used for the purposes described above in the free acid form, in ester form, and in the pharmacologically acceptable salt form. When the ester form is used, the ester is any of those within the above definition of R 4 . However, it is preferred that the ester be alkyl of one to 12 carbon atoms, inclusive. Of the alkyl esters, methyl and ethyl are especially preferred for optimum absorption of the compound by the body or experimental animal system; and straight-chain octyl, nonyl, decyl, undecyl, and dodecyl are especially preferred for prolonged activity in the body or experimental animal.
Pharmacologically acceptable cations within the scope of R 4 include pharmacologically acceptable metal cations, ammonium, amine cations, or quaternary ammonium cations.
Especially preferred metal cations are those derived from the alkali metals, e.g., lithium, sodium, and potassium, and from the alkaline earth metals, e.g., magnesium and calcium, although cationic forms of other metals, e.g., aluminum, zinc, and iron are within the scope of this invention.
Pharmacologically acceptable amine cations are those derived from primary, secondary, or tertiary amines. Examples of suitable amines are methylamine, dimethylamine, trimethylamine, ethylamine, dibutylamine, triisopropylamine, N-methylhexylamine, decylamine, dodecylamine, allylamine, crotylamine, cyclopentylamine, dicyclohexylamine, benzylamine, dibenzylamine, α-phenylethylamine, β-phenylethylamine, ethylenediamine, diethylenetriamine, and the like, aliphatic, cycloaliphatic, araliphatic amines containing up to and including about 18 carbon atoms, as well as heterocyclic amines, e.g., piperidine, morpholine, pyrrolidine, piperazine, and lower-alkyl derivatives thereof, e.g., 1-methylpiperidine, 4-ethylmorpholine, 1-isopropylpyrrolidine, 2-methylpyrrolidine, 1,4-dimethylpiperazine, 2-methylpiperidine, and the like, as well as amines containing water-solubilizing or hydrophilic groups, e.g., mono-, di-, and triethanolamine, ethyldiethanolamine, N-butylethanolamine, 2-amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, tris(hydroxymethyl)aminomethane, N-phenylethanolamine, N-(p-tert-amylphenyl)-diethanolamine, glactamine, N-methylglycamine, N-methylglucosamine, ephedrine, phenylephrine, epinephrine, procaine, and the like. Further useful amine salts are the basic amino acid salts, e.g., lysine and arginine.
Examples of suitable pharmacologically acceptable quaternary ammonium cations are tetramethylammonium, tetraethylammonium, benzyltrimethylammonium, phenyltriethylammonium, and the like.
Certain compounds of the present invention are preferred to obtain the optimal combination of biological response, specificity, potency, and duration of activity. Thus, compounds of the formula I, wherein N 1 is --COOH or --COOCH 3 ; M 1 is --(CH 2 ) 2 --C(R 3 ) 2 -- (wherein R 3 is hydrogen or fluoro); or trans-CH 2 --CH═CH--, R 1 is methyl; Q 1 is α-OR 8 :β-R 7 or α-R 7 :β-OR 8 , wherein R 7 and R 8 are hydrogen or methyl; wherein L 1 is α-R 9 :β-R 10 , α-R 10 :β-R 9 , α-OR 8 :β-R 7 , or α-R 7 :β-OR 8 , (wherein R 7 , R 8 , R 9 and R 10 are hydrogen or methyl); or R 2 is --O--(PhX) wherein PhX is metachlorophenyl), --(CH 2 ) 3 --CH 3 , --(CH 2 ) 4 --CH 3 --CH 2 CH 2 --CH═C(CH 3 ) 2 , --CH(CH 3 --(CH 2 ) 3 --CH 3 (S or R), or (CH 2 ) 5 --CH 3 , are preferred. Compounds which satisfy two or more of these preferences are more preferred and compounds wherein all of the above variables are a preferred substituent are most preferred.
The compounds of the present invention are prepared by the procedures set out in Charts A and B. In the charts, R 18 is an acid hydrolyzable protecting group or a silyl protecting group of the formula Si(G 1 ) 3 . Both of these groups are described more fully below. All other variables are as defined above.
Referring to Chart A, the reactive functional groups of a PGA compound of the formula X, are protected by means well known in the art, as set out below. Thus, all variables containing reactive functional groups (e.g., OH or oxo), are meant to include a protectable group of the Formula R 18 where appropriate. Conjugate addition of an alkyl group of the formula R 1 (wherein R 1 is as defined above) to the enone system of formula X is accomplished by the addition of a compound of the formula (R 1 ) 2 LiCu or by a copper mediated Grignard addition.
The ketone function of the compound of the formula XI thus formed is reduced to a hydroxyl group with sodium borohydride or lithium trisec-butylborohydride (L-Selectride®; Aldrich Chemical Co.), with subsequent chromatographic separation of the C-9 epimers of the formula XII.
The formula XII compound is then converted first to its iodo ether and then to its enol ether by procedures well known in the art. See, e.g., U.S. Pat. No. 4,205,178. The enol ether function of this compound is then hydrolyzed by means well known in the art to the Formula XIII compound.
The hydroxyl function of formula XIII compound thus formed is then oxidized to a ketone by procedures known in the art employing well known oxidation agents set out below. The protecting groups are removed, yielding the final products of formula XIV.
Alternatively, the compounds of the present invention are prepared by the method of Chart B, which is exemplified more fully by the Preparations and Examples set out below.
Referring to Chart B, the hydroxyl function of the lactone of the formula XXI is protected with a protecting group of the formula R 18 , yielding the formula XXII compound. The lactone function is reduced using DIBAL (diisobutylaluminum hydride), by methods well known in the art. See, e.g., U.S. Pat. No. 4,205,178. The formula XXIII compound is converted to the formula XXIV compound by an appropriate Wittig reaction, e.g., reaction with carboxyalkyltriphenylphosphonium bromide. The hydroxyl function is then oxidized to a keto function using well known procedures.
The formula XXV compound thus formed is then depyranylated and then hydrated using the procedures described in U.S. Pat. No. 4,026,909, to yield the formula XXVI compound, which is then converted to the formula XXVII compound by the conjugate addition of R 1 as described above. Subsequent reduction of the ketone function, and formation of the iodo ether and enol ether, proceeds as described above for Chart A, ultimately yielding the formula XXIX compound after mild acid hydrolysis. Reductive removal of the benzyl ether group and simultaneous methyl ketal formation is carried out by catalytic hydrogenolysis in methanol in the presence of palladium-on-carbon, to yield the formula XXX compound. Collins oxidation to the corresponding aldehyde, followed by a Wittig-Horner reaction (see, e.g., U.S. Pat. No. 4,016,184), yields the formula XXXI compound. The ketone function is then reduced to the corresponding epimeric alcohols, using, for example, sodium borohydride as described above. The 15-hydroxyl function is protected, and the methyl ketal is hydrolyzed to yield the formula XXXII compound. The conversion of the formula XXXII compound to the final products of formula XXXIII proceeds by well known methods as described above for Chart A and set out more fully below.
R 18 can be a silyl protecting group of the formula --Si(G 1 ) 3 . G 1 is alkyl of one to 4 carbon atoms, cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, inclusive, phenyl, or phenyl substituted with one or 2 fluoro, chloro, or alkyl of one to 4 carbon atoms, with the proviso that in a --Si(G 1 ) 3 moiety the various G 1 's are the same or different and at least one G 1 is hindered (such as tert-butyl). Silyl groups within the scope of --Si(G 1 ) 3 include dimethylphenylsilyl, triphenylsilyl, t-butyldimethylsilyl, or methylphenylbenzylsilyl. With regard to G 1 , examples of alkyl are methyl, ethyl, propyl, isobutyl, butyl, sec-butyl, tert-butyl, and the like. Examples of aralkyl are benzyl, phenethyl, α-phenylethyl, 3-phenylpropyl, α-naphthylmethyl, and 2-(α-maphthyl)ethyl. Examples of phenyl substituted with halo or alkyl are p-chlorophenyl, m-fluorophenyl, o-tolyl, 2,4-dichlorophenyl, p-tert-butylphenyl, 4-chloro-2-methylphenyl, and 2,4-dichloro-3-methylphenyl. Tert-butyldimethylsilyl is most preferred as a silylating agent.
These silyl groups are known in the art. See for example, Pierce "Silylating of Organic Compounds," Pierce Chemical Company, Rockford Ill. (1968). When silylated products of the charts below are intended to be subjected to chromatographic purification, then the use of silyl groups known to be unstable to chromatography is to be avoided. Further, when silyl groups are to be introduced selectively, silylating agents which are readily available and known to be useful in selective silylations are employed. For example, triphenylsilyl and t-butyldimethylsilyl groups are employed when selective introduction is required. A particularly useful silyl group for this purpose is t-butyldimethylsilyl, although other silyl groups are likewise employed.
The acid hydrolyzable protective groups within the scope of R 18 are any group which replaces a hydroxy hydrogen and is neither attacked by nor is as reactive to the reagents used in the transformations used herein as a hydroxy is and which is subsequently replaceable by acid hydrolysis with hydrogen in the preparation of the prostaglandin-type compounds. Several such protective groups are known in the art, e.g., tetrahydropyranyl and substituted tetrahydropyranyl. See for reference E. J. Corey, Proceedings of the Robert A. Welch Foundation Conferences on Chemical Research, XII Organic Synthesis, pgs. 51-79 (1969). These blocking groups which have been found useful include:
(a) tetrahydropyranyl;
(b) tetrahydrofuranyl; and
(c) a group of the formula --C(OR 11 )(R 12 )--CH(R 13 )(R 14 ), wherein R 11 is alkyl of one to 18 carbon atoms, inclusive, cycloalkyl of 3 to 10 carbon atoms, inclusive, aralkyl of 7 to 12 carbon atoms, inclusive, phenyl or phenyl substituted with one to 3 alkyl of one to 4 carbon atoms, inclusive, wherein R 12 and R 13 are alkyl of one to 4 carbon atoms, inclusive, phenyl, phenyl substituted with one, 2, or 3 alkyl of one to 4 carbon atoms, inclusive, or when R 12 and R 13 are taken together --(CH 2 ) a -- or when R 12 and R 13 are taken together --(CH 2 ) b --O--(CH 2 ) c , wherein a is 3, 4, or 5 and b is one, 2 or 3, and c is one, 2, or 3, with the proviso that b plus c is 2, 3, or 4, with the further proviso that R 12 and R 13 may be the same or different, and wherein R 14 is hydrogen or phenyl.
When the blocking group of R 18 is tetrahydropyranyl, the tetrahydropyranyl ether derivative of any hydroxy moieties of the PG-type intermediates herein is obtained by reaction of the hydroxy-containing compound with 2,3-dihydropyran in an inert solvent, e.g., dichloromethane, in the presence of an acid condensing agent such as p-toluenesulfonic acid or pyridine hydrochloride. The dihydropyran is used in large stoichiometric excess, preferably 4 to 100 times the stoichiometric amount. The reaction is normally complete in less than an hour at 20°-50° C.
When the protective group is tetrahydrofuranyl, 2,3-dihydrofuran is used, as described in the preceding paragraph, in place of the 2,3-dihydropyran.
When the protective group is of the formula --C(OR 11 )(R 12 )--CH--(R 13 )(R 14 ), wherein R 11 , R 12 , R 13 , and R 14 are as defined above; a vinyl ether or an unsaturated cyclic or heterocyclic compound, e.g., 1-cyclohexen-1-yl methyl ether, or 5,6-dihydro-4-methoxy-2H-pyran is employed. See C. B. Reese, et al., Journal of the Chemical Society 86, 3366 (1967). The reaction conditions for such vinyl ethers and unsaturated compounds are similar to those for dihydropyran above.
The protective groups as defined above are removed by mild acidic hydrolysis. For example, by reaction with (1) hydrochloric acid in methanol; (2) a mixture of acetic acid, water, and tetrahydrofuran, or (3) aqueous citric acid or aqueous phosphoric acid in tetrahydrofuran, at temperatures below 55° C., hydrolysis of the blocking group is achieved.
Suitable oxidation agents to prepare the compounds of this invention include: Jones Reagent (acidified chromic acid, see Journal of American Chemical Society, 39 (1946)), Collins Reagent (chrominium trioxide in pyridine, see Collins, et al., Tetrahedron Lett., 3363 (1968)), mixtures of chromium trioxide in pyridine, see Journal of the American Chemical Society 75, 422 (1953)), tert-butyl chromate in pyridine (see Biological Chemistry Journal, 84 195 (1962)), and mixtures of dicyclohexylcarbodimide and dimethylsulfoxide (see Journal of the American Chemical Society, 87, 5661 (1965)).
For compounds wherein N 1 is --COOH, the corresponding ester is converted to its free acid by any of the known methods, e.g., treatment with aqueous potassium hydroxide. Alternatively, the corresponding acid may be obtained by enzymatic hydrolysis using Plexaura homomalla-derived esterase. See, for example W. P. Schneider, et al., J. Am. Chem. Soc. 99:1222 (1977).
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is more fully understood by the Examples set out below.
PREPARATION 1
5α-Hydroxy-3α-(tetrahydropyran-2-yloxy)-2β-(benzyloxymethyl)-cyclopentyl-1-acetic acid, γ-lactone
Refer to Chart B (conversion of Formula XXI to XXII).
A one liter flask, equipped with nitrogen, is charged with 10.7 g (0.04079 moles) of 3α,5α-dihydroxy-2β-(benzyloxymethyl)-cyclopentyl-1-acetic acid, γ-lactone and 250 ml of methylene chloride. The mixture is degassed and flushed twice with nitrogen. To the solution is added 0.4 g of pyridine hydrochloride followed by 35 ml of dihydropyran. The reaction is stirred for 6 hr at room temperature. The reaction mixture is concentrated in vacuo to approximately 75 ml, diluted with brine, and extracted twice with ethyl acetate. The combined organic layers are washed with sodium bicarbonate, brine, and concentrated in vacuo. The crude product is filtered through 500 g of silica gel, packed and eluted with a 1:1 mixture of ethyl acetate-hexane. 40 ml Fractions are collected after an initial 700 ml fraction. Fractions 21-53 are combined to yield 13.0 g of the titled product.
NMR (CDCl 3 ; TMS) peaks are as follows: δ1.23-2.95 (complex m, 12H); 3.25-4.35 (m, 5H); 4.52 (s, 2H); 4.65 (s, 1H); 4.81-5.08 (m, 1H), and 7.35 (s, 5H).
IR (νmax; film) peaks are as follows: 2930, 2850, 1770, 1490, 1460, 1360, 1190, 1170, 1110, 1070, 1020, 970, 910, 870, 790, and 690 cm -1 .
TLC analysis reveals: Rf=0.37 in 1:1 ethyl acetate-hexane.
PREPARATION 2
5α-Hydroxy-3α-(tetrahydropyran-2-yloxy)-2β-(benzylmethyl)-cyclopentyl-1-acetaldehyde, γ-lactol.
Refer to Chart B (conversion of Formula XXII to XXIII).
A 1-neck one liter flask equipped as in Preparation 1 is charged with 13.0 g (0.0375 moles) of the Formula XXII compound from Preparation 1 and 450 ml of toluene. The mixture is degassed and flushed with nitrogen, cooled to -78° C., and 43 ml of DIBAL (diisobutylaluminum hydride) in toluene is added. The reaction is stirred for 35 min at -78° C. TLC analysis indicates that the reaction is complete. To this reaction is added 200 ml of 1:1 tetrahydrofuran (THF):water. The reaction is warmed to room temperature, diluted with brine, and extracted twice with diethyl ether. The organic phases are washed twice with a 1:1 mixture of 1 normal sodium hydroxide:water, twice with brine, and dried over magnesium sulfate. The mixture is concentrated in vacuo to yield 13.09 g of the titled product is a pale yellow oil.
NMR (CDCl 3 , TMS) peaks are as follows: δ 1.30-2.50 (complex m, 13H); 3.21-4.28 (m, 5H); 4.35-5.03 (m, 2H); 4.53 (s, 2H); 5.27-5.74 (m, 1H); and 7.40 (s, 5H).
IR (ν max; film) peaks are as follows: 3375 (broad s), 2935, 2850, 1440, 1350, 1190, 1110, 1018, 910, 730, and 690 cm -1 .
TLC analysis reveals: Rf=0.28 in 1:1 ethyl acetate-hexane.
PREPARATION 3
5α-Hydroxy-3α-(tetrahydropyran-2-yloxy)-2β-(benzyloxymethyl)-1α-[1-(methoxycarbonyl)-cis-4-hexen-6-yl]-cyclopentane
Refer to Chart B (conversion of Formula XXIII to XXIV).
A 3-neck 500 ml flask equipped with addition funnel and nitrogen inlet is charged with 6.62 g (0.166 mole) of sodium hydride (which has been rinsed twice with hexane) and 200 ml of dry DMSO (dimethylsulfoxide). The mixture is heated at 65° C. for 1.5 hr, cooled to room temperature, and 36.7 g (0.0828 mole) of 4-carboxybutyltriphenylphosphonium bromide is added dropwise while the mixture is cooling in a water bath. The red mixture is stirred 1/2 hr at room temperature. A solution of 7.21 g (0.0207 mole) of the Formula XXIII compound from Preparation 2 in 15 ml of tetrahydrofuran (THF) is added dropwise. TLC analysis indicates the reaction is complete after 1 hr. The reaction is allowed to stir a total of 2.5 hr, and is quenched with water, diluted with brine, and extracted with diethyl ether. The organic layer is washed in sodium hydroxide, and all aqueous phases are combined, acidified to pH 3 with cold hydrochloric acid, and extracted twice with ethyl acetate. The organic phases are washed with brine, dried, and concentrated in vacuo to yield crude 5α-hydroxy-3α-(tetrahydropyran-2-yloxy)-2β-(benzyloxymethyl)-1α-(1-carboxy-cis-4-hexen-6-yl)-cyclopentane (Formula XXIV; N 1 =COOH). This product is chromatographed over 500 g of silica gel eluted with a 40:60 mixture of ethyl acetate:Skellysolve B (SSB). Fractions of 40 ml are collected after an initial 600 ml fraction. Fractions 25-80 yield 9.12 g of the above Formula XXIV (N 1 =COOH) compound. Spectual analysis of this compound is as follows:
NMR (CDCl 3 ; TMS) peaks are: δ 1.07-2.48 (m, 18H); 3.05-4.33 (m, 8H), 4.51 (s, 2H); 4.57-4.77 (m, 1H); 4.24-5.60 (m, 2H); 7.33 (s, 5H).
IR (ν max; film) peaks are: 3450, 2940, 2840, 1705, 1440, 1330, 1190, 1010, 735, and 675 cm -1 .
9.12 g (0.0211 moles) of the product of the previous paragraph, 36.8 ml (0.0211 moles) of diisopropylethylamine, and 10.5 ml (0.169 moles) of methyl iodide are added to 300 ml of acetonitrile. The reaction mixture was stirred at 25° C. for 24 hr, diluted with brine and extracted with ethyl acetate. The organic layer was washed with 0.5 M potassium bisulfate-brine (1:1) and dried over magnesium sulfate to yield 8.8 g of the titled product. TLC analysis of this product reveals an Rf of 0.23 in a 35:65 mixture of ethyl acetate:Skellysolve B (a commercial mixture of essentially n-hexane with a boiling point of approximately 60°-68° C.).
PREPARATION 4
5-Oxo-3α-(tetrahydropyran-2-yloxy-2β-(benzyloxymethyl)-1α-[1-(methoxycarbonyl)-cis-4-hexen-6-yl]-cyclopentane
Refer to Chart B (conversion of Formula XXIV to XXV).
A 3-necked 500 ml flask equipped with nitrogen inlet is charged with 8.8 g (0.01971 mole) of the Formula XXIV compound from Preparation 3 in 200 ml of dry acetone is degassed and flushed twice with nitrogen, cooled to -25° C. 9.8 ml of 2.67 molar Jones reagent is added dropwise. TLC analysis indicates complete conversion after 45 min at -20° to -30° C. 12 ml of isopropanol are added and the mixture is stirred for approximately 10 min at -25° C., diluted with brine, and extracted three times with diethyl ether. The ether layers are washed with sodium bicarbonate (three times), brine (twice), and dried over magnesium sulfate. The mixture is concentrated in vacuo to yield the crude titled product. This mixture is dissolved in methylene chloride and eluted over 300 g of silica gel using a 35:65 mixture of ethyl acetate:hexane. An initial 340 ml fraction is collected and then 40 ml fractions are collected. Fractions 11-25 yield 7.20 g of the pure titled product.
NMR (CDCl 3 , TMS) peaks are as follows: δ 1.27-2.50 (m, 18H); 3.26-3.83 (m, 5H); 3.65 (s, 3H); 4.40-4.65 (m, 1H); 4.49 (s, 2H); 5.20-5.43 (m, 2H); and 7.33 (s, 5H).
IR (ν max; film) peaks are as follows: 2930, 2850, 1738, 1458, 1432, 1360, 1317, 1200, 1150, 1075, 1035, 970, 910, 870, 820, 740, and 700 cm -1 .
TLC analysis reveals: Rf=0.39 in 35:65 ethyl acetate-hexane.
PREPARATION 5
5-Oxo-2β-(benzyloxymethyl)-1α-[1-(methoxycarbonyl)-cis-4-hexen-6-yl]-3-cyclopentene
Refer to Chart B (conversion of Formula XXV to XXVI).
A. 5-Oxo-3α-hydroxy-2β-(benzyloxymethyl)-1α-[methoxycarbonyl)-cis-4-hexen-6-yl]-cyclopentane
7.2 g (0.0162 mole) of the Formula XXV compound from Preparation 4 was added to 200 ml of a 20:10:3 solution of acetic acid:water:tetrahydrofuran. The reaction mixture is stirred at 25° C. for 18 hr and at 45° C. for 2 hr, diluted with brine and extracted with ethyl acetate. The organic phase is washed with water twice, sodium bicarbonate twice and brine. The organic phase is then dried over sodium sulfate to yield the crude titled compound. The crude sample is applied to a 300 g silica gel column and eluted with 35:65 solution of ethyl acetate:Skellysolve B. After an initial 340 ml fraction, 40 ml fractions were collected. Fractions 25-70 contained the titled product.
NMR (CDCl 3 , TMS) peaks are as follows: δ 1.44-2.69 (m, 12H); 3.10 (s, 1H); 3.34-4.40 (m, 3H); 3.63 (s, 3H); 4.55 (s, 2H); 5.22-5.50 (m, 2H); and 7.33 (s, 5H).
IR (ν max; film) peaks are as follows: 3440, 2890, 2860, 1740, 1490, 1450, 1430, 1360, 1310, 1150, 1090, 1070, 1030, 910, 860, 740, and 700 cm -1 .
TLC analysis reveals: Rf=0.15 in 35:65 ethyl acetate-Skellysolve B.
B. 5-Oxo-2β-(benzyloxymethyl)-1α-[1-(methoxycarbonyl)-cis-4-hexen-6-yl]-3-cyclopentane
To a stirred solution of 4.79 g (0.0133 mole) of the product of the previous paragraph in 95 ml of methylene chloride, which has been degassed and flushed with nitrogen and cooled to 0° C. is added 10.7 ml of pyridine followed by 9.3 ml of trifluoroacetic anhydride. The reaction is stirred 20 min at 0° C. 18.5 ml of triethylamine are added dropwise. The reaction is stirred for 20 min at 0° C. Then 18.6 ml of triethylamone are added. The reaction is stirred at 0° C. for 2 hr and at room temperature for 1/2 hr and at 40° C. for 1 hr. The reaction is diluted with brine and cold 0.5 M potassium bisulfate, and extracted with ether twice. Me ether layers are washed with 0.5 M potassium bisulfate, brine, sodium bicarbonate, brine and dried over magnesium sulfate. The ethereal solution is concentrated in vacuo and the residue is applied to a 400 g silica gel column packed and eluted with a 25:75 mixture of ethyl acetate-Skellysolve B. After an initial 400 ml fraction is collected, 40 ml fractions are collected. Fractions 29-70 contain 5.0 g of the titled product.
NMR (CDCl 3 , TMS) peaks are as follows: δ 0.96-2.55 (m, 10H); 3.15-3.73 (m, 2H); 3.64 (s, 3H); 4.54 (s, 2H); 5.26-5.54 (m, 2H); 6.20 (dd, J=2 and 6 Hz, 1H); 7.32 (s, 5H); 7.67 (dd, J=2 and 6 Hz, 1H).
IR (ν max; film) peaks are as follows: 2925, 2850, 1725, 1700, 1645, 1590, 1450, 1430, 1350, 1195, 1140, 1010, 870, 740, and 700 cm -1 .
TLC analysis reveals: Rf=0.38 in 35:65 ethyl acetate-Skellysolve B.
PREPARATION 6
5-Oxo-2β-(benzyloxymethyl)-1α-[1-(methoxycarbonyl)-cis-4-hexen-6-yl]-3α-methyl-cyclopentane
Refer to Chart B (conversion of Formula XXVI to XXVII).
To an oven-dried 3-neck 500 ml flask equipped with dropping funnel and nitrogen inlet is charged 4.72 g (0.02476 mole) of cuprous iodide and 200 ml of diethyl ether. The mixture is cooled to 0° C. and 38.1 ml of 1.3 molar methyl lithium in diethyl ether is added dropwise. The reaction turns from a dark yellow to a colorless solution. 4.24 g (0.0124 mole) of the Formula XXVI compound from Preparation 5 in 40 ml of diethylether is added. The reaction is stirred for 15 min at 0° C. and quenched with 13 ml of acetic acid, diluted with brine, and extracted with diethyl ether. The ether layers are washed with saturated sodium carbonate four times, and again with brine. The mixture is dried over magnesium sulfate and concentrated in vacuo. The crude product is applied to 400 g of silica gel and eluted with 20:80 ethyl acetate-Skellysolve B. After an initial 300 ml fraction, 40 ml fractions are collected. The titled product is found in fractions 27-45.
NMR (CDCl 3 , TMS) peaks are as follows: δ 1.10 (d, 3H); 1.30-2.49 (m, 13H); 3.57 (d, 2H); 3.65 (s, 3H); 4.50 (s, 2H); 5.17-5.42 (m, 2H); 7.33 (s, 5H).
IR (ν max; film) peaks are as follows: 2950, 2850, 1730, 1450, 1430, 1355, 1240, 1200, 1150, 1090, 740, and 700 cm -1 .
TLC analysis reveals: Rf=0.24 in 25:75 ethyl acetate-Skellysolve B.
PREPARATION 7
5α-Hydroxy-3α-methyl-2β-(benzyloxymethyl)-1α-[methoxycarbonyl)-cis-4-hexen-6-yl]-cyclopentane
Refer to Chart B (conversion of Formula XXVII to XXVIII).
An oven-dried 3-necked 100 ml flask equipped with addition funnel and nitrogen inlet is charged with 12.9 ml of L-Selectride®, and cooled to -78° C. 3.09 g (18.6 mmole) of the Formula XXVII compound from Preparation 7 in 12 ml of tetrahydrofuran is added dropwise. The reaction is stirred 30 min at -78° C. TLC analysis indicates that the reaction is complete. 3.1 ml of 1 N sodium hydroxide and 3.1 ml of 30% hydrogen peroxide are added dropwise while the reaction is maintained at 0° C. The reaction is stirred 15 min at 0°, diluted with water, and extracted with diethyl ether. The ether layers are washed with 1 N sodium hydroxide, and 3 times with brine. The ether phase is dried over magnesium sulfate and concentrated in vacuo. The crude product is applied in methylene chloride to a 400 g silica gel column. The column is eluted with 24% ethyl acetate:74% Skellysolve B: 1% acetic acid. After an initial 450 ml fraction, 40 ml fractions were collected. The product was located in fractions 20-35.
NMR (CDCl 3 , TMS) peaks are as follows: δ 1.10 (d, 3H); 1.17-2.45 (m, 14H); 3.50 (d, 2H); 3.71 (s, 3H); 4.05-4.27 (m, 1H); 4.57 (s, 2H); 5.16-5.67 (m, 2H); and 7.37 (s, 5H).
IR (ν max; film) peaks are as follows: 3450, 2925, 2850, 1730, 1485, 1455, 1440, 1360, 1317, 1245, 1205, 1100, 1025, 740, and 700 cm -1 .
TLC analysis reveals: Rf=0.14 in 1:3 ethyl acetate-Skellysolve B.
PREPARATION 8
5α-Hydroxy-3α-methyl-2β-(benzyloxymethyl)-1α-[1-(methoxycarbonyl)-5-oxohex-6-yl]-cyclopentane
Refer to Chart B (conversion of Formula XXVIII to XXIX).
A. (15,5R)-oxa-3ξ-[1-(methoxycarbonyl)-4ξ-iodbut-1-yl]-6β-(benzyloxymethyl)-7α-methyl-bicyclo[3.3.0]octane
A 1 liter 1-necked flask equipped with nitrogen inlet was charged with 220 g (6.629 mmole) of the Formula XXVIII compound from Preparation 7. 100 ml of methylene chloride and 1.4 g (13.16 mmole) of sodium bicarbonate are added. The solution is cooled to 0° C. and 1.59 g of iodine is added over 1 min. The mixture is stirred for 50 min at 0° C. and is diluted with 65 ml of 10% sodium sulfite. The organic layer is separated, and the aqueous layers are reextracted with chloroform. The combined organic layers are washed with brine and concentrated in vacuo to yield crude titled product. This product is applied to 150 g of silica gel, packed and eluted with 25:75 ethyl acetate-Skellysolve B. After a 200 ml fraction, 20 ml fractions are collected. Fractions 10-21 contain the titled product.
NMR (CDCl 3 , TMS) peaks are as follows: δ 1.01 (d, 3H); 1.17-2.68 (m, 14H); 3.22-4.73 (m, 4H); 3.70 (s, 3H); 4.51 (s, 2H); and 7.34 (s, 5H).
IR (ν max; film) peaks are as follows: 2940, 2850, 1730, 1485, 1455, 1365, 1200, 1160, 1100, 730, and 700 cm -1 .
TLC analysis reveals: Rf=0.22 and 0.24 (isomers at C-5) in 25:75 ethyl acetate-Skellysolve B.
B. 5α-Hydroxy-3α-methyl-2β-(benzyloxymethyl)-1α-[1-(methoxycarbonyl)-5-oxohex-6-yl]-cyclopentane
To a solution of 2.45 g (5.037 mmole) of the product of the previous paragraph in 125 ml of toluene is added 5 ml of DBN. The reaction is stirred under nitrogen for 48 hr at room temperature and then heated to 40° C. for 4 hours and at room temperature for 16 hr. The reaction is diluted with brine, extracted with ethyl acetate twice, and the combined extracts are washed with brine, 0.5 molar potassium bisulfate, saturated aqueous sodium bicarbonate, and again with brine. The extract is finally dried over sodium sulfate and concentrated in vacuo to afford a pale green oil. This oil is dissolved in 50 ml of acetone and reacted with 10 ml of water and 1 ml of 1 N hydrochloric acid. After 1.5 hr the reaction mixture is diluted with brine and extracted with ethyl acetate. The extract is washed with brine, dried over magnesium sulfate to give the crude titled product. The product is applied to 150 g of silica gel, packed and eluted with 35:65 ethyl acetate-Skellysolve B. 20 ml Fractions were collected, and fractions 31-63 contain the titled product.
NMR (CDCl 3 , TMS) peaks are as follows: δ 1.03 (d, 3H); 1.13-2.74 (m, 16H); 3.28-3.52 (m, 2H); 3.64 (s, 3H); 4.27-4.68 (m, 3H); and 7.31 (s, 5H).
TLC analysis reveals: Rf=0.29 in 25:75 ethyl acetate-Skellysolve B.
PREPARATION 9
(15,5R)-2-Oxa-3ξ-methoxy-3ξ-[1-(methoxycarbonyl)-but-4-yl]-6β-hydroxymethyl-7α-methyl-bicyclo[3.3.0]octane
Refer to Chart B (conversion of Formula XXIX to XXX).
A mixture of 0.79 g (2.098 mmole) of the Formula XXIX compound from Preparation 8, 20 ml of methanol, and a total of 300 mg of a 10% palladium on carbon catalyst are hydrogenated for approximately 2 hr. A total of 54.2 ml of hydrogen are absorbed. The calculated uptake is 52 ml. The product is filtered through Celite® and concentrated in vacuo. The crude residue is diluted with 30 ml of methanol and a catalytic amount of p-toluene sulfonic acid and stirred for 1 hr at room temperature under nitrogen, when triethylamine is added. The mixture is concentrated in vacuo, and applied to a 130 g silica gel column packed and eluted with a 1:1 mixture of ethyl acetate:Skellysolve B containing 1% triethylamine. Fractions 26 to 60 are combined and yield the titled product.
NMR (CDCl 3 , TMS) peaks are as follows: δ 0.80-2.66 (m, 19H); 3.23 (s, 3H); 3.33-3.82 (m, 2H); 3.73 (s, 3H); and 4.46-4.57 (m, 1H).
TLC analysis reveals: Rf=0.22 and 0.26 (isomers at C-3) in 50:50 ethyl acetate-Skellysolve B.
PREPARATION 10
(11R)-6-Oxo-11-deoxy-11,16,16-trimethyl-15-dehydro-PGF 1 α, methyl ester, methyl acetal
Refer to Chart B (conversion of Formula XXX to XXXI).
A 250 ml 3-necked flask is charged with 30 ml of tetrahydrofuran, cooled to 0° C., and 0.18 g of a 60% oil dispersion of sodium hydride is added. 1.1 g (4.52 mmole) of dimethyl 2-oxo-3,3-dimethylheptylphosphonate in 5 ml of tetrahydrofuran is added. The reaction is stirred for 5 min at 0° C. and 1 hr at room temperature and then cooled to 0° C.
A 250 ml 3-necked flask equipped with nitrogen inlet is charged with 80 ml of methylene chloride and 2.19 ml of pyridine (27.12 mmole) and cooled to 0° C. With vigorous stirring is added 1.36 g of chromium trioxide and the mixture is stirred at room temperature for 30 min. 0.68 g (2.26 mmoles) of the Formula XXX alcohol from Preparation 9 is added in a small amount of methylene chloride. The reaction is stirred at room temperature for 45 min and then cooled to 0° C. The mixture is decanted through a powder funnel with a glass wool plug into the phosphonate anion prepared above. Reaction is stirred at room temperature for 2 hr when an additional 4.52 mmole of phosphonate anion is added to the solution. After 1 additional hr no aldehyde remains. The reaction is poured into a 1:1 brine saturated sodium carbonate solution and extracted with ethyl acetate three times. The organic layers are combined, washed with brine, dried over sodium sulfate, and concentrated in vacuo to afford the crude titled product. The crude product is applied in Skellysolve B to a 130 g silica gel column packed in 15% ethyl acetate:84% Skellysolve B:1% triethylamine. The sample is eluted with 20% ethyl acetate:79% Skellysolve B:1% triethylamine. 20 ml Fractions are collected. The titled product is located in fractions 20-37.
NMR (CDCl 3 , TMS) peaks are as follows: δ 0.87 (d, 3H); 1.10 (s, 6H); 0.64-2.60 (m, 24H); 3.09 and 3.12 (2s, 3H, isomers at C-6); 3.62 (s, 3H); 4.31-4.64 (m, 1H); and 6.45-6.86 (m, 2H).
IR (ν max; film) peaks are as follows: 2950, 2860, 1735, 1665, 1618, 1460, 1370, 1315, 1240, 1170, 1045 and 985 cm -1 .
TLC analysis reveals: Rf=0.41 in 25:75 ethyl acetate-Skellysolve B.
PREPARATION 11
(11R,5RS)-6-Oxo-11-deoxy-11,16,16-trimethyl-PGF 1 α, methyl ester, 15-acetate
Refert to Chart B (conversion of Formula XXI to XXXII).
A. (11R, 15RS)-6-Oxo-11-deoxy-11,16,16-trimethyl-PGF 1 α, methyl ester, methyl acetal
A mixture of 0.8 g (1.89 mmole) of the Formula XXXI compound from Preparation 10 in 15 ml of methanol is cooled to 0° C. 0.14 g (3.69 mmole) of sodium borohydride is added. The solution is stirred for 30 min at -20° C. when TLC analysis reveals no starting material remaining. The reaction is poured into brine, extracted twice with ethyl acetate, and the combined organic layers are washed with brine, dried over magnesium sulfate and concentrated in vacuo to yield 0.8 g of the crude titled product.
NMR (CDCl 3 , TMS) peaks are as follows: δ 0.51-2.57 (m, 3.4H); 3.17 and 3.20 (2s, 3H, isomers at C-6); 3.70 (s, 3H); 3.67 (m, 1H); 4.27-4.73 (m, 1H); and 5.33-5.61 (m, 2H).
TLC analysis reveals: 0.20, 0.24 and 0.28 (isomers at C-6 and C-15) in 25:75 ethyl acetate-Skellysolve B.
B. (11R, 15RS)-6-Oxo-11-deoxy-11,16,16-trimethyl-PGF 1 α, methyl ester, 15-acetate
Refer to Chart B (conversion of Formula XXI to XXXII).
A mixture of 0.8 g (1.89 mmole) of the product of the previous paragraph, 12 ml of pyridine and 1.2 ml of acetic anhydride are stirred under nitrogen for 1 hr. A catalytic amount of 4-dimethylaminopyridine is added. The reaction is stirred an additional 4 hr when TLC analysis indicates a complete reaction. The reaction is diluted with 0.5 molar potassium bisulfate and extracted twice with ethyl acetate. The combined extracts are washed with 0.5 molar potassium bisulfate, brine, and dried over magnesium sulfate and concentrated in vacuo to afford the C-15 protected methyl acetal 6-methoxy compound. The work-up is completed and the crude product is diluted with 30 ml of a 20:10:3 water:acetic acid:THF solution and stored in a freezer (-20° C.) overnight. The reaction is diluted with brine and extracted with ethyl acetate. The combined organic layers are washed with saturated sodium bicarbonate three times and once with brine, and dried over magnesium sulfate. Finally the mixture is concentrated in vacuo and azeotroped with toluene to remove excessive acetic acid, yielding the titled product.
NMR (CDCl 3 , TMS) δ 0.53-2.64 (m, 37H); 3.68 (s, 3H); 4.17-4.74 (m, 1H); 4.89-5.10 (m, 1H); and 5.28-5.53 (m, 2H).
EXAMPLE 1
(11R)-6-Oxo-11-deoxy-11,16,16-trimethyl-PGE 1 , methyl ester, 15-acetate and (11R,15S)-6-oxo-11-deoxy-11,16,16-trimethyl-PGE 1 , methyl ester, 15-acetate
Refer to Chart B (conversion of Formula XXXII to XXXIII).
To a solution of 0.8 g (1.89 mmole) of the Formula XXXII compound from Preparation 11 in 25 ml of acetone which has been cooled to -25° C. in 100 ml 3-necked flask is added 0.94 ml (2.52 mmole) of Jones reagent. The reaction is stirred for 1 hr at -25° C. when isopropanol (approximately 1.3 ml) is added to quench the reaction. The reaction is stirred for 10 min at -25° C., diluted with brine, extracted with diethyl ether three times. The ether layers are washed with sodium bicarbonate three times, brine three times, and dried over magnesium sulfate. Finally the mixture is concentrated in vacuo to yield the crude titled products. The crude products were purified by high performance liquid chromatography eluting with 25:75 ethyl acetate-hexane (20 ml fractions). The less polar isomers (Formula XXXIII: M 1 =--(CH 2 ) 3 --;k N 1 =CO 2 CH 3 ; R 1 =CH 3 , E 1 =trans--CH═CH; Q 1 =α-OCOCH 3 , β-H; L 1 =CH 3 , CH 3 ; R 2 =--(CH 2 ) 3 CH 3 ) was isolated in fractions 63-86 and exhibited NMR absorbances (CDCl 3 , TMS) at δ 0.78 and 0.82 (2s, 6H); 1.01 (d, 3H); 1.08-2.62 (m, 24H); 1.98 (s, 3H); 3.59 (s, 3H); 4.88-5.01 (m, 1H); and 5.32-5.48 (m, 2H).
IR (ν max; film) peaks are as follows: 2955, 2875, 1730, 1450, 1430, 1240, 1165, 1010, 970, and 785 cm -1 .
TLC analysis reveals: Rf=0.19 in 25:75 ethyl acetate-hexane.
The more polar isomer (Formula XXXIII; Q 1 =α-H, β-OCOCH 3 , is isolated in fractions 87-107 and exhibits NMR absorbances (CDCl 3 , TMS) at: δ 0.79 (s, 6H); 1.02 (d, 3H); 1.08-2.64 (m, 24H); 1.98 (s, 3H); 3.40 (s, 3H); 4.87-5.02 (m, 1H); 5.34-5.47 (m, 2H).
IR (ξ max; film) peaks are as follows: 2940, 2875, 1730, 1460, 1430, 1365, 1240, 1165, 1025, and 970 cm -1 .
TLC analysis reveals: Rf=0.16 in 25:75 ethyl acetate-hexane.
EXAMPLE 2
(11R)-6-Oxo-11-deoxy-11,16,16-trimethyl-PGE 1
A solution of 0.36 g of the less polar isomer from Example 1 in 10 ml of 5% potassium hydroxide in 9:1 methanol-water is stirred at room temperature under nitrogen for 4 hr when TLC analysis indicates a complete reaction. The reaction is diluted with brine, acidified to pH 2 with 0.5 M potassium bisulfate, and extracted twice with ethyl acetate. The combined organic layers are washed with brine, concentrated in vacuo to afford the crude titled product. The crude product is applied in methylene chloride to a 10 g acid-washed silica gel column, packed and eluted with 40:60 ethyl acetate-hexane. 20 ml Fractions were collected, and fractions containing the pure titled compound were combined to give 0.298 g.
NMR (CDCl 3 , TMS) peaks are as follows: δ 0.77 and 0.83 (2s, 6H); 0.87-2.79 (m, 27H); 3.80 (d, 1H); 4.47 (broad s, 2H); and 5.42-5.62 (m, 2H).
IR (ν max film) peaks are as follows: 3450, 2950, 2870, 1735, 1470, 1440, 1405, 1370, 1275, 1247, 1095, 1015, and 975 cm -1 .
TLC analysis reveals: Rf=0.20 in 40% ethyl acetate: 59% Skellysolve B: 1% acetic acid.
Mass spectral analysis reveals the following:
Calcd for C 22 H 39 O 5 Si: 439.2336. Found: 439.2350
Other ions are observed at m/e 73, 57, 75, 111, 55, 129, 231, 97, 182, and 175. ##STR1## | The present invention provides novel (11R)-11-deoxy-11-alkyl-6-oxo-prostaglandins which are useful for curing and preventing duodenal ulcers and for preventing or treating gastrointestinal cell damage caused by the use of other pharmacological agents. | 2 |
BACKGROUND OF THE INVENTION
The invention relates to improvements in suspended ceiling grid construction and, in particular, to improvements in connector clips for ceiling grid members.
PRIOR ART
Suspended ceiling grid members or runners typically comprise relatively long main runners and shorter cross runners. Both types of grid runners have connectors to join their ends to the ends of like members to construct a ceiling expanse of greater size than the length of individual main or cross runners. These end connectors, as the industry has advanced, are typically separate clip elements permanently attached to the grid runners themselves. The end connectors or clips are metal stampings, ordinarily of steel, formed with features that enable them to couple with identical units when one connector is pushed endwise into a lap joint with an opposing end connector. Depending on the clip design, the clips may directly abut or may have runner web areas disposed between them. In general, the features stamped or otherwise formed into a connector that establish a connection are a lateral projection and the edge of a hole. The projection of one connector is received in the hole of the opposing connector and, vise versa, the projection of the opposing connector is received in the hole of the one connector. The result is a joint with two locks. In practice, a connection may fail under tension at a force level substantially below the design or normally expected capacity of the joint. This can occur when the joined connectors slip sideways and disconnect one lock engagement resulting in a severe reduction in the load capacity of the joint.
SUMMARY OF THE INVENTION
The invention provides an end connector clip for suspended ceiling grid runners with improved clip-to-clip locking action. The improved locking function, in accordance with the invention, is achieved by orienting the locking surfaces with an angle relative to the plane of the clip body proper greater than what results from conventional practice. A preferred manner of forming the inventive locking surfaces is by increasing the clearance between the punch and die elements that create the locking surfaces. This technique, it has been found, develops an orientation of a locking surface that, in use, counteracts forces that tend to laterally separate mating locking surfaces of a pair of coupled clips which otherwise could result in a major loss of retention force. Ideally, the inventive technique is applied to both a locking projection and a projection receiving area of the clip.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates portions of grid members, in the conventional form of inverted tees, for suspending ceiling panels;
FIG. 1A is an enlarged fragmentary perspective view of the locking surfaces of a grid member end connector or clip;
FIG. 2 is a side elevational view of the clip and end portion of a grid tee;
FIG. 3A is a diagrammatic presentation of the locking areas of the clip;
FIG. 3B is a diagrammatic presentation of tooling, in vertical alignment with FIG. 3A , used according to the invention to make the locking surfaces of the clip; and
FIG. 3C shows a cross-section of portions of joined clips in a longitudinal plane transverse to the planes of the main body of the clips.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings and in particular to FIG. 1 , portions of generally conventional suspended ceiling grid runners, in the form of tees 10 , 11 , are depicted. A main tee 10 has a vertically oriented slot 12 , one of many at regularly spaced intervals along its length in a central web 13 . End portions of opposed cross tees 11 are positioned in line with the main tee slot. The tees 10 , 11 are preferably roll-formed from light gauge sheet metal stock as is customary. The main tee 10 can have a typical length of 10 or 12 feet or metric equivalent and the cross tees 11 can have lengths of 4 feet, 2 feet, and 1 foot, or metric equivalent. The cross tees 11 have identical end connectors or clips 14 fixed to their ends such as by staking portions of the tee sheet metal stock through holes provided in the connectors.
The illustrated connectors 14 are of the general type disclosed in U.S. Pat. Nos. 5,517,796 and 5,761,868, the disclosures of which are incorporated herein by reference. Typically, the connectors 14 are stamped from steel sheet stock that is stronger and harder than that of the tees 10 , 11 . The numeral 16 indicates the forward end of a connector 14 .
When two connectors 14 are positioned from opposite sides of the main tee 10 into a common slot 12 , they form a joint of their respective cross tees 11 by establishing a double connector-to-connector lock. The relationship between a pair of joined connectors 14 is analogous to a handshake. More specifically, when clips 14 are joined they lap one another, preferably in direct abutment. The clips 14 are locked together when a lock area 17 of one clip 14 snaps or is otherwise received behind a forward one of two opposing projections 18 , 19 stamped into the body of the other clip 14 . This same action occurs where the corresponding lock area 17 of the other clip is received behind the forward projection 18 of the one clip 14 . With both sets of lock areas 17 and projections 18 engaged, a double lock clip connection is established. The lock area 17 and projection 18 interengagement serves to resist tensile loads on the associated cross tees 11 tending to separate them and under proper conditions can sustain relatively high forces.
Experience reveals that a joint between a pair of clips 14 will separate under relatively low forces if one of a set of locking area 17 and projection 18 slips laterally, i.e. perpendicular to the planes of the clips 14 . This can leave only one lock set between a lock area 17 and projection 18 .
Such sidewise slipping may result, inter alia, from variations in the clip material, the clip manufacturing process, deviation from an ideal clip shape, installation technique, and eccentric forces imposed on the joined clips or combinations of these factors.
The failure of a lock set by lateral movement between lock area 17 and projection 18 is related to the orientation of their respective contacting edges, designated 21 , 22 . The closer these edge surfaces 21 , 22 are to lying in planes that are perpendicular or are obtuse to the planes of the clip bodies, the greater the risk that they will separate laterally. Locking surfaces with such orientations have little or no resistance to forces tending to laterally separate the clips 14 and when the angle is measurably obtuse a reaction force is developed by the locking surfaces in response to a tensile force between the tees that may actually cause the clips to spring laterally apart and out of contact. A locking edge surface of a projection corresponding to the projection 18 when produced with conventional practice is prone to assume an obtuse angle relative to the plane of the clip. When this edge surface is originally formed by stamping a hole in the plane of the original sheet stock forming the clip it can be slightly acute, i.e. less than 90 degrees. However, when the projection is thereafter formed out of the plane of the main part of the clip body, the edge surface can be drawn into an obtuse orientation.
FIGS. 3A and 3B are diagrams projected vertically relative to one another illustrating aspects of the invention. In FIG. 3A , the lock area 17 is rearwardly bound by a locking area edge surface 21 . Also in FIG. 3A , the eventual projection 18 and an associated lock edge 22 are indicated.
As shown in FIG. 3B , punch elements 26 , 27 cooperating with die sections 28 , 29 form holes 31 , 32 , respectively. A forward edge or boundary of the hole 31 is the lock area edge 21 and a forward edge of a bow tie shaped hole 32 forms the projection lock edge 22 .
In FIG. 3C , the forward ends of a pair of mating clips 14 are diagrammatically illustrated. The images of FIGS. 3A and 3B correspond to the clip 14 on the left in FIG. 3C .
FIG. 3B shows, on an exaggerated scale, a high degree of clearance between the punches 26 , 27 and die openings 33 , 34 at locations corresponding to the lock edges 21 , 22 . As a general rule in the metal stamping industry, a punch is slightly smaller than the hole or spaced from the die or cutting edge it operates with. Typically, the clearance between the punch and die at a side of a hole is about 8% to 10% of the thickness of the material being pierced. A hole punched in a metal sheet by a punch and die generally has a diameter or hole size at the punch side equal to the punch and at the die hole side equal to the diameter or size of the die hole. This means that the punched hole, if round, is actually slightly tapered, i.e. conical, across the thickness of the sheet material or if the hole has a different configuration its walls are tapered from the size of the punch to the size of the die hole or die edge.
It has been discovered that by significantly departing from traditional practice and increasing the clearance between the punch elements 26 , 27 , and die openings 33 and 34 , the angularity of the lock edges 21 , 22 can be advantageously increased. For example, the clearance between the punch elements 26 and 27 and their respective die openings 33 , 34 corresponding to the lock edges 21 , 22 can be about 25% of the thickness of the sheet metal used to form the connector or clip 14 . The illustrated clip 14 can be formed of 0.015/0.017 inch high tensile steel (160 KSI), stress relieved or type 301 / 302 stainless steel, half hard. FIG. 3B shows that the punched or sheared locking edges 21 , 22 are in planes forming acute angles with respect to the side of the clip engaged by the clip 14 R on the right. From the foregoing, it can be understood that the cotangent of the acute angle is the clearance divided by the material thickness. Thus, where the clearance of the prior art was less than 10% of the material thickness, the cotangent of the acute angle would be less than 0.1. With the present invention, the cotangent is substantially greater than 0.1, approaching 0.25, and the angle is substantially less than existing in the prior art. These edge surface angles are retained in the finish form of a clip 14 . In the case of the projection locking surface 22 which is stamped up out of the main plane of the clip body, the angularity, i.e. deviation from perpendicularity to the clip body, may be somewhat diminished but still prominent.
FIG. 3C shows that the angles of the locking edge 21 of the lock or receiving area 17 of one clip and the projection lock edge 22 of the other clip are complementary. Moreover, the angles of these surfaces 21 , 22 create a force component biasing the clips 14 together when a tension force exists in the pair of tees 11 connected to the clips. Consequently, clips 14 with the acutely angled locking edge surfaces 21 , 22 significantly increase the reliability of a connection. The clips 14 are less susceptible to separating at one lock area and then failing at a reduced tension level.
Those skilled in the art will recognize the applicability of the invention to main tee clips such as shown, for example, in U.S. patent application Ser. No. 11/135,058 and U.S. Pat. No. 6,523,313. In the clips shown in U.S. Pat. No. 6,523,313, the material of the tee web is interposed in the area of the locks; nevertheless, the invention has application in such constructions where the connectors, while separated by grid runner stock, are lapped with one another and the locking edges serve the same function as described herein.
It should be evident that this disclosure is by way of example and that various changes may be made by adding, modifying or eliminating details without departing from the fair scope of the teaching contained in this disclosure. The invention is therefore not limited to particular details of this disclosure except to the extent that the following claims are necessarily so limited. | An end clip for joining runners of suspended ceilings by coupling with an identical clip, the clip being stamped from sheet metal stock with lead and trailing ends, a lateral projection and a projection receiving area behind the lead end, the clip being arranged such that when an identical clip oriented in the opposite direction of the clip and caused to laterally overlap the clip the projection of the clip is locked in the receiving area of the identical clip and, vice versa, at least one of the projection and projection receiving area having a rearward facing sheared edge forming an acute angle with the clip plane resulting from being sheared with tooling having a clearance between tooling substantially greater than 10% of the thickness of the sheet from which the clip is stamped. | 4 |
FIELD OF THE INVENTION
[0001] The present invention relates to novel polyheterocyclic based compounds with both linear and macrocyclic structure, especially with tri-heterocyclic functional groups, which are highly potent and effective to inhibit the NS3 protease replication of hepatitis C virus (HCV). The invention also relates to preparation and the uses thereof as HCV inhibitors.
BACKGROUND OF THE INVENTION
[0002] Hepatitis C virus (HCV) is the major causative agent for most cases of non-A, non-B hepatitis. The virus is a single-stranded positive RNA virus in the Flaviviridae family. It includes a nucleocapsid protein (C), envelope proteins (E1 and E2), and several non-structural proteins (NS1, NS2, NS3, NS4a, NS5a, and NS5b). The NS3 protein possesses serine protease activity and is considered essential for viral replication and infectivity, and the essentiality of the NS3 protease was inferred from the fact that mutations in the yellow fever virus NS3 protease decreased viral infectivity [reference: Chamber et al, Proc. Natl. Acad. Sci. USA 87, 8898-8902 (1990).
[0003] So far, HCV infection is one of major human health problems since HCV infection leads to chronic liver disease such as cirrhosis and hepatocellular carcinoma. Due to the fact that the number of HCV infected individuals is estimated 2-15% of the world's population while no any effective vaccines or therapeutic agents are available to control or cure HCV [reference: WO 89/04669; Lavanchy, J. Viral Hepatitis, 6, 35-47 (1999); Alter, J. Hepatology, 31 (Suppl. 1), 88-91 (1999); and Alberti et al, J. Hepatology, 31 (Suppl. 1), 17-24 (1999)].
[0004] It has been demonstrated that mutations at the active site of the HCV NS3 protease completely inhibited the HCV infection in chimpanzee model [reference: Rice et al, J. Virol. 74 (4) 2046-51 (2000)]. Furthermore, the HCV NS3 serine protease has been found to facilitate proteolysis at the NS3/NS4a, NS4a/NS4b, NS4b/NS5a, NS5a/NS5b junctions and is thus responsible for generating four viral proteins during viral replication [reference: US 2003/0207861]. Consequently, the HCV NS3 serine protease enzyme is an attractive and effective target to develop new inhibitors for HCV infection. So far, there are different kinds of potential NS3 HCV protease inhibitors reported by global research institutes and pharmaceuticals, such as WO2010033466, WO2010075127, US20100003214, US20100022578, US20100029715, US20100041889, WO2009134624, WO2009010804, US20090269305, WO2008057209, WO2008057208, WO2007015787, WO2005037214, WO200218369, WO200009558, WO200009543, WO199964442, WO199907733, WO199907734, WO199950230, WO199846630, WO199817679, U.S. Pat. No. 5,990,276, Dunsdon et al, Biorg. Med. Chem. Lett. 10, 1571-1579 (2000); Llinas-Brunet et al, Biorg. Med. Chem. Lett. 10, 2267-2270 (2000); and S. LaPlante et al., Biorg. Med. Chem. Lett. 10, 2271-2274 (2000).
[0005] Currently, due to lack of immunity or remission associated with HCV infection, hepatitis caused by HCV infection is more difficult to treat comparing to other forms of hepatitis. Now, the only available anti-HCV therapies are interferon-a, interferon-a/ribavirin combination, and pegylated interferon-a. However, sustained response rates for interferon-a or interferon-a/ribavirin combination were found to be <50% and patients suffer greatly from side effects of these therapeutic agents [reference: Walker, DDT, 4, 518-529 (1999); Weiland, FEMS Microbial. Rev., 14, 279-288 (1994); and WO 02/18369]. Based on the significant importance for controlling HCV infection, the aim of the present invention is to develop more effective and better-tolerated therapeutic drugs for inhibiting HCV NS3 protease replication.
SUMMARY OF THE INVENTION
[0006] The present invention relates to two classes of novel polyheterocyclic based compounds of the following formulas Ia-Ib with macrocyclic structure and IIa-IIb with linear structure, especially with tri-heterocyclic functional groups, which has been evaluated to be highly potent and effective for inhibiting the NS3 protease replication of hepatitis C virus (HCV). This invention further relates to pharmaceutical compositions comprising one or more of new developed compounds (in a pure form or mixture of stereoisomers, solvates, hydrates, tautomers, prodrugs, or pharmaceutically acceptable salts thereof) and another agent(s) developed as therapeutic drugs for HCV treatment.
[0007] In the first aspect, the present invention provides polyheterocyclic based compounds having the following macrocyclic structure Ia and Ib:
[0000]
[0008] and/or stereoisomers, solvates, hydrates, tautomers, esterification or amidation prodrugs, pharmaceutically acceptable salt, or mixtures thereof,
[0000] wherein:
[0009] m=0, 1 or 2;
[0010] n=0, 1 or 2;
[0011] p=0, 1 or 2;
[0012] q=0, 1 or 2;
[0013] r=0, 1, 2 or 3;
[0014] each dashed line “ ” is, independently, a single bond or double bond;
[0015] wherein when D and E are connected by a single bond, D and E are each, independently, selected from the group consisting of O, S, amino, and —C(Ra)(Rb)-; and R 10 is hydrogen, oxygen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0016] wherein when D and E are connected by a double bond, D and E each, independently, selected from the group consisting of N or —C(Rc)-;
[0017] wherein when E 1 and G are connected by a single bond, E 1 and G are each, independently, selected from the group consisting of O, S, amino, and —C(Ra)(Rb)-; and R 10 is hydrogen, oxygen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0018] wherein when E 1 and G are connected by a double bond, E 1 and G are each, independently, selected from the group consisting of N or —C(Rc)-;
[0019] wherein when the dashed line connecting R 10 to the macrocycle is a double bond, R 10 is O or S;
[0020] wherein when the dashed line connecting R 10 to the macrocycle is a single bond, R 10 is hydrogen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0021] Ra, Rb and Rc are each, independently, selected from the group consisting of hydrogen, halogen atom, cyano, nitro, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, C 2 -C 20 heterocyclic alkoxycarbonyl, C 2 -C 20 heterocyclic aryl, C 1 -C 20 alkylamino, C 2 -C 20 heterocyclic amino, C 6 -C 20 aryl amino, C 1 -C 20 aminocarbonyl, C 1 -C 20 amido, C 1 -C 20 amidocarbonyl, C 1 -C 20 carbonylamino, C 1 -C 20 alkylsulfonamido, C 2 -C 20 heterocyclic sulfonamido, C 6 -C 20 arylsulfonamido, and C 1 -C 20 aminosulfonamido group;
[0022] wherein when r=0, E is nothing, and the D group is directly linked to the E 1 group;
[0023] L is oxygen, sulfur, —S(O)—, —S(O) 2 —, carbonyl, —C(Rb)(Rc)-, —C(Rb)=C(Rc)-, C 1 -C 20 alkoxy, C 2 -C 20 heterocyclyl, C 2 -C 20 heterocyclic alkoxy, —N(Ra)-, C 1 -C 20 aminocarbonyl, C 1 -C 20 alkoxycarbonyl, C 6 -C 20 aryl, C 6 -C 20 aryloxy, or C 6 -C 20 aryloxycarbonyl group, wherein Ra, Rb and Rc are as defined above;
[0024] T is N, O or CH, wherein when T is O, R 1 is not present;
[0025] U is C, S, —S(O)—, P or phosphate;
[0026] W is O or S;
[0027] X is O, S or —NRa-, wherein Ra is defined above;
[0028] Y is N or CH;
[0029] Z is hydroxyl, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkoxy, C 3 -C 20 cycloalkoxy, C 1 -C 20 alkylamino, C 3 -C 20 cycloalkylamino, C 2 -C 20 heterocyclic amino, C 6 -C 20 aryl, C 6 -C 20 arylamino, C 4 -C 20 heteroarylamino, C 1 -C 20 alkyl sulfonamido, C 3 -C 20 cycloalkylsulfonamido, C 6 -C 20 arylsulfonamido, C 1 -C 20 alkoxy sulfonamido, C 3 -C 20 cycloalkoxy sulfonamido, C 1 -C 20 alkylamino sulfonamido, C 3 -C 20 cycloalkylamino sulfonamido, C 6 -C 20 arylamino sulfonamido, C 1 -C 20 uramido, C 1 -C 20 thioureido, C 1 -C 20 phosphate, or C 1 -C 20 borate;
[0030] R 1 and R 2 are each, independently, selected from the group consisting of hydrogen, hydroxyl, amino, C 1 -C 2 alkyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkoxy, C 3 -C 20 cycloalkoxy, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 alkylamino, C 3 -C 20 cycloalkylamino, C 2 -C 20 heterocyclic amino, C 6 -C 20 arylamino, C 1 -C 20 alkoxycarbonylamino, C 6 -C 20 aryloxycarbonylamino, C 1 -C 20 alkylsulfonamido, C 3 -C 20 cycloalkylsulfonamido, C 2 -C 20 heterocyclic sulfonamido, C 6 -C 20 arylsulfonamido, and C 1 -C 20 aminosulfonamido group;
[0031] R 3 , R 4 , R 5 and R 6 are each, independently, selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylamino, C 2 -C 20 heterocyclicamino, C 6 -C 20 aryl, C 6 -C 20 arylamino, C 1 -C 20 alkylsulfonamido, C 2 -C 20 heterocyclic sulfonamido, and C 6 -C 20 arylsulfonamido group; and
[0032] R 7 , R 8 and R 9 are each, independently, selected from the group consisting of hydrogen, cyano, nitro, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, and C 2 -C 20 heterocyclic group.
[0033] In the second aspect, the present invention provides a kind of novel polyheterocyclic based compounds having the following structure IIa and IIb:
[0000]
[0034] and/or its stereoisomers, solvates, hydrates, tautomers, esterification or amidation prodrugs, pharmaceutically acceptable salt, or mixtures thereof.
[0035] wherein:
[0036] p=0, 1 or 2;
[0037] q=0, 1 or 2;
[0038] r=0, 1, 2 or 3,
[0039] each dashed line “ ” is, independently, a single bond or double bond;
[0040] wherein when D and E are connected by a single bond, D and E are each, independently, selected from the group consisting of O, S, amino, and —C(Ra)(Rb)-; and R 10 is hydrogen, oxygen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0041] wherein when D and E are connected by a double bond, D and E each, independently, selected from the group consisting of N or —C(Rc)-;
[0042] wherein when E 1 and G are connected by a single bond, E 1 and G are each, independently, selected from the group consisting of O, S, amino, and —C(Ra)(Rb)-; and R 10 is hydrogen, oxygen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0043] wherein when E 1 and G are connected by a double bond, E 1 and G are each, independently, selected from the group consisting of N or —C(Rc)-;
[0044] wherein when the dashed line connecting R 10 to the macrocycle is a double bond, R 10 is O or S;
[0045] wherein when the dashed line connecting R 10 to the macrocycle is a single bond, R 10 is hydrogen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0046] Ra, Rb and Rc are each, independently, selected from the group consisting of hydrogen, halogen atom, cyano, nitro, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, C 2 -C 20 heterocyclic alkoxycarbonyl, C 2 -C 20 heterocyclic aryl, C 1 -C 20 alkylamino, C 2 -C 20 heterocyclic amino, C 6 -C 20 aryl amino, C 1 -C 20 aminocarbonyl, C 1 -C 20 amido, C 1 -C 20 amidocarbonyl, C 1 -C 20 carbonylamino, C 1 -C 20 alkylsulfonamido, C 2 -C 20 heterocyclic sulfonamido, C 6 -C 20 arylsulfonamido, and C 1 -C 20 aminosulfonamido group;
[0047] wherein when r=0, E is nothing, and the D group is directly linked to the E 1 group;
[0048] W is O or S;
[0049] X is O, S or —NRa-, wherein Ra is defined above;
[0050] Y is N or CH;
[0051] Z is hydroxyl, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkoxy, C 3 -C 20 cycloalkoxy, C 1 -C 20 alkylamino, C 3 -C 20 cycloalkylamino, C 2 -C 20 heterocyclic amino, C 6 -C 20 aryl, C 6 -C 20 arylamino, C 4 -C 20 heteroarylamino, C 1 -C 20 alkyl sulfonamido, C 3 -C 20 cycloalkylsulfonamido, C 6 -C 20 arylsulfonamido, C 1 -C 20 alkoxy sulfonamido, C 3 -C 20 cycloalkoxy sulfonamido, C 1 -C 20 alkylamino sulfonamido, C 3 -C 20 cycloalkylamino sulfonamido, C 6 -C 20 arylamino sulfonamido, C 1 -C 20 uramido, C 1 -C 20 thioureido, C 1 -C 20 phosphate, or C 1 -C 20 borate;
[0052] R 1 and R 2 are each, independently, selected from the group consisting of hydrogen, hydroxyl, amino, C 1 -C 2 alkyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkoxy, C 3 -C 20 cycloalkoxy, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 alkylamino, C 3 -C 20 cycloalkylamino, C 2 -C 20 heterocyclic amino, C 6 -C 20 arylamino, C 1 -C 20 alkoxycarbonylamino, C 6 -C 20 aryloxycarbonylamino, C 1 -C 20 alkylsulfonamido, C 3 -C 20 cycloalkylsulfonamido, C 2 -C 20 heterocyclic sulfonamido, C 6 -C 20 arylsulfonamido, and C 1 -C 20 aminosulfonamido group;
[0053] R 3 , R 4 , R 5 and R 6 are each, independently, selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylamino, C 2 -C 20 heterocyclicamino, C 6 -C 20 aryl, C 6 -C 20 arylamino, C 1 -C 20 alkylsulfonamido, C 2 -C 20 heterocyclic sulfonamido, and C 6 -C 20 arylsulfonamido group; and
[0054] R 7 , R 8 and R 9 are each, independently, selected from the group consisting of hydrogen, cyano, nitro, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, and C 2 -C 20 heterocyclic group; and
[0055] R 11 is hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkylcarbonyl, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 6 -C 20 aryl, C 6 -C 20 arylcarbonyl, C 6 -C 20 aryloxycarbonyl, C 1 -C 20 alkylsulfonamido, C 6 -C 20 arylsulfonamido, C 1 -C 20 aminosulfonamido, C 2 -C 20 heterocyclic group.
[0056] In the third aspect, the present invention provides a kind of novel polyheterocyclic based compounds having the following structure Va and Vb:
[0000]
[0000] wherein:
[0057] p=0, 1 or 2;
[0058] q=0, 1 or 2;
[0059] r=0, 1, 2 or 3;
[0060] each dashed line “ ” is, independently, a single bond or double bond;
[0061] wherein when D and E are connected by a single bond, D and E are each, independently, selected from the group consisting of O, S, amino, and —C(Ra)(Rb)-; and R 10 is hydrogen, oxygen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0062] wherein when D and E are connected by a double bond, D and E each, independently, selected from the group consisting of N or —C(Rc)-;
[0063] wherein when E 1 and G are connected by a single bond, E 1 and G are each, independently, selected from the group consisting of O, S, amino, and —C(Ra)(Rb)-; and R 10 is hydrogen, oxygen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 12 heterocyclic group;
[0064] wherein when E 1 and G are connected by a double bond, E 1 and G are each, independently, selected from the group consisting of N or —C(Rc)-;
[0065] wherein when the dashed line connecting R 10 to the macrocycle is a double bond, R 10 is O or S;
[0066] wherein when the dashed line connecting R 10 to the macrocycle is a single bond, R 10 is hydrogen, halogen atom, cyano, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, or C 2 -C 20 heterocyclic group;
[0067] Ra, Rb and Rc are each, independently, selected from the group consisting of hydrogen, halogen atom, cyano, nitro, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, C 2 -C 20 heterocyclic alkoxycarbonyl, C 2 -C 20 heterocyclic aryl, C 1 -C 20 alkylamino, C 2 -C 20 heterocyclic amino, C 6 -C 20 aryl amino, C 1 -C 20 aminocarbonyl, C 1 -C 20 amido, C 1 -C 20 amidocarbonyl, C 1 -C 20 carbonylamino, C 1 -C 20 alkylsulfonamido, C 2 -C 20 heterocyclic sulfonamido, C 6 -C 20 arylsulfonamido, and C 1 -C 20 aminosulfonamido group;
[0068] wherein when r=0, E is nothing, and the D group is directly linked to the E 1 group;
[0069] R 7 , R 8 and R 9 are each, independently, selected from the group consisting of hydrogen, cyano, nitro, trifluoromethyl, C 1 -C 20 alkyl, C 1 -C 20 alkoxy, C 1 -C 20 alkylthio, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 1 -C 20 carbonylamino, C 6 -C 20 aryl, C 6 -C 20 aryloxy, C 6 -C 20 aryloxycarbonyl, and C 2 -C 20 heterocyclic group; and
[0070] R 13 is hydrogen, C 1 -C 20 alkyl, C 1 -C 20 alkylcarbonyl, C 1 -C 20 alkoxycarbonyl, C 1 -C 20 cycloalkoxycarbonyl, C 1 -C 20 aminocarbonyl, C 6 -C 20 aryl, C 6 -C 20 arylcarbonyl, C 6 -C 20 aryloxycarbonyl, C 1 -C 20 alkylsulfonyl, C 6 -C 20 arylsulfonyl, C 1 -C 20 aminosulfonyl, or C 2 -C 20 heterocyclic group.
[0071] The fourth aspect of the present invention provides a pharmaceutical composition comprising one or more compounds selected from the structure Ia-Ib or IIa-IIb.
[0072] The fifth aspect of the present invention provides a pharmaceutical combination of any one or more compounds of the structure Ia-Ib or IIa-IIb in a therapeutically effective dose and/with a second or a third medicament in a therapeutically effective dose. Thus, the present invention provides a pharmaceutical composition, comprising at least one compound described above in a therapeutically effective dose and at least one additional medicament in a therapeutically effective dose
[0073] The sixth aspect of the present invention provides a pharmaceutical combination of any compound of the structure Ia-Ib or IIa-IIb and/with any HIV inhibitor including but not limited to Ritonavir. Thus, the present invention provides a A pharmaceutical composition, comprising at least one compound described above in a therapeutically effective dose and at least one HIV inhibitor in a therapeutically effective dose.
[0074] The seventh aspect of the present invention provides a pharmaceutical combination of at least one compound described above and any-hepatitis B virus (HBV) inhibitor including but not limited to Heptodin, Sebivo, Hepsera, Emtriva, Baraclude, or Viread.
[0075] The eighth aspect of the present invention provides a method for inhibiting HCV by using one or more compounds of the structure Ia-Ib or IIa-IIb in a therapeutically effective dose and a second or a third medicament in a therapeutically effective dose. Thus, the present invention provides a method of inhibiting HCV, comprising administering an effect amount of a compound or composition described above to a subject in need thereof.
[0076] The ninth aspect of the present invention provides a method for inhibiting HCV by using one or more compounds of the structure Ia-Ib or IIa-IIb and in combination with any or combined one or more of (1) Immune modulators including but not limited to Interferons, pegulated-interferons, or interferon derivatives, (2) HCV protease inhibitors, (3) HCV polymerase inhibitors, (4) nucleosides and its derivatives, (5) Cyclophilin inhibitors, (6) Glucosidase I inhibitors, (7) IMPDH inhibitors, (8) Caspase inhibitors, (9) TLR agonists, (10) HIV inhibitors, (11) anti-inflammatory drugs, (12) Cancer drugs, or (13) other compounds not covered from above (1)-(12).
[0077] Overall, furthermore, all prepared new polyheterocyclic based compounds have been evaluated for their potency in vitro and in vivo, and the present invention explores the relationship between the structures of new polyheterocyclic compounds and efficacy of HCV inhibition and provides valuable clue and potential HCV inhibitors.
DETAILED DESCRIPTION OF THE INVENTION
[0078] Details of the present invention are set forth in the following description for preparation and biological activity study of new HCV inhibitors Ia-Ib and IIa-IIb. The advantages of the present invention will be significantly observed from the following detailed description.
[0079] As used herein, the term “alkyl” refers to any linear or branched chain alkyl group having a number of carbon atoms and/or “alkylene” in the specified range, wherein one or more hydrogens could be replaced by one or more halogens.
[0080] The term “alkoxy” refers to an “alkyl-O—” group.
[0081] The term “cycloalkyl” refers to any cyclic ring of an alkane or alkene having a number of carbon atoms and/or “alkylene” in the specified range, wherein one or more hydrogens could be replaced by one or more halogens.
[0082] The term “halogen” (or “halo”) refers to fluorine, chlorine, bromine and iodine atoms (or referred as fluoro, chloro, bromo, and iodo).
[0083] The term “carbonyl” refers to an “—C(O)—” group.
[0084] The term “alkyl carbonyl” refers to an “alkyl-C(O)—” group.
[0085] The term “alkoxy carbonyl” refers to an “alkyl-O—C(O)—” group.
[0086] The term “alkylamino carbonyl” refers to an “alkyl-NH—C(O)—” or “dialkyl-N—C(O)—” group.
[0087] The term “sulfonamido” refers to an “—S(O) 2 NH—” or “—S(O) 2 N(R)—” group, wherein R is alkyl or alkylcarbonyl group.
[0088] The term “alkyl sulfonamido” refers to an “alkyl-S(O) 2 NH—” or “alkyl-S(O) 2 N(R)—” group, wherein R is alkyl or alkylcarbonyl group.
[0089] The term “alkoxy sulfonamido” refers to an “alkyl-O—S(O) 2 NH—” or “alkyl-O—S(O) 2 N(R)—” group, wherein R is alkyl or alkylcarbonyl group.
[0090] The term “polyheterocyclic” refers to a tri-cyclic or tetra-cyclic functional group with 1-5 hetero atoms (e.g., O, N, S, and P) in one or more fused rings.
[0091] The term “composition” is intended to encompass a product comprising the specified ingredients, as well as any product which results, directly or indirectly, from combining the specified ingredients.
[0092] The term “pharmaceutically acceptable” means that the ingredients of the pharmaceutical composition must be compatible with each other and not deleterious to the recipient thereof.
[0093] The term “effective amount” means that amount of active compound or pharmaceutical agent that elicits the biological or medicinal response in a tissue, system, animal or human that is being sought by a researcher, veterinarian, medical doctor or other clinician. The term also includes herein the amount of active compound sufficient to inhibit HCV NS3 protease and thereby elicit the response being sought (i.e., an “inhibition effective amount”). When the active compound (i.e., active ingredient) is administered as the salt, references to the amount of active ingredient are to the free acid or free base form of the compound.
[0094] The present invention provides two classes of novel polyheterocyclic based compounds Ia-Ib and IIa-IIb, and pharmaceutically acceptable salts, and/or hydrates as HCV NS3 protease inhibitors with high potency. Moreover, toxicity study is is determined to be non-toxic (LD 50 >10,000) for most of highly potent HCV inhibitors.
[0095] Synthesis of New Polyheterocyclic Based Compounds with General Structure Ia-Ib and IIa-IIb:
[0096] Using previously published and the synthetic methods described herein, different kinds of synthetic methods have been carried out effectively to prepare different compounds with the structure Ia-Ib and IIa-IIb.
[0097] In the present invention, compounds VIa-VIf are prepared first as in the following Scheme 1:
[0000]
[0098] In Scheme 1, in the presence of inorganic base (e.g., sodium hydroxide, sodium methoxide, or sodium hydrogen), SM-1 was dissolved in organic solvents (methanol, THF, DMF, or DMSO) and heated to 30-120° C., then reacted with ClCH 2 Cl, ClCH 2 CH 2 Cl, or BrCH 2 CH 2 CH 2 Br, respectively, to form five, six, or seven membered polyheterocyclic compound 1-1, 1-2, or 1-3, followed by deprotection to obtain the key tri-heterocyclic compounds VIa-VIc by removing the protecting group (Bn: benzyl) with Pd/C catalyst and hydrogen in methanol or ethanol.
[0000]
[0099] In Scheme 2, SM-2 was dissolved in organic solvents (methanol, THF, DMF, or DMSO) and heated to 30-120° C., then reacted with BrCH 2 CH 2 CH 2 Br, ClCH 2 CH 2 Cl or ClCH 2 Cl, respectively, to form seven, six or five membered polyheterocyclic compound 2-1, 2-2, or 2-3, followed by deprotection to obtain the key tri-heterocyclic compounds VId-VIf by removing the protecting group (Bn: benzyl) with Pd/C catalyst and hydrogen in methanol or ethanol.
[0100] Preparation of the following specific compounds IIIa-IIIb has been carried out as follows in Scheme 3.
[0000]
[0101] R 11 is preferred to be selected from the following group: SM-4a (Boc) or SM-4b:
[0000]
[0102] In the presence of coupling reagent CDI, starting material SM-4 (e.g., SM-4a or SM-4b) was reacted with compounds VIa-VIf, respectively to obtain polyheterocyclic compounds 4a-4h and 6a-6d (IIIa-IIIb) as shown below amidation reaction.
[0000]
[0103] After the key intermediates 4a-4f and 6a-6f were prepared, there were several synthetic methods developed as in Schemes 4-11 for preparation of different kinds of new HCV inhibitors. The detail for each reaction condition and analytical results of products is listed in the detailed examples.
[0000]
[0104] In Scheme 4 above, the product 4 (e.g., compounds 4a-4f and 6a-6f) prepared as shown in Scheme 3 was deprotected to obtain an intermediate carboxylic acid (5) by removing HCl group, followed by amidation with an N-Boc protected amino acid SM-5 to form compound 6 in the presence of coupling reagent HATU. After hydrolysis of compound 6 in LiOH-Water/MeOH solution, another carboxylic acid (7) was obtained, and followed by amidation with another amino acid (methyl or ethyl ester) SM-6 in the presence of coupling reagent HATU to form product 9 (e.g., compounds 9a-9f shown below). In anhydrous oxygen-free organic solvents (DCM, DCE, or toluene), Diene 9 intermediate was carried out an olefin ring-closing metathesis (RCM) reaction in the presence of metathesis catalyst (e.g., Zhan catalyst-1 or Zhan catalyst-1B used in this invention) at 20-80□ to form 14-16 membered macrocyclic olefin-linked product 10, then the methyl/ethyl ester was hydrolyzed with LiOH in water-MeOH solution to offer a new carboxylic acid 11. Finally, in the presence of a coupling reagent such as EDCI or HATU, the carboxylic acid 11 reacted with different kinds of alkylsulfonamide, cycloalkylsulfonamide or arylsulfonamide [RdS(O) 2 NH 2 ], respectively, to form a series of novel polyheterocyclic based macrocyclic compounds Ia-Ib, such as 12a-12xx shown below).
[0000]
[0105] The structure of Zhan catalysts (Zhan Catalyst-1 & 1B) used for RCM of diene intermediate 9 is shown below:
[0000]
[0106] In order to obtain more compounds efficiently for potency screening, there is another alternative synthetic route developed effectively for preparation of different new macrocyclic compounds Ia-Ib in Scheme 5.
[0000]
[0107] In Scheme 5, first of all, the protecting group (Boc) in the starting material SM-7 was removed by HCl acid, followed by amidation with an N-Boc protected amino acid SM-5 to form compound 8 in the presence of coupling reagent HATU. In the presence of coupling reagent CDI, compound 8 was reacted with compounds VIa-VIf, respectively, to obtain polyheterocyclic compounds 9. In anhydrous oxygen-free organic solvents (DCM, DCE, or toluene), an olefin ring-closing metathesis (RCM) reaction was carried out for the diene 9 intermediate in the presence of metathesis catalyst (e.g., Zhan catalyst-1 or Zhan catalyst-1B used in this invention) at 20-80□ to form 14-16 membered macrocyclic olefin-linked product 10, then the methyl/ethyl ester was hydrolyzed with LiOH in water-MeOH solution to offer a new carboxylic acid 11 as shown below.
[0000]
[0000] Finally, in the presence of a coupling reagent such as EDCI or HATU, the carboxylic acid product 11 reacted with different kinds of alkylsulfonamide, cycloalkylsulfonamide or arylsulfonamide [RdS(O) 2 NH 2 ], respectively, to form a series of novel polyheterocyclic based macrocyclic compounds Ia-Ib.
[0108] In order to optimize efficacy and biological property of new HCV inhibitors, there are more structure modified compounds designed and synthesized in Schemes 6-11. In Scheme 6, there is a kind of cycloalkylsulfonamide products prepared for potency screening.
[0000]
[0109] In Scheme 6 above, the compound 10c-d prepared in Schemes 4 and 5 were used for deprotection first by removing Boc with HCl acid, followed by amidation with an alkylsulfonyl chloride reagent (RdSO 2 Cl or R 17 SO 2 Cl, SM-9) to obtain an alkylsulfonamide product 13. In the presence of inorganic base (e.g., NaOH or KOH), the intramolecular cyclization was conducted to form sulfonamide compound 11. Finally, in the presence of a coupling reagent such as EDCI or HATU, the carboxylic acid 11 reacted with different kinds of alkylsulfonamide, cycloalkylsulfonamide or arylsulfonamide [RdS(O) 2 NH 2 , SM-8], respectively, to form a series of novel polyheterocyclic based macrocyclic compounds Ia-Ib, such as 12j-12m as shown below. Furthermore, the compound 10c-d was deprotected first by removing Boc with HCl acid, followed by amidation with an alkylsulfonyl chloride reagent (RdSO 2 Cl or R 17 SO 2 Cl, SM-9) to obtain another kind of alkylsulfonamide product 13, then in the presence of a base (e.g., NaH or NaOMe), the alkylsulfonamide product 13 was reacted with another reagent R 16 —Cl (or R 16 —Br, SM-10) or (Boc) 2 O to form another kind of new desired products Ia-Ib (12s-12u) as herein, wherein, R 16 is C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxycarbonyl, C 3 -C 6 cycloalkoxycarbonyl, C 6 -C 10 aryl, C 6 -C 10 arylcarbonyl, C 6 -C 10 aryloxycarbonyl or C 2 -C 10 heterocyclic group.
[0000]
[0110] In the following Scheme 7, the product 12 (e.g., 12a-12f and 12-Ref) was used for deprotection first by removing Boc with HCl acid, followed by either alkylation or amidation with reagent SM-10 (R 16 —Cl or R 16 —Br) to obtain an N-alkylated product 15 or amidation with an alkylsulfonyl or arylsulfonyl chloride reagent SM-9 [R 17 S(O) 2 Cl)] to form product 16, wherein R 16 and R 17 each is C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxycarbonyl, C 3 -C 6 cycloalkoxycarbonyl, C 6 -C 10 aryl, C 6 -C 10 arylcarbonyl, C 6 -C 10 aryloxycarbonyl or C 2 -C 10 heterocyclic group, which generates more polyheterocyclic compounds 15a-15b and 16a-16c shown below.
[0000]
[0111] In order to optimize efficacy and biological property of new HCV inhibitors, there are two more different macrocyclic structure designed and synthesized in the following Schemes 8 and 9.
[0000]
[0112] In Scheme 8, in the presence of coupling reagent HATU, an acid SM-11 was reacted with another amine SM-12 to form a diene product 17 by amidation, followed by RCM reaction in the presence of Zhan catalyst-1B to form a 14-16 membered macrocyclic product 18. In the presence of coupling reagent CDI, product 18 was reacted with compounds VIa-VIf, respectively to obtain polyheterocyclic compounds 21a-21f, then the methyl/ethyl ester was hydrolyzed with LiOH in water-MeOH solution to offer a new carboxylic acid 11. Finally, in the presence of a coupling reagent such as EDCI or HATU, the carboxylic acid 20 reacted with different kinds of alkylsulfonamide, cycloalkylsulfonamide or arylsulfonamide [RdS(O) 2 NH 2 ], respectively, to form a series of novel polyheterocyclic based macrocyclic compounds Ia-Ib (21a-21j), shown below:
[0000]
[0000]
[0113] In Scheme 9, in the presence of coupling reagent CDI, SM-7 was reacted with compounds VIa-VIf, respectively to obtain polyheterocyclic compounds 23a-23f, followed by reacting with a reagent chloroformic acid 4-nitrophenyl ester and SM-12 to form a diene product 24. In the presence of Zhan catalyst-1B, the diene product 24 was conducted a RCM reaction to form a desired macrocyclic product 25, then the methyl/ethyl ester was hydrolyzed with LiOH in water-MeOH solution to offer a new carboxylic acid 26. Finally, in the presence of a coupling reagent such as EDCI or HATU, the carboxylic acid 26 reacted with different kinds of alkylsulfonamide, cycloalkylsulfonamide or arylsulfonamide [RdS(O) 2 NH 2 ], respectively, to form a series of novel polyheterocyclic based macrocyclic compounds Ia-Ib (27a-27c and 27-Ref), shown below:
[0000]
[0114] To evaluate the difference in potency and other biological activities between the macrocyclic and linear structures for the novel polyheterocyclic based HCV inhibitors, there are different kinds of linear compounds IIa-IIb (30 and 33) with polyheterocyclic groups VIa-VIf prepared as shown in the following Schemes 10 and 11, respectively.
[0000]
[0115] In Scheme 10 above, in the presence of coupling reagent EDCI, an amine SM-13 was reacted with a sulfonamide RdS(O) 2 NH 2 ], (SM-8) to form product 28, followed by removing Boc protecting group to obtain a de-Boc product 29. Finally, in the presence of a coupling reagent such as EDCI or HATU, the amine intermediate 29 was reacted with different kinds of amino acid derivatives SM-14 selected from a list of chemical reagents shown below to form various products IIa-IIb (30a-30ar) as shown as follows, wherein Rd and R 18 each is C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl group, and R 19 is C 1 -C 20 alkyl, C 1 -C 20 alkylcarbonyl, C 1 -C 20 alkoxycarbonyl, or C 1 -C 20 alkylsulfonamido groups as shown below from compounds 30a-30ar.
[0000]
[0000]
[0116] In Scheme 11 above, in the presence of coupling reagent HATU in DMF, an acid SM-15 was reacted with another amine reagent SM-16 to form an amide product 31 by amidation, followed by removing Boc protecting group with HCl-THF solution to obtain an amine product 32. Finally, in the presence of a coupling reagent such as EDCI or HATU, the amine intermediate 32 reacted with various carboxylic acids SM-14, respectively to form different kinds of novel polyheterocyclic based linear compounds IIa-IIb (33a-33d) shown as follows, wherein R 18 each is C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl group, and R 19 is C 1 -C 20 alkyl, C 1 -C 20 alkylcarbonyl, C 1 -C 20 alkoxycarbonyl, or C 1 -C 20 alkylsulfonamido groups.
[0000]
[0117] Additional polyheterocyclic based compounds within the scope of the present invention can be prepared using other suitable starting materials through the above synthetic routes or other developed procedures as reported from different references. The methods described in Schemes 1-11 above may also additionally include steps, either before or after the steps described specifically herein, to add or remove suitable protecting groups in order to ultimately allow synthesis of the compounds in this invention. In addition, various synthetic steps may be performed in an alternate sequence or order to give the desired compounds.
[0118] Synthetic chemistry transformations and protecting group methodologies (protection and deprotection) useful in synthesizing applicable compounds in this invention are known in the art and include, for example, those described in R. Larock, Comprehensive Organic Transformations , VCH Publishers (1989); T. W. Greene and P. G. M. Wuts, Protective Groups in Organic Synthesis, 2 nd Ed., John Wiley and Sons (1991); L. Fieser and M. Fieser, Fieser and Fieser's Reagents for Organic Synthesis , John Wiley and Sons (1994); and L. Paquette, ed., Encyclopedia of Reagents for Organic Synthesis , John Wiley and Sons (1995) and subsequent editions thereof.
[0119] The compounds mentioned herein may contain a non-aromatic double bond and one or more asymmetric centers. Thus, they can occur as racemates and racemic mixtures, single enantiomers, individual diastereomers, diastereomeric mixtures, tautomers, and cis- or trans-isomeric forms, and/or hydrates. All such isomeric forms are contemplated.
[0120] So far, there is no any effective animal model for scientists to evaluate the efficacy of new compounds for inhibiting the HCV NS3 protease. The compounds described above in the present invention can be preliminarily screened by evaluating the IC 50 and/or EC 50 results for their activity and efficacy in treating HCV infection by an in vitro and/or in vivo assay as follows, then have some highly potent HCV inhibitors selected for other PK and toxicity studies before clinic trial during new drug development. Other methods will also be apparent for scientists in pharmaceuticals.
[0121] HCV NS3-4A Protease Assay In Vitro.
[0122] The assay was conducted in Buffer A containing 30 mM NaCl, 5 mM CaCl 2 , 10 mM DTT, 50 mM Tris (pH7.8), using the Ac-Asp-Glu-Asp(EDANS)-Glu-Glu-Abu-ψ-[COO]-Ala-Ser-Lys (DABCYL)-NH 2 (FRET-S) fluorescent peptide (AnaSpec, USA) as substrate. Briefly, 140 μL buffer A, 20 μL compounds dissolved in buffer A with different concentration and 20 μL HCV NS3-4A protease diluted in buffer A were added into 96-well plate respectively and mixed well. The reaction was initiate with adding 20 μL of FRET-S. Reactions were continuously monitored at 37° C. using a BMG Polarstar Galaxy (MTX Lab Systems, Inc. USA), with excitation and emission filters of 355 nm and 520 nm, respectively. The 50% inhibitory concentration (IC 50 ) was calculated with Reed & Muench methods.
[0123] Antiviral Assay:
[0124] Antiviral assays were carried out in black-walled, clear bottomed 96-well plates. Renila luciferase reporter replicon cells were seeded at a density of 7×10 3 cells/well in 100 μl complete DMEM culture without selection antibiotics. Eight twofold serial dilutions of compounds were prepared in complete DMEM and added to the appropriate wells, yielding final concentrations in 200 μl of complete DMEM culture. Following 3 days of incubation, cells were incubated with 100 μl fresh culture containing EnduRen™ Live Cell Substrate (Promega) at final concentrations of 60 μM at 37° C. in 5% CO 2 for 2 h in the dark. Luminescence was then measured using an EnVision (Perkin-Elmer) microplate reader. Data were normalized to percentage of the control, and the 50% effective concentration (EC 50 ) values were calculated using the method of Reed-Muench.
[0125] Acute Toxicity Study (MTD):
[0126] Materials and Methods for MTD Study are as follows:
[0127] Animals:
[0128] 320 KM mice, Certificate Number: 2007000510144, male and female were each half, 40 Wistar rats, certificate number: 2007000510555, male and female were each half. Animals were purchased from SLAC Laboratory Animal Limited Co., Feed: Breeding fodder of Radiation, special for rats and mice, was purchased from SLAC Laboratory Animal Limited Co.
[0129] Test Group:
[0130] Animals were fed freely for adaptation more than 1 week. Healthy rats, body weight between 170-190 g, were divided randomly into 3 groups, 5 male and 5 female in each group. Healthy mice, body weight between 18-20 g, were divided randomly into 22 groups, 5 male and 5 female in each group.
[0131] Administration Method:
[0132] In rats, the compound weighing 21.00 g, serial number 1-3 respectively, adding 0.7% sodium carboxymethyl cellulose solution 30.00 g, high-speed homogenizer machine 15000 RPM, 10 min mixing, the rats were fed once, oral dose 10000 mg/kg. In mice, the compound weighing 2.00 g, serial number 4-25 respectively, adding 0.7% sodium carboxymethyl cellulose solution 8.00 g, high-speed homogenizer machine 10000 RPM, 10 min mixing, the mice were fed once, oral dose 10000 mg/kg.
[0133] Clinical Observation:
[0134] Animals were observed every hour after administration in the first day, and behavior observation daily continuous for a week. Dead animals were necropsied, gross pathology of the organs were observed and recorded.
[0135] Evaluation of Toxicity:
[0136] Toxicity was evaluated by animal mortality, signs of clinical behavior and others.
[0137] Among all of synthesized polyheterocyclic compounds 11a-11p, 12a-12u, 15a-15b, and 16a-16c, 30a-30ar, 33a-33d and some reference compounds 12-Ref, 21-Ref, 27-Ref, the results of HCV protease (HCV NS3-4A) inhibition test are listed in Table 1; where the scope of potent activity (IC 50 ): ≧200 nM labeled “A”, active in the range of 30-200 nM labeled “B”, active range ≦30 nM labeled “C”.
[0000]
TABLE 1
Activity of Novel Polyheterocyclic Based Compounds
for Inhibiting HCV NS3 Protease
NS3-NS4A
Entry
Compound
IC 50
1
11a
A
2
11b
A
3
11c
A
4
11d
A
5
12a
C
6
12b
C
7
12c
C
8
12d
C
9
12e
C
10
12f
C
11
12g
C
12
12h
C
13
12j
B
14
12k
C
15
12m
B
16
12n
C
17
12p
C
18
12q
C
19
12r
C
20
12s
C
21
12t
C
22
12u
C
23
12-Ref
C
24
15a
C
25
15b
C
26
16a
C
27
16b
C
28
16c
C
29
21a
B
30
21b
B
31
21c
C
32
21d
B
33
21e
C
34
21f
B
35
27a
B
36
27b
B
37
27c
B
38
27-Ref
B
39
27-Ref-2
B
40
30a
C
41
30b
C
42
30c
C
43
30d
C
44
30e
C
45
30f
C
46
30g
C
47
30h
C
48
30j
C
49
30k
C
50
30m
C
51
30n
C
52
30p
C
53
30r
C
54
30s
C
55
30t
C
51
30v
C
52
30w
C
53
30x
C
54
30y
C
55
30z
C
56
30aa
C
57
30ab
C
58
30ac
C
59
30ad
B
60
30ae
B
61
30af
C
62
30ag
C
63
30ah
C
64
30aj
C
65
30ak
C
66
30am
C
67
30an
C
68
30ap
C
69
30aq
C
70
30ar
C
71
30-Ref
C
72
33a
B
73
33b
B
74
33c
B
75
33d
A
76
30-Ref
B
[0138] The potent screening results in Table 1 show that: (1) the polyheterocyclic based macrocyclic compounds (e.g., 12a-12u) containing cyclopropyl sulfonamide and isopropylsulfonamide have much better HCV inhibition activity than the polyheterocyclic based carboxyl acid products (e.g., 11a-11m) that do not have cyclopropylsulfonamide or isopropylsulfonamide group incorporated by amidation, (2) in general, the polyheterocyclic based macrocyclic compounds Ia-Ib (e.g., 12a-12u) have better efficacy and biological activity than the polyheterocyclic based linear compounds IIa-IIb (e.g., 30a-30ar and 33a-33d), and (3) several of the novel polyheterocyclic based macrocyclic sulfonamide compounds Ia-Ib (e.g., 12a-12d, 12q-12u) are highly effective (EC 50 : 0.001-1.0 uM) as HCV inhibitors, and many of new polyheterocyclo based HCV inhibitors have excellent biological activities to inhibit HCV in comparison with some referred HCV inhibitors already in clinical Phase II and III, such as InterMune (ITMN-191, 12Ref)-Roche, and Merck MK-7009.
[0139] Overall, all prepared new polyheterocyclic based compounds have been evaluated for their potency and efficacy in vitro and/or in vivo, and there are two novel classes of polyheterocyclic based compounds found highly effective to inhibit HCV. Moreover, the present invention explores the insight relationship between the structures of new polyheterocyclic compounds and efficacy of HCV inhibition, which provides valuable clue to develop an effective potential HCV inhibitors among the developed novel polyheterocyclic compounds Ia-Ib and IIa-IIb.
[0140] Abbreviations of chemical materials, reagents, and solvents related to the present invention are listed as follows:
[0141] SM4: N-Boc-trans-4-hydroxy-L-proline methyl ester
[0142] SM5: Boc-L-2-amino-8-azelaic acid
[0143] SM6: (1R,2S)-1-amino-2-cyclopropyl methyl vinyl
[0144] AIBN: azobisisobutyronitrile
[0145] (Boc)2O: di-tert-butyl carbonate
[0146] CDI: N,N′-carbonyldiimidazole imidazole
[0147] DBU: 1,8-Diazabicyclo[5.4.0]undec-7-ene
[0148] EDCI: N-ethyl-N-(3-dimethyl aminopropyl)carbodiimide hydrochloride
[0149] HATU: 2-(7-benzotriazole azo)-N,N,N′,N′-tetramethyl urea phosphate hexafluoride
[0150] NBS: N-bromosuccinimide
[0151] DMAP: 4-dimethylaminopyridine
[0152] DIEA: N,N-diisopropyl ethylamine
[0153] SOCl2: thionyl chloride
[0154] Pd/C: Palladium carbon
[0155] HMTA: hexamethylene tetramine
[0156] HOAc: acetic acid
[0157] HBr: Hydrobromic acid
[0158] HCl: hydrochloric acid
[0159] TFA: trifluoroacetic acid
[0160] TsOH: p-toluenesulfonate
[0161] NaOH: sodium hydroxide
[0162] ACN: acetonitrile
[0163] DCM: dichloromethane
[0164] DCE: dichloroethane
[0165] DMF: N,N-dimethylformamide
[0166] DMSO: dimethyl sulfoxide
[0167] Et2O: diethyl ether
[0168] EA: ethyl acetate
[0169] PE: petroleum ether
[0170] THF: tetrahydrofuran
[0171] TBME: tert-butyl methyl ether
EXAMPLES
General
[0172] Infrared (IR) spectra were recorded on a Fourier Transform AVATAR™ 360 E.S.P™ spectrophotometer (Unit: cm −1 ). Bands are characterized as broad (br), strong (s), medium (m), and weak (w). 1 H NMR spectra were recorded on a Varian-400 (400 MHz) spectrometer. Chemical shifts are reported in ppm from tetramethylsilane with the solvent resonance as the internal standard (CDCl 3 : 7.26 ppm). Data are reported as follows: chemical shift, multiplicity (s=singlet, d=doublet, t=triplet, q=quartet, br=broad, m=multiplet), coupling constants (Hz), integration, and assignment. 19 F and 31 P NMR spectra were recorded on a Varian-400 (400 MHz) and Varian-500 (500 MHz) spectrometers. The chemical shifts of the fluoro resonances were determined relative to trifluoroacetic acid as the external standard (CF 3 CO 2 H, 0.00 ppm), and the chemical shifts of the phosphorus resonances were determined relative to phosphoric acid as the external standard (H 3 PO 4 : 0.00 ppm). Mass spectra were obtained at Thermo Finnigan LCQ Advantage. Unless otherwise noted, all reactions were conducted in oven- (135° C.) and flame-dried glassware with vacuum-line techniques under an inert atmosphere of dry Ar. THF and Et 2 O were distilled from sodium metal dried flask, DCM, pentane, and hexanes were distilled from calcium hydride. Most chemicals were obtained from commercial sources or ordered by contract synthesis from Zannan SciTech Co., Ltd. in China. General procedures for preparation of different polyheterocyclic intermediates and products (Ia-Ib and IIa-IIb) are described in the following examples, respectively.
Example 1
Synthesis of Compound VIa
[0173] SM-1 (12.2 g, 0.5 mol) and 100 mL DCM were added into a 250 mL reaction flask, then NaOH (5 g) and DMSO (50 mL) were added and heated to 100° C. After the reaction was completed, the mixture was poured into ice water and extracted three times with DCM. The combined organic layer was washed with brine, then dried and concentrated, finally purified by column chromatography with silica gel to obtain the cyclized product 1-1 (7.7 g), yield 61%. ESI-MS (M+H + ): m/z calculated: 253.1, founded: 253.2.
[0174] The product 1-1 (5.0 g, 0.2 mol) was dissolved in ethanol, catalyst Pd/C (0.5 g) was added under hydrogen pressure (0.6 MPa). When the reaction was completed, the mixture was filtered and washed with ethanol, then the filtrate was concentrated to offer crude product (3.0 g). After purified by flash column, the desired product VIa (2.5 g) was obtained with purity over 99%, yield 76%. Total yield for two steps: 46%.
[0175] 1 H-NMR for the product VIa (CDCl3, 500 MHz): δ 6.71 (s, 2H), 5.91 (s, 2H), 4.20 (s, 2H), 4.15 (s, 2H), 2.22 (s, 1H, NH). ESI-MS (M+H + ): m/z calculated 164.1, founded 164.2.
Example 2
Synthesis of Compound VIb
[0176] SM-1 (12 g, 0.5 mol) and 30 mL DCE were added to a 250 mL reaction flask, then NaOH (5 g) and DMSO (50 mL) were added and heated to 100° C. After the reaction was completed, the mixture was poured into ice water and extracted three times with DCM. The combined organic layer was washed with brine, then dried and concentrated. After purified by flash column, the desired product 1-2 (9.4 g) was obtained, yield 71%. ESI-MS (M+H + ): m/z calculated 268.1, founded 268.2.
[0177] The product of 2-1 (5.0 g) was dissolved in ethanol, Pd/C (0.5 g) was added with hydrogen pressure (0.6 MPa). When the reaction was completed, the mixture was filtered and washed with ethanol, the filtrate was concentrated to give crude product (3.0 g). After purified by flash column, the desired product VIb (2.9 g) was obtained. Total yield for two steps: 61%.
[0178] 1 H-NMR for the product VIb (CDCl3, 500 MHz): δ 6.77-6.75 (d, J=8.0 Hz, 1H), 6.72-6.70 (d, J=8.0 Hz, 1H), 4.29-4.28 (m, 2H), 4.27-4.26 (m, 2H), 4.19 (s, 2H), 4.17 (s, 2H), 2.27 (s, 1H, NH). ESI-MS (M+H + ): m/z calculated 178.1, founded 178.2.
Example 3
Synthesis of Compound VIc
[0179] SM-1 (12 g, 0.5 mol) and Br(CH2)3Br (20 mL) were added to a 250 mL reaction flask, then NaOH (5 g) and DMSO (50 mL) were added and heated to 100° C. The reaction condition was the same as done in Example 2. After the cyclization and purification, the desired product VIc was obtained. Total yield for two steps: 47%.
[0180] 1H-NMR for the product VIc (CDCl3, 500 MHz): δ 10.09 (s, 2H), 6.96-6.94 (d, J=8.0 Hz, 1H), 6.92-6.90 (d, J=7.5 Hz, 1H), 4.40-4.39 (m, 4H), 4.20-4.17 (t, J=5.0 Hz, 2H), 4.13-4.11 (t, J=5.0 Hz, 2H), 2.19-2.09 (m, 2H). ESI-MS [(M+H)+]: m/z calculated 192.1, founded 192.1.
Example 4
Synthesis of Ru Complex VId
[0181] SM-2 (12 g, 0.5 mol) and Br(CH2)3Br (20 mL) were added to a 250 mL reaction flask, then NaOH (5 g) and DMSO (50 mL) were added and heated to 100° C. The reaction condition was the same as done in Example 2. After the cyclization and purification, the desired product VIc was obtained. Total yield for two steps: 41%.
[0182] 1 H-NMR for the product VId (CDCl3, 500 MHz): δ 6.86 (s, 2H), 4.30 (brs, 1H), 4.20 (s, 4H), 4.15-4.17 (t, J=5.8 Hz, 4H), 2.16-2.18 (m, 2H). ESI-MS [(M+H) + ]: m/z calculated 192.1, founded 192.1.
Example 5
Synthesis of Compound VIe
[0183] SM-2 (12 g, 0.5 mol) and DCE (30 mL) were added to a 250 mL reaction flask, then NaOH (5 g) and DMSO (50 mL) were added and heated to 100° C. The reaction condition was the same as done in Example 2. After the cyclization and purification by flash column, the desired product VIe was obtained. Total yield for two steps: 56%.
[0184] 1H-NMR for the product VIe (CDCl3, 500 MHz): δ 6.74 (s, 2H), 4.23 (s, 4H), 4.13 (s, 4H). ESI-MS (M+H+): m/z calculated 178.1, founded 178.2.
Example 6
Synthesis of Compound VIf
[0185] SM-2 (12 g, 0.5 mol) and DCM (100 mL) were added to a 250 mL reaction flask, then NaOH (5 g) and DMSO (50 mL) were added and heated to 100° C. The reaction condition was the same as done in Example 1. After the cyclization and purification is by flash column, the desired product VIf was obtained. Total yield for two steps: 51%.
[0186] 1H-NMR for the product VIf (CDCl3, 500 MHz): δ 6.69 (s, 2H), 5.95 (s, 2H), 4.14 (s, 4H). ESI-MS (M+H+): m/z calculated 164.1, founded 164.2.
Example 7
Synthesis of Compound 4a
[0187] SM-4 (5.37 g, 21.9 mmol) and CDI (14.2 g, 87.5 mmol, 4 eq.) were dissolved in 100 mL anhydrous dichloromethane (DCM) and stirred overnight, followed by adding another compound VIa (43.7 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 4a (5.2 g) was obtained, yield 71%.
[0188] 1 H-NMR for the product 4a (CDCl 3 , 500 MHz): δ 6.78-6.80 (m, 1H), 6.69-6.75 (m, 1H), 6.00 (s, 2H), 5.34 (m, 1H), 4.67-4.70 (d, J=13.5 Hz, 2H), 4.60-4.63 (d, J=15 Hz, 2H), 4.40-4.48 (m, 1H), 3.66-3.78 (m, 5H), 2.48 (m, 1H), 2.24-2.26 (m, 1H), 1.48 (s, 4H), 1.45 (s, 5H). ESI-MS (M+H + ): m/z calculated 435.2, founded 435.3.
Example 8
Synthesis of Compound 4b
[0189] SM-4 (5.37 g, 21.9 mmol) and CDI (14.2 g, 87.5 mmol, 4 eq.) were dissolved in 100 mL anhydrous dichloromethane and stirred at room temperature overnight, followed by adding another compound VIb (43.7 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 4b (6.1 g), yield 82%.
[0190] 1 H-NMR for the product 4b (CDCl 3 , 500 MHz): δ 6.81-6.84 (m, 1H), 6.68-6.75 (m, 1H), 5.33 (m, 1H), 4.67 (s, 2H), 4.60 (s, 2H), 4.39-4.48 (m, 1H), 4.30 (m, 2H), 4.28 (m, 2H), 3.63-3.79 (m, 5H), 2.47-2.49 (m, 1H), 2.22-2.26 (m, 1H), 1.48 (s, 4H), 1.45 (s, 5H). ESI-MS (M+H + ): m/z calculated 449.2, founded 449.3.
Example 9
Synthesis of Compound 4c
[0191] SM-4 (5.37 g, 21.9 mmol) and CDI (14.2 g, 87.5 mmol, 4 eq.) were dissolved in 100 mL anhydrous dichloromethane and stirred at room temperature overnight, followed by adding another compound VIc (43.7 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 4c (6.1 g), yield 82%.
[0192] The product 4c was confirmed by ESI-MS (M+H + ): m/z calculated 449.2, founded 449.3.
Example 10
Synthesis of Compound 4d
[0193] SM-4 (5.37 g, 21.9 mmol) and CDI (14.2 g, 87.5 mmol, 4 eq.) were dissolved in 100 mL anhydrous dichloromethane and stirred at room temperature overnight, followed by adding another compound VId (43.7 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 4d (6.1 g), yield 82%.
[0194] The product 4d was confirmed by ESI-MS (M+H + ): m/z calculated 449.2, founded 449.3.
Example 11
Synthesis of Compound 4e
[0195] SM-4 (5.37 g, 21.9 mmol) and CDI (14.2 g, 87.5 mmol, 4 eq.) were dissolved in 100 mL anhydrous dichloromethane and stirred at room temperature overnight, followed by adding another compound VIe (43.7 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 4e (5.7 g), yield 75%.
[0196] 1 H-NMR for the product 4e (CDCl 3 , 500 MHz): δ 6.77 (s, 1H), 6.73 (s, 1H), 5.32 (m, 1H), 4.63 (s, 2H), 4.56 (s, 2H), 4.37-4.48 (m, 1H), 4.26 (s, 4H), 3.64-3.79 (m, 5H), 2.47 (m, 1H), 2.21-2.26 (m, 1H), 1.48 (s, 4H), 1.44 (s, 5H). ESI-MS (M+H + ): m/z calculated 449.2, founded 449.3.
Example 12
Synthesis of Compound 4f
[0197] SM-4 (5.37 g, 21.9 mmol) and CDI (14.2 g, 87.5 mmol, 4 eq.) were dissolved in 100 mL anhydrous dichloromethane and stirred at room temperature overnight, followed by adding another compound VIf (43.7 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 4f (5.9 g), yield 74%.
[0198] 1 H-NMR for the product 4f (CDCl 3 , 500 MHz): δ 6.71 (s, 1H), 6.67 (s, 1H), 5.97 (s, 2H), 5.32 (m, 1H), 4.63 (s, 2H), 4.57 (s, 2H), 4.38-4.47 (m, 1H), 3.64-3.76 (m, 5H), 2.47 (m, 1H), 2.23-2.25 (m, 1H), 1.47 (s, 4H), 1.44 (s, 5H). ESI-MS (M+H + ): m/z calculated 435.2, founded 435.3.
Example 13
Synthesis of Compound 6a
[0199] The product of 4a (2 g, 4.9 mmol) was dissolved in 40 mL 4N HCl/Et 2 O solvent and stirred at 30° C. until the completely deprotecting of Boc to give product 5a.
[0200] The concentrated 5a was dissolved in 50 mL DMF, compound SM-5 (1.40 g, 5.14 mmol, 1.05 eq.) and HATU (2.05 g, 5.39 mmol, 1.1 eq.) were added. After cooled in ice bath for 15 minute, DIEA (2.53 g, 19.6 mmol, 4 eq.) was added dropwise, the mixture was warmed to room temperature and stirred overnight until completed (monitored by HPLC-ELSD). The organic layer was separated and the water phase was extracted twice with ethyl acetate (2×100 mL). The combined organic layer as was washed with 1N hydrochloric acid, water, saturated sodium bicarbonate, and brine, dried and evaporated, finally purified by flash column to obtain desired product 6a (2.5 g), yield 87%, confirmed by ESI-MS (M+H + ): m/z calculated: 588.3, founded: 588.3.
Example 14
Synthesis of Compound 7a
[0201] The product of 6a (2.3 g, 4.2 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (0.54 g, 12.8 mmol, 3 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 7a (2.18 g), yield >95%, confirmed by ESI-MS (M+H + ): m/z calculated 574.3, founded 574.4.
Example 15
Synthesis of Compound 8
[0202] The raw material SM-7 (6.5 g, 18 mmol) was dissolved in HCl/Et 2 O solution (4M, 80 mL) and stirred at 30° C. until completed.
[0203] The above de-Boc product was concentrated and dissolved in 150 mL DMF. Compound (L)-N-Boc-2-amino-8-azelaic acid (SM-5, 5.2 g, 19 mmol, 1.05 eq.) and HATU (7.6 g, 20 mmol, 1.1 eq.) were added. After cooled in ice bathed for 15 minute, DIEA (9.5 g, 76 mmol, 4 eq.) was added dropwise, the mixture was warmed to room temperature and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 8 (2.5 g), yield 87%.
[0204] 1 H-NMR for the product 8 (CDCl3, 500 MHz): δ 7.73 (s, 1H), 5.70-5.79 (m, 2H), 5.27-5.31 (d, 1H, J=17 Hz), 5.22-5.24 δ (d, 1H, J=8 Hz), 5.11-5.13 (m, 1H), 4.93-5.01 (m, 2H), 4.68-4.71 (t, 1H, J=7.5 Hz), 4.54 (br, 1H), 4.36-4.37 (m, 1H), 3.94-3.97 (d, 1H, J=11.5 Hz), 3.65 (s, 3H), 3.55-3.58 (m, 1H), 3.39 (br, 1H), 2.97 (s, 1H), 2.89 (s, 1H), 2.49-2.52 (m, 1H), 2.12-2.16 (m, 1H), 2.02-2.04 (m, 4H), 1.83-1.85 (m, 1H), 1.74-1.78 (m, 1H), 1.59-1.61 (m, 1H), 1.43 (s, 9H), 1.31-1.40 (m, 4H), confirmed by ESI-MS (M+H + ): m/z calculated: 508.3, founded: 508.5.
Example 16
Synthesis of Compound 9a
[0205] The two methods of synthesis of compounds 9a-9d shown above.
[0206] Method I:
[0207] The product 7a (2.0 g, 4 mmol) and vinyl substituted cyclopropyl amino acid methyl ester reagents SM-6 (1.3 g, 4.2 mmol, 1.05 eq.) and the coupling reagent HATU (1.83 g, 4.82 mmol, 1.1 eq.) were dissolved in 80 mL DMF. After cooled in ice bathed for 15 minute, DIEA (2.27 g, 17.5 mmol, 4 eq.) was added dropwise, the mixture was warmed to room temperature and stirred overnight, followed by adding the product VIa (5.12 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9a (2.4 g), yield 81%, confirmed by ESI-MS (M+H + ): m/z calculated 699.3, founded 699.4.
[0208] Method II:
[0209] The product of the above Experiment 9 8 (1.3 g, 2.56 mmol) and CDI (1.66 g, 10.2 mmol, 4 eq.) were dissolved in 50 mL anhydrous dichloromethane and stirred at room temperature overnight. When HPLC-ELSD shows the reaction was completed, the product of Experiment 1 VIa (5.12 mmol, 2 eq.) was added and stirred at room temperature until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9a (1.4 g), yield 86%, confirmed by ESI-MS (M+H + ): m/z calculated: 699.3, founded: 699.4.
Example 17
Synthesis of Compound 9b
[0210] The synthesis of compounds 9b adopted method II shown above: the product 8 (1.3 g, 2.56 mmol) and CDI (1.66 g, 10.2 mmol, 4 eq.) were dissolved in 50 mL of anhydrous dichloromethane at room temperature overnight, followed by adding the product VIb (5.12 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9b (1.6 g), yield 94%, confirmed by ESI-MS (M+H + ): m/z calculated 711.4, founded 711.5.
Example 18
Synthesis of Compound 9c
[0211] The synthesis of compounds 9c adopted method II shown above: the product 8 (1.3 g, 2.56 mmol) and CDI (1.66 g, 10.2 mmol, 4 eq.) were dissolved in 50 mL of anhydrous dichloromethane at room temperature overnight, followed by adding the product VIc (5.12 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9c (1.3 g), yield 77%, confirmed by ESI-MS (M+H + ): m/z calculated 711.4, founded 711.5.
Example 19
Synthesis of Compound 9d
[0212] The synthesis of compounds 9d adopted method II shown above: the product 8 (1.3 g, 2.56 mmol) and CDI (1.66 g, 10.2 mmol, 4 eq.) were dissolved in 50 mL of anhydrous dichloromethane at room temperature overnight, followed by adding the product VId (5.12 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9d (1.3 g), yield 77%, confirmed by ESI-MS (M+H + ): m/z calculated 711.4, founded 711.5.
Example 20
Synthesis of Compound 9e
[0213] The synthesis of compounds 9e adopted method II shown above: the product of the above mentioned Experiment 9 8 (1.3 g, 2.56 mmol) and CDI (1.66 g, 10.2 mmol, 4 eq.) were dissolved in 50 mL of anhydrous dichloromethane at room temperature overnight, followed by adding the product VIe (5.12 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9e (1.4 g), yield 83%, and confirmed by ESI-MS (M+H + ): m/z calculated 711.4, founded 711.5.
Example 21
Synthesis of Compound 9f
[0214] The synthesis of compounds 9f adopted method II shown above: the product 8 (1.3 g, 2.56 mmol) and CDI (1.66 g, 10.2 mmol, 4 eq.) were dissolved in 50 mL of anhydrous dichloromethane at room temperature overnight, followed by adding the product VIf (5.12 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9f (1.3 g), yield 78%, and confirmed by ESI-MS (M+H + ): m/z calculated: 697.3, founded: 697.4.
Example 22
Synthesis of Compound 9-Ref
[0215] Synthesis of compounds 9-Ref adopted method II shown above: the product 8 (1.3 g, 2.56 mmol) and CDI (1.66 g, 10.2 mmol, 4 eq.) were dissolved in 50 mL of anhydrous DCE at room temperature overnight, followed by adding another compound SM-8 (43.7 mmol, 2 eq.) until completed. The reaction mixture was worked out and purified by flash column to obtain the product 9e (1.4 g), yield 81%.
[0216] 1 H-NMR for the product 9-Ref (CDCl 3 , 500 MHz): δ 7.65-7.70 (d, 1H, J=9 Hz), 6.96-7.07 (m, 2H), 5.72-5.78 (m, 2H), 5.40 (br, 1H), 5.28-5.31 (d, 1H, J=16.5 Hz), 5.12-5.14 (d, 1H, J=10.5 Hz), 5.07-5.09 (d, 1H, J=7.5 Hz), 4.93-5.00 (m, 2H), 4.64-4.79 (m, 5H), 4.36-4.37 (m, 1H), 4.06 (m, 1H), 3.72-3.75 (m, 1H), 3.67 (s, 3H), 2.78 (m, 1H), 2.26 (m, 1H), 2.14-2.16 (m, 1H), 2.01-2.03 (m, 2H), 1.86-1.88 (m, 1H), 1.70-1.73 (m, 1H), 1.57-1.60 (m, 1H), 1.45-1.49 (m, 2H), 1.37-1.40 (m, 4H), 1.32 (s, 4H), 1.29 (s, 5H), and confirmed by Mass spectrometry, ESI-MS (M+H + ): m/z calculated 691.3, founded 691.4.
Example 23
Synthesis of Compound 10a
[0217] Under argon protection atmosphere, compound 9a (2.25 mmol) was dissolved in 450 mL of anhydrous dichloromethane, and Zhan Catalyst-1B (RC-303, 74.4 mg, 0.113 mmol, 0.05 eq.) was added. The reaction flask was stirred in a preheated oil bath at 80° C. overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 10a (1.2 g), yield 64%, and confirmed by ESI-MS (M+H + ): m/z calculated 669.3, founded 669.4.
Example 24
Synthesis of Compound 10b
[0218] Under argon protection atmosphere, compound 9b (2.25 mmol) was dissolved in 450 mL of anhydrous dichloromethane, and Zhan Catalyst-1B (RC-303, 74.4 mg, 0.113 mmol, 0.05 eq.) was added. The reaction flask was stirred in a preheated oil bath at 80° C. overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 10b (1.3 g), yield 67%, and confirmed by ESI-MS (M+H + ): m/z calculated 683.3, founded 683.5.
Example 25
Synthesis of Compound 10e
[0219] Under argon protection atmosphere, compound 9c (2.25 mmol) was dissolved in 450 mL of anhydrous dichloromethane, and Zhan Catalyst-1B (RC-303, 74.4 mg, 0.113 mmol, 0.05 eq.) was added. The reaction flask was stirred in a preheated oil bath at 80° C. overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 10c (1.2 g), yield 56%, and confirmed by ESI-MS (M+H + ): m/z calculated 683.3, founded 683.5.
Example 2
Synthesis of Compound 10d
[0220] Under argon protection atmosphere, compound 9d (2.25 mmol) was dissolved in 450 mL of anhydrous dichloromethane, and Zhan Catalyst-1B (RC-303, 74.4 mg, 0.113 mmol, 0.05 eq.) was added. The reaction flask was stirred in a preheated oil bath at 80° C. overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 10d (1.3 g), yield 61%, and confirmed by ESI-MS (M+H + ): m/z calculated 683.3, founded 683.5.
Example 27
Synthesis of Compound 10e
[0221] Under argon protection atmosphere, compound 9e (2.25 mmol) was dissolved in 450 mL of anhydrous dichloromethane, and Zhan Catalyst-1B (RC-303, 74.4 mg, 0.113 mmol, 0.05 eq.) was added. The reaction flask was stirred in a preheated oil bath at 80° C. overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 10e (1.1 g), yield 51%, and confirmed by ESI-MS (M+H + ): m/z calculated 683.3, founded 683.5.
Example 28
Synthesis of Compound 10f
[0222] Under argon protection atmosphere, compound 9f (2.25 mmol) was dissolved in 450 mL of anhydrous dichloromethane, and Zhan Catalyst-1B (RC-303, 74.4 mg, 0.113 mmol, 0.05 eq.) was added. The reaction flask was stirred in a preheated oil bath at 80° C. overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 10f (0.9 g), yield 47%, and confirmed by ESI-MS (M+H + ): m/z calculated 669.3, founded 669.4.
Example 29
Synthesis of Compound 10-Ref
[0223] Under argon protection atmosphere, compound 9-Ref (2.25 mmol) was dissolved in 450 mL of anhydrous dichloromethane, and Zhan Catalyst-1B (RC-303, 74.4 mg, 0.113 mmol, 0.05 eq.) was added. The reaction flask was stirred in a preheated oil bath at 80° C. overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 10-Ref (1.4 g), yield 71%.
[0224] 1 H-NMR for the product 10-Ref (CDCl 3 , 500 MHz): δ 6.96-7.07 (m, 3H), 5.53-5.55 (m, 1H), 5.39 (m, 1H), 5.23-5.28 (m, 2H), 4.69-4.84 (m, 5H), 4.49 (m, 1H), 4.05-4.07 (m, 1H), 3.86-3.89 (m, 1H), 3.67 (s, 3H), 2.82-2.85 (m, 1H), 2.25-2.27 (m, 1H), 2.16-2.19 (m, 3H), 1.85-1.88 (m, 2H), 1.56-1.73 (m, 3H), 1.38-1.43 (m, 4H), 1.35 (s, 4H), 1.34 (s, 5H), and confirmed by ESI-MS (M+H + ): m/z calculated 643.3, founded 643.5.
Example 30
Synthesis of Compound 11a
[0225] The compound 10a (0.6 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (122.9 mg, 2.93 mmol, 5 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11a (466 mg), yield >95%, and confirmed by ESI-MS (M+H + ): m/z calculated 655.3, founded 655.3.
Example 31
Synthesis of Compound 11b
[0226] The compound 10b (0.6 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (122.9 mg, 2.93 mmol, 5 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11b (439 mg), yield >95%, and confirmed by ESI-MS (M+H + ): m/z calculated 669.3, founded 669.3.
Example 32
Synthesis of Compound 11c
[0227] The compound 10c (0.6 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (122.9 mg, 2.93 mmol, 5 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11c (453 mg), yield >95%, and confirmed by ESI-MS (M+H + ): m/z calculated 673.3, founded 673.3.
Example 33
Synthesis of Compound 11d
[0228] The compound 10d (0.6 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (122.9 mg, 2.93 mmol, 5 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11d (457 mg), yield >95%, and confirmed by ESI-MS (M+H + ): m/z calculated 673.3, founded 673.3.
Example 34
Synthesis of Compound 11e
[0229] The compound 10e (0.6 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (122.9 mg, 2.93 mmol, 5 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11e (418 mg), yield 85%, and confirmed by ESI-MS (M+H + ): m/z calculated 669.3, founded 669.3.
Example 35
Synthesis of Compound 11f
[0230] The compound 10f (0.6 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (122.9 mg, 2.93 mmol, 5 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11f (453 mg), yield >95%, and confirmed by ESI-MS (M+H + ): m/z calculated 655.3, founded 655.4.
Example 36
Synthesis of Compound 11j
[0231] Compound 10e (0.55 g, 0.81 mmol) was suspended in 10 mL 4N HCl/ether solvent, stirred for 2 h and concentrated. 10 mL DCM and triethylamine (0.82 g, 8 mmol) were added and cooled to 0-5° C. The raw material sulfonyl chloride (0.29 g, 1.6 mmol) was added slowly and the reaction was stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column, and the product 13j (0.43 g, yield: 73%).
[0232] Compound 13j (0.4 g) was to added to the mixture solvent of NaOH (120 mg, 3 mmol), 10 mL methanol and 0.5 mL of water. The reaction mixture was stirred at 60° C. for 5 hr until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11j (0.31 g, yield: 80%).
[0233] 1 H-NMR for the product 11j (CDCl 3 , 500 MHz): δ 7.30 (s, 1H); 6.76 (s, 1H); 6.68 (s, 1H); 5.69 (q, J=8.0 Hz, 1H); 5.48 (s, 1H); 5.15 (t, J=8.0 Hz, 1H); 4.63-4.48 (m, 5H); 4.24 (s, 4H); 4.23-4.14 (m, 2H); 3.86 (m, 1H); 3.71 (m, 1H); 3.39 (m, 1H); 3.07-2.91 (m, 2H); 2.57 (m, 1H); 2.44 (m, 1H); 2.36-2.22 (br, 4H); 2.04 (m, 1H); 1.93 (m, 1H); 1.81 (m, 1H); 1.64-1.55 (br, 3H); 1.46-1.29 (br, 4H); 1.24-1.20 (br, 2H), and confirmed by ESI-MS (M+H + ): m/z calculated 673.2, founded 673.3.
Example 37
Synthesis of Compound 11k
[0234] The synthesis of compound 11k was the same as 11j.
[0235] Compound 10f (0.55 g, 0.81 mmol) was suspended in 10 mL 4N HCl/ether solvent, stirred for 2 h and concentrated. 10 mL DCM and triethylamine (0.82 g, 8 mmol) were added and cooled to 0-5° C. The raw material sulfonyl chloride (0.29 g, 1.6 mmol) was added slowly and the reaction was stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column, and the product 13k (0.48 g, yield: 91%).
[0236] Compound 13k (0.4 g) was added to the mixture solvent of NaOH (120 mg, 3 mmol), 10 mL methanol and 0.5 mL of water. The reaction mixture was stirred at 60° C. for 5 hr until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11k (0.30 g, yield: 78%).
[0237] 1 H-NMR for the product 11k (CDCl 3 , 500 MHz): δ 7.32 (s, 1H); 6.71 (s, 1H); 6.63 (s, 1H); 5.96 (s, 2H); 5.69 (q, J=8.0 Hz, 1H); 5.48 (s, 1H); 5.15 (t, J=8.0 Hz, 1H); 4.64-4.49 (m, 5H); 4.23-4.15 (m, 2H); 3.89 (m, 1H); 3.72 (m, 1H); 3.40 (m, 1H); 3.09-2.89 (m, 2H); 2.58 (m, 1H); 2.48 (m, 1H); 2.39-2.26 (br, 4H); 2.08 (m, 1H); 1.96 (m, 1H); 1.82 (m, 1H); 1.69-1.54 (br, 3H); 1.46-1.29 (br, 4H); 1.26-1.20 (br, 2H) and confirmed by ESI-MS (M+H + ): m/z calculated 659.2, founded 659.3.
Example 38
Synthesis of Compound 11m
[0238] The synthesis of compound 11m was the same as 11j.
[0239] Compound 10-Ref (0.55 g, 0.81 mmol) was suspended in 10 mL 4N HCl/ether solvent, stirred for 2 h and concentrated. 10 mL DCM and triethylamine (0.82 g, 8 mmol) were added and cooled to 0-5° C. The raw material sulfonyl chloride (0.29 g, 1.6 mmol) was added slowly and the reaction was stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column, and the product 13m (0.35 g, yield: 65%).
[0240] Compound 13m (0.3 g) was added to the mixture solvent of NaOH (120 mg, 3 mmol), 10 mL methanol and 0.5 mL of water. The reaction mixture was stirred at 60° C. for 5 hr until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11m (0.21 g, yield: 76%).
[0241] 1 H-NMR for the product 11m (CDCl 3 , 500 MHz): δ 7.25 (m, 1H); 7.06-6.95 (m, 2H); 5.71 (q, J=8.0 Hz, 1H); 5.49 (s, 1H); 5.32 (s, 1H); 5.14 (t, J=8.0 Hz, 1H); 4.80-4.4.61 (m, 5H); 4.31 (m, 1H); 4.16 (m, 1H); 3.86 (m, 1H); 3.72 (q, J=5.6 Hz, 1H); 3.40 (q, J=5.6 Hz, 1H); 3.02 (m, 1H); 2.92 (m, 1H); 2.61 (br, 1H); 2.52-2.41 (br, 2H); 2.33-2.24 (br, 3H); 2.06 (br, 1H); 1.93 (br, 1H); 1.83 (br, 1H); 1.63-1.54 (br, 3H); 1.42-1.22 (br, 6H) and confirmed by ESI-MS (M+H + ): m/z calculated 633.2, founded 633.3.
Example 39
Synthesis of Compound 11-Ref
[0242] Synthesis of compound 11-Ref was the same as 11a.
[0243] The compound 10-Ref (0.6 mmol) was dissolved in 30 mL THF, 15 mL methanol and 15 mL water. Lithium hydroxide monohydrate (122.9 mg, 2.93 mmol, 5 eq.) was added and stirred overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 11-Ref (438 mg), yield >95%.
[0244] 1 H-NMR for the product 11-Ref (CDCl 3 , 500 MHz): δ 7.16 (m, 1H), 6.96-7.07 (m, 2H), 5.63-5.64 (m, 1H), 5.32 (m, 1H), 5.20-5.28 (m, 2H), 4.68-4.78 (m, 5H), 4.34-4.40 (m, 1H), 4.19 (m, 1H), 3.89 (m, 1H), 2.68-2.78 (m, 1H), 2.32 (m, 2H), 2.21 (m, 1H), 2.10 (m, 1H), 1.84-1.87 (m, 2H), 1.59-1.62 (m, 2H), 1.40-1.45 (m, 5H), 1.32 (s, 4H), 1.30 (s, 5H) and confirmed by ESI-MS (M+H + ): m/z calculated 629.3, founded 629.4.
Example 40
Synthesis of Compound 12a
[0245] Compound 11a (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0246] The obtained solid mixture above was dissolved in 10 mL of anhydrous DCE, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.36 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12a (56 mg; Yield: 58%).
[0247] 1 H-NMR for the product 12a (CDCl 3 , 500 MHz): δ 10.29-10.30 (d, 1H), 6.97-7.02 (d, 2H), 6.60-6.78 (m, 2H), 5.98-5.99 (m, 2H), 5.70-5.73 (m, 1H), 5.47 (m, 1H), 4.98-5.08 (m, 2H), 4.56-4.70 (m, 5H), 4.37-4.40 (m, 1H), 4.21-4.23 (m, 1H), 3.84-3.86 (m, 1H), 2.90-2.93 (m, 1H), 2.50-2.56 (m, 2H), 2.46-2.48 (m, 1H), 2.25-2.28 (m, 1H), 1.89-1.95 (m, 2H), 1.74-1.79 (m, 2H), 1.46-1.58 (m, 6H), 1.36-1.39 (m, 2H), 1.29 (s, 4H), 1.25 (s, 5H), 1.08-1.16 (m, 2H), 0.90-0.95 (m, 1H); and confirmed by ESI-MS (M+H + ): m/z calculated 758.3, founded 758.4.
Example 41
Synthesis of Compound 12b
[0248] Compound 11b (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0249] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.36 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12b (53 mg; Yield: 51%).
[0250] 1 H-NMR for the product 12b (CDCl 3 , 500 MHz): δ 10.25-10.25 (d, 1H), 6.88-6.91 (m, 1H), 6.77-6.80 (m, 1H), 6.58-6.60 (m, 1H), 5.68-5.74 (m, 1H), 5.45 (m, 1H), 4.98-5.06 (m, 2H), 4.64-4.68 (m, 2H), 4.52-4.60 (m, 3H), 4.35-4.39 (m, 1H), 4.22-4.29 (m, 5H), 3.82-3.84 (m, 1H), 2.88-2.91 (m, 1H), 2.45-2.56 (m, 2H), 2.41-2.45 (m, 1H), 2.23-2.29 (m, 1H), 1.82-1.93 (m, 1H), 1.60-1.79 (m, 3H), 1.36-1.56 (m, 8H), 1.23-1.29 (m, 9H), 0.93-1.06 (m, 2H), 0.89-0.93 (m, 1H); and confirmed by ESI-MS (M+H + ): m/z calculated 772.3, founded 773.4.
Example 42
Synthesis of Compound 12c
[0251] Compound 11e (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0252] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.36 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12c (47 mg; Yield: 42%).
[0253] 1 H-NMR for the product 12c (CDCl 3 , 500 MHz): δ 10.27 (s, 1H), 6.92 (s, 1H), 6.77 (s, 1H), 6.65 (s, 1H), 5.72-5.73 (m, 1H), 5.46 (m, 1H), 5.09 (m, 1H), 5.00 (m, 1H), 4.64 (m, 2H), 4.53-4.56 (m, 3H), 4.37-4.40 (m, 1H), 4.25 (m, 5H), 3.84-3.86 (m, 1H), 2.90 (m, 1H), 2.46-2.53 (m, 3H), 2.27-2.29 (m, 1H), 1.87-1.94 (m, 2H), 1.72 (m, 2H), 1.58 (m, 1H), 1.47 (m, 5H), 1.38 (m, 2H), 1.31 (s, 9H), 1.11 (m, 2H), 0.91 (m, 1H); and confirmed by ESI-MS (M+H + ): m/z calculated 772.3, founded 773.4.
Example 43
Synthesis of Compound 12d
[0254] Compound 11f (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0255] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.36 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12d (65 mg; Yield: 67%).
[0256] 1 H-NMR for the product 12d (CDCl 3 , 500 MHz): δ 10.24 (s, 1H), 6.80 (s, 1H), 6.72 (s, 1H), 6.59 (s, 1H), 5.98 (s, 2H), 5.70-5.76 (m, 1H), 5.47 (m, 1H), 5.03 (m, 2H), 4.65 (m, 2H), 4.53-4.57 (m, 3H), 4.38-4.41 (m, 1H), 4.23 (m, 1H), 3.85 (d, 1H), 2.92 (m, 1H), 2.51-2.57 (m, 2H), 2.45 (m, 1H), 2.28 (m, 1H), 1.95 (m, 2H), 1.59 (m, 1H), 1.59-1.65 (m, 2H), 1.48 (m, 5H), 1.38 (m, 2H), 1.30 (s, 9H), 1.12 (m, 2H), 0.92 (m, 1H).
[0257] ESI-MS (M+H + ): m/z calculated 758.3, founded 758.5.
Example 44
Synthesis of Compound 12e
[0258] Compound 11a (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0259] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=isopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12e (53 mg; Yield: 49%).
[0260] 1 H-NMR for the product 12e (CDCl 3 , 500 MHz): δ 9.91-9.93 (d, 1H), 6.72-6.83 (m, 3H), 5.95-5.99 (m, 2H), 5.72-5.73 (m, 1H), 5.47 (m, 1H), 4.99-5.05 (m, 2H), 4.57-4.71 (m, 5H), 4.40-4.42 (m, 1H), 4.22 (m, 1H), 3.83-3.85 (d, 1H), 3.70-3.72 (m, 1H), 2.55-2.57 (m, 2H), 2.46-2.48 (m, 1H), 2.27-2.30 (m, 1H), 1.97 (m, 1H), 1.76-1.86 (m, 3H), 1.42-1.46 (m, 6H), 1.32-1.37 (m, 4H), 1.24-1.28 (d, 9H), 0.89-0.91 (m, 3H). ESI-MS (M+H + ): m/z calculated 760.3, founded 760.4.
Example 45
Synthesis of Compound 12f
[0261] Compound 11b (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0262] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=isopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12f (50 mg; Yield: 46%).
[0263] 1 H-NMR for the product 12f (CDCl 3 , 500 MHz): δ 9.94 (s, 1H), 6.73-6.78 (m, 2H), 6.59-6.73 (m, 1H), 5.69-5.75 (m, 1H), 5.47 (m, 1H), 4.99-5.05 (m, 2H), 4.63-4.67 (m, 2H), 4.42-4.53 (m, 3H), 4.29-4.38 (m, 1H), 4.25-4.29 (m, 5H), 3.83-3.86 (m, 1H), 3.68-3.75 (m, 1H), 2.53-2.58 (m, 2H), 2.43-2.48 (m, 1H), 2.28-2.30 (m, 1H), 1.96-2.00 (m, 1H), 1.69-1.93 (m, 3H), 1.42-1.47 (m, 6H), 1.32-1.44 (m, 4H), 1.24-1.29 (m, 9H), 0.86-0.93 (m, 3H); and confirmed by ESI-MS (M+H + ): m/z calculated 774.3, founded 774.4.
Example 46
Synthesis of Compound 12g
[0264] Compound 11c (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0265] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=isopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out to obtain the white solid product 12g (45 mg; Yield: 38%).
[0266] 1 H-NMR for the product 12g (CDCl 3 , 500 MHz): δ 9.91 (s, 1H), 6.77-6.78 (m, 2H), 6.65 (s, 1H), 5.69-5.75 (m, 1H), 5.47 (m, 1H), 5.01-5.03 (m, 2H), 4.60-4.64 (m, 2H), 4.53-4.60 (m, 3H), 4.39-4.42 (m, 1H), 4.26 (m, 5H), 3.84-3.85 (m, 1H), 3.69-3.72 (m, 1H), 2.54-2.56 (m, 2H), 2.43-2.48 (m, 1H), 2.28-2.29 (m, 1H), 1.96 (m, 1H), 1.74-1.86 (m, 2H), 1.59 (m, 1H), 1.37-1.43 (m, 7H), 1.32-1.33 (m, 15H); and confirmed by ESI-MS (M+H + ): m/z calculated 774.3, founded 774.4.
Example 47
Synthesis of Compound 12h
[0267] Compound 11d (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0268] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=isopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12h (53 mg; Yield: 48%).
[0269] 1 H-NMR for the product 12h (CDCl 3 , 500 MHz): δ 9.95 (s, 1H), 6.90 (s, 1H), 6.71 (s, 1H), 6.59 (s, 1H), 5.98 (s, 2H), 5.73 (m, 1H), 5.47 (m, 1H), 5.04 (m, 2H), 4.65 (m, 2H), 4.53-4.57 (m, 3H), 4.39-4.41 (m, 1H), 4.23 (m, 1H), 3.84-3.85 (d, 1H), 3.70 (m, 1H), 2.53 (m, 2H), 2.48 (m, 1H), 2.28 (m, 1H), 1.95 (m, 1H), 1.76-1.86 (m, 3H), 1.57 (m, 1H), 1.41-1.46 (m, 7H), 1.30 (m, 15H); and confirmed by ESI-MS (M+H + ): m/z calculated 760.3, founded 760.4.
Example 48
Synthesis of Compound 12j
[0270] Compound 11j (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0271] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12j (73 mg; Yield: 61%).
[0272] 1 H-NMR for the product 12j (CDCl 3 , 500 MHz): δ 10.35 (s, 1H), 7.35 (s, 1H), 6.74 (s, 1H), 6.67 (s, 1H), 5.72-5.77 (q, 1H, J=8.5 Hz), 5.52 (m, 1H), 5.00-5.04 (t, 1H, J=9.5 Hz), 4.57-4.64 (m, 2H), 4.46-4.57 (m, 3H), 4.23-4.25 (m, 5H), 4.08-4.11 (d, 1H), 3.88-3.90 (m, 1H), 3.65-3.69 (m, 1H), 3.32-3.37 (m, 1H), 2.92-3.05 (m, 2H), 2.88-2.92 (m, 1H), 2.66-2.74 (m, 1H), 2.40-2.53 (m, 2H), 2.26-2.35 (m, 3H), 1.80-2.05 (m, 3H), 1.48-1.68 (m, 3H), 1.26-1.48 (m, 6H), 1.08-1.13 (m, 2H), 0.90-0.94 (m, 1H). ESI-MS (M+H + ): m/z calculated 776.3, founded 776.4.
Example 49
Synthesis of Compound 12k
[0273] Compound 11k (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0274] The obtained solid was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12k (54 mg; Yield: 38%).
[0275] 1 H-NMR for the product 12k (CDCl 3 , 500 MHz): δ 10.36 (s, 1H), 7.39 (s, 1H), 6.70 (s, 1H), 6.64 (s, 1H), 5.97 (s, 2H), 5.74-5.76 (m, 2H), 5.53 (m, 1H), 5.01-5.05 (t, 1H, J=9.5 Hz), 4.46-4.64 (m, 5H), 4.24-4.26 (d, 1H), 4.10-4.13 (m, 1H), 3.88-3.91 (m, 1H), 3.66-3.68 (m, 1H), 3.33-3.38 (m, 1H), 2.90-3.03 (m, 3H), 2.71 (m, 1H), 2.49-2.51 (m, 1H), 2.42-2.45 (m, 1H), 2.28-2.34 (m, 3H), 1.81-2.02 (m, 4H), 1.62-1.69 (m, 4H), 1.44-1.49 (m, 4H), 1.08-1.14 (m, 2H), 0.86-0.96 (m, 1H). ESI-MS (M+H + : m/z calculated 762.2, founded 762.3.
Example 50
Synthesis of Compound 12m
[0276] Compound 11m (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0277] The obtained solid was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12m (61 mg; Yield: 52%).
[0278] 1 H-NMR for the product 12m (CDCl 3 , 500 MHz): δ 10.38-10.41 (d, 1H), 7.51-7.55 (d, 1H, J=20 Hz), 6.94-7.05 (m, 2H), 5.73-5.79 (m, 2H), 5.54 (m, 1H), 5.02-5.06 (t, 1H, J=9.5 Hz), 4.75-4.85 (m, 2H), 4.54-4.64 (m, 3H), 4.29-4.33 (t, 1H, J=11 Hz), 4.08-4.10 (d, 1H), 3.85-3.89 (m, 1H), 3.65-3.68 (m, 1H), 3.31-3.36 (m, 3H), 2.73-2.74 (m, 1H), 2.51-2.52 (m, 2H), 2.27-2.36 (m, 3H), 1.72-2.02 (m, 4H), 1.27-1.66 (m, 9H), 1.09-1.13 (m, 2H), 0.91-0.95 (m, 1H). ESI-MS (M+H): m/z calculated 736.2, founded 736.4.
Example 51
Synthesis of Compound 12n
[0279] Compound 11c (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0280] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.36 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12n (47 mg; Yield: 42%).
[0281] 1 H-NMR for the product 12n (CDCl 3 , 500 MHz): δ10.27 (s, 1H), 6.89-6.92 (m, 2H), 6.67-6.79 (m, 1H), 5.72-5.74 (m, 1H), 5.46-5.47 (m, 1H), 4.99-5.07 (m, 2H), 4.55-4.69 (m, 5H), 4.39 (m, 1H), 4.21-4.25 (m, 5H), 3.84-3.86 (m, 1H), 2.90-2.93 (m, 1H), 2.45-2.56 (m, 3H), 2.19-2.29 (m, 3H), 1.89-1.95 (m, 2H), 1.71-1.79 (m, 2H), 1.58 (m, 1H), 1.34-1.50 (m, 7H), 1.29 (s, 5H), 1.25 (s, 4H), 1.08-1.16 (m, 2H), 0.92-0.94 (m, 1H). ESI-MS (M+H + ): m/z calculated 786.3, founded 786.4.
Example 52
Synthesis of Compound 12p
[0282] Compound 11d (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0283] The obtained solid mixture was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.36 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12p (65 mg; Yield: 67%).
[0284] 1 H-NMR for the product 12p (CDCl 3 , 500 MHz): δ 10.28 (s, 1H), 7.00 (s, 1H), 6.87 (s, 1H), 6.75 (s, 1H), 5.70-5.72 (m, 1H), 5.45 (m, 1H), 4.97-5.09 (m, 2H), 4.52-4.63 (m, 5H), 4.35-4.38 (m, 1H), 4.14-4.22 (m, 5H), 3.83-3.84 (m, 1H), 2.88-2.91 (m, 1H), 2.44-2.53 (m, 3H), 2.17-2.27 (m, 3H), 1.76-1.91 (m, 4H), 1.57 (m, 1H), 1.37-1.51 (m, 7H), 1.28 (s, 9H), 1.06-1.13 (m, 2H), 0.89-0.93 (m, 1H). ESI-MS (M+H + : m/z calculated 786.3, founded 786.4.
Example 53
Synthesis of Compound 12q
[0285] Compound 12d (0.18 mmol) was dissolved in 20 mL HCl-Et 2 O (2N) and stirred at 30° C. until completed to obtain de-Boc product, followed by reacting with another reagent iPrOC(O)Cl (1.2 eq) to obtain the product 12q. yield: 72%.
[0286] 1 H-NMR for the product 12q (CDCl 3 , 500 MHz): δ10.27 (s, 1H), 6.97 (br, 1H), 6.70 (s, 1H), 6.59 (s, 1H), 5.95 (s, 2H), 5.70 (q, J=8.1 Hz, 1H), 5.44 (s, 1H), 5.14 (s, 1H), 4.99 (t, J=8.1 Hz, 1H), 4.65-4.47 (m, 5H), 4.35 (m, 2H), 4.24 (br, 1H), 3.82 (m, 1H), 2.91 (m, 1H), 2.45 (m, 3H), 2.23 (m, 1H), 1.92 (br, 2H), 1.74 (br, 2H), 1.59 (m, 1H), 1.47-1.27 (br, 8H), 1.11-1.06 (br, 5H), 1.01 (d, J=4.7 Hz, 3H), 0.96 (m, 1H). ESI-MS (M+H + ): m/z calculated 744.3, founded 744.3.
Example 54
Synthesis of Compound 12r
[0287] Compound 12d (0.18 mmol) was dissolved in 20 mL HCl-Et 2 O (2N) and stirred at 30° C. until completed to obtain de-Boc product, followed by reacting with another reagent iPrOC(O)Cl (1.2 eq) to obtain the product 12r. yield: 76%.
[0288] 1 H-NMR for the product 12r (CDCl 3 , 500 MHz): δ 10.35 (s, 1H), 7.26 (s, 1H), 6.68 (s, 1H), 6.57 (s, 1H), 5.92 (s, 2H), 5.67 (q, J=8.1 Hz, 1H), 5.42 (s, 1H), 4.95 (t, J=8.1 Hz, 1H), 4.58 (m, 5H), 4.29 (m, 2H), 3.81 (m, 1H), 2.86 (m, 1H), 2.42 (br, 3H), 2.24 (m, 1H), 1.77 (m, 4H), 1.58-1.25 (m, 18H), 1.07 (m, 2H), 0.90 (m, 1H). ESI-MS (M+H + ): m/z calculated 770.3, founded 770.4.
Example 55
Synthesis of Compound 12s
[0289] The synthetic procedure is the same as in Examples 48-50 starting 10f with in 0.3 mmol scale. Finally, 32 mg of product 12s was obtained, and confirmed by ESI-MS (M+H + ): m/z calculated 770.3, founded 770.4.
Example 56
Synthesis of Compound 12t
[0290] The synthetic procedure is the same as in Examples 48-50 starting 10f with in 0.3 mmol scale. Finally, 41 mg of product 12s was obtained, and confirmed by ESI-MS (M+H + ): m/z calculated 770.3, founded 770.4.
Example 57
Synthesis of Compound 12u
[0291] The synthetic procedure is the same as in Examples 48-50 starting 10-Ref with in 0.3 mmol scale. Finally, 52 mg of product 12u was obtained, and confirmed by ESI-MS (M+H + ): m/z calculated 810.3, founded 810.4.
Example 58
Synthesis of Compound 12-Ref
[0292] Compound 11-Ref (0.18 mmol) was dissolved in 10 mL anhydrous dichloromethane, EDCI (69.8 mg, 0.36 mmol, 2 eq.) was added and stirred at room temperature overnight until completed. The reaction mixture was worked out and concentrated.
[0293] The obtained solid was dissolved in 10 mL of anhydrous dichloromethane, DBU (61.0 mg, 0.40 mmol) and RSO 2 NH 2 (0.363 mmol, R=cyclopropyl) were added and stirred at room temperature overnight until completed. The reaction mixture was worked out and purified by flash column to obtain the product 12-Ref (62 mg; Yield: 53%).
[0294] 1 H-NMR for the product 12-Ref (CDCl3, 500 MHz): δ 10.28-10.29 (d, 1H), 6.87-7.07 (m, 3H), 5.72-5.74 (m, 1H), 5.48 (br, 1H), 4.99-5.03 (m, 2H), 4.58-4.79 (m, 5H), 4.42 (m, 1H), 4.21 (m, 1H), 3.83-3.85 (m, 1H), 2.90-2.93 (m, 1H), 2.48-2.57 (m, 3H), 2.27-2.30 (m, 1H), 1.88-1.97 (m, 2H), 1.67-1.79 (m, 2H), 1.45-1.58 (m, 6H), 1.34-1.40 (m, 2H), 1.27 (s, 4H), 1.24 (s, 5H), 1.08-1.15 (m, 2H), 0.91-0.94 (m, 1H). ESI-MS (M+H + ): m/z calculated 732.3, founded 732.5.
Example 59
Synthesis of Compound 15a
[0295] Compound 12d (3.0 mmol) was dissolved in 30 mL HCl-Et2O (4N) to remove Boc group, followed by adding phenyl borate and Cu(AcO)2 (2 eq/each) in DCE (30 mL) to obtain the product 15a (Yield: 62%). ESI-MS (M+H + ): m/z calculated 734.3, founded 734.4.
Example 60
Synthesis of Compound 15b
[0296] Compound 12d (3.0 mmol) was dissolved in 30 mL HCl-Et2O (4N) to remove Boc group, followed by adding m-fluorophenyl borate and Cu(AcO)2 (2 eq/each) in DCE (30 mL) to obtain the product 15b (Yield: 53%). ESI-MS (M+H + ): m/z calculated 752.3, founded 752.3.
Example 61
Synthesis of Compound 16a
[0297] Compound 12d (3.0 mmol) was dissolved in 30 mL HCl-Et2O (4N) to remove Boc group, followed by adding p-chlorophenylsulfonyl chloride (1.3 eq) in DCE (30 mL) to obtain the product 16a (Yield: 81%). ESI-MS (M+H + ): m/z calculated 832.2, founded 832.2.
Example 62
Synthesis of Compound 16b
[0298] Compound 12d (3.0 mmol) was dissolved in 30 mL HCl-Et2O (4N) to remove Boc group, followed by adding phenylsulfonyl chloride (1.3 eq)) in DCE (30 mL) to obtain the product 16b (Yield: 74%). ESI-MS (M+H + ): m/z calculated 798.2, founded 798.3.
Example 63
Synthesis of Compound 16c
[0299] Compound 12d (3.0 mmol) was dissolved in 30 mL HCl-Et2O (4N) to remove Boc group, followed by adding p-methoxyphenylsulfonyl chloride (1.3 eq) in DCE (30 mL) to obtain the product 16c (Yield: 79%). ESI-MS (M+H + ): m/z calculated: 828.2, founded: 828.3.
Example 64
Synthesis of Compound 17
[0300] SM-11 (35 g), DMF (350 mL) were added to a flask, followed by adding SM-12 (17 g) and HATU (10.4 g) into the reaction mixture in ice-water bath. After stirred for 10 minutes, DIEA (125 mL) was added, the mixture was allowed to room temperature. The mixture was stirred overnight and concentrated under reduced pressure. The reaction mixture was worked out and purified by flash column to obtain the foamy solid product 17 (18.6 g). Confirmed by ESI-MS (M+H + ): m/z calculated 407.3, founded 407.5.
Example 65
Synthesis of Compound 21a
[0301] The synthetic procedure starting with intermediate 17 is the same as in Examples 16-47 for preparation of 12a-12h in 1.0 mmol scale to prepare 21a. After purification, 59 mg of product 21a was obtained. Confirmed by ESI-MS (M+H + ): m/z calculated 669.3, founded 669.4.
Example 66
Synthesis of Compound 21b
[0302] The synthetic procedure starting with intermediate 17 is the same as in Examples 16-47 for preparation of 12a-12h in 1.0 mmol scale to prepare 21b. After purification, 46 mg of product 21b was obtained. Confirmed by ESI-MS (M+H + ): m/z calculated 683.3, founded 683.4.
Example 67
Synthesis of Compound 21c
[0303] The synthetic procedure starting with intermediate 17 is the same as in Examples 16-47 for preparation of 12a-12h in 1.0 mmol scale to prepare 21c. After purification, 49 mg of product 21c was obtained. Confirmed by ESI-MS (M+H + ): m/z calculated 643.3, founded 643.4.
Example 68
Synthesis of Compound 21d
[0304] The synthetic procedure starting with intermediate 17 is the same as in Examples 16-47 for preparation of 12a-12h in 1.0 mmol scale to prepare 21d. After purification, 63 mg of product 21d was obtained. Confirmed by ESI-MS (M+H + ): m/z calculated 683.3, founded 683.4.
Example 69
Synthesis of Compound 21e
[0305] The synthetic procedure starting with intermediate 17 is the same as in Examples 16-47 for preparation of 12a-12h in 1.0 mmol scale to prepare 21e. After purification, 63 mg of product 21e was obtained.
[0306] 1 H-NMR for the product 21e (CDCl 3 , 500 MHz): δ 10.60 (s, 1H), 7.10 (s, 1H), 6.61-6.74 (m, 3H), 5.95 (s, 2H), 5.65-5.69 (m, 1H), 5.26-5.29 (m, 1H), 4.98-5.09 (m, 1H), 4.65-4.68 (m, 1H), 4.41-4.56 (m, 4H), 3.88-3.91 (m, 1H), 3.47-3.53 (m, 2H), 3.19-3.26 (m, 1H), 3.07 (s, 1H), 2.96-3.01 (m, 1H), 2.90 (s, 3H), 2.50-2.64 (m, 1H), 2.24-2.28 (m, 1H), 2.04-2.16 (m, 3H), 1.67-1.99 (m, 4H), 1.08-1.49 (m, 8H), 0.86-0.96 (m, 2H). ESI-MS (M+H + ): m/z calculated 657.3, founded 657.4
Example 70
Synthesis of Compound 21f
[0307] The synthetic procedure starting with intermediate 17 is the same as in Examples 16-47 for preparation of 12a-12h in 1.0 mmol scale to prepare 21f. After purification, 63 mg of product 21f was obtained. Confirmed by ESI-MS (M+H + ): m/z calculated 669.3, founded 669.5.
Example 71
Synthesis of Compound 27a
[0308] The synthetic procedure starting with SM-7 in 5.0 mmol scale is the same as in Examples 7-47 for preparation of 12a-12h to prepare 27a. After purification, 69 mg of product 27a was obtained.
[0309] 1 H-NMR for the product 27a (CDCl 3 , 500 MHz): δ 6.71 (s, 1H), 6.66 (s, 1H), 5.97-5.98 (s, 2H), 5.70-5.73 (m, 1H), 5.31-5.37 (m, 1H), 5.13-5.17 (m, 1H), 4.83-4.86 (m, 1H), 4.51-4.62 (m, 4H), 3.80-3.83 (m, 1H), 3.78-3.79 (m, 1H), 3.52-3.54 (m, 1H), 3.06-3.09 (m, 1H), 2.90 (s, 3H), 2.48-2.49 (m, 1H), 2.23-2.35 (m, 2H), 2.00-2.08 (m, 4H), 1.63-1.72 (m, 2H), 1.38-1.51 (m, 8H), 1.80-1.82 (m, 3H). ESI-MS (M+H + ): m/z calculated 658.3, founded 658.4.
Example 72
Synthesis of Compound 27b
[0310] The synthetic procedure starting with SM-7 in 5.0 mmol scale is the same as in Examples 7-47 for preparation of 12a-12h to prepare 27b. After purification, 83 mg of product 27b was obtained.
[0311] 1 H-NMR for the product 27b (CDCl 3 , 500 MHz): δ 6.72-6.76 (m, 2H), 5.71-5.72 (m, 1H), 5.36-5.37 (m, 1H), 5.15-5.17 (m, 1H), 4.84-4.85 (m, 1H), 4.53-4.61 (m, 4H), 4.25 (s, 4H), 3.79-3.82 (m, 2H), 3.51-3.53 (m, 1H), 2.93-3.04 (m, 2H), 2.89 (s, 3H), 2.48-2.49 (m, 1H), 2.24-2.35 (m, 2H), 1.93-2.03 (m, 3H), 1.69-1.73 (m, 1H), 1.49-1.51 (m, 2H), 1.27-1.38 (m, 3H), 1.06-1.14 (m, 2H), 0.80-0.88 (m, 3H). ESI-MS (M+H + ): m/z calculated 672.3, founded 672.4.
Example 73
Synthesis of Compound 27c
[0312] The synthetic procedure starting with SM-7 in 5.0 mmol scale is the same as in Examples 7-47 for preparation of 12a-12h to prepare 27c. After purification, 57 mg of product 27c was obtained. Confirmed by ESI-MS (M+H + ): m/z calculated 630.3, founded 630.5
Example 74
Synthesis of Compound 27-Ref
[0313] The synthetic procedure starting with SM-7 in 5.0 mmol scale is the same as in Examples 7-47 for preparation of 12a-12h to prepare 27-Ref. After purification, 89 mg of product 27-Ref was obtained.
[0314] 1 H-NMR for the product 21e (CDCl 3 , 500 MHz): δ 7.41-7.43 (m, 1H), 6.96-7.07 (m, 2H), 5.71-5.73 (m, 1H), 5.38-5.39 (m, 1H), 5.13-5.18 (m, 1H), 4.84-4.88 (m, 1H), 4.73-4.77 (m, 2H), 4.67-4.70 (m, 2H), 3.80-3.84 (m, 1H), 3.65-3.68 (m, 1H), 3.52-3.56 (m, 1H), 3.06-3.09 (m, 1H), 2.93-2.96 (m, 1H), 2.89 (s, 3H), 2.49-2.52 (m, 2H), 2.24-2.36 (m, 2H), 2.00-2.10 (m, 2H), 1.68-1.69 (m, 2H), 1.48-1.51 (m, 2H), 1.27-1.38 (m, 5H), 1.07-1.31 (m, 2H). ESI-MS (M+H + ): m/z calculated 632.3, founded 632.4.
Example 75
Synthesis of Compound 27-Ref-2
[0315] The synthetic procedure starting with SM-7 in 5.0 mmol scale is the same as in Examples 7-47 for preparation of 12a-12h to prepare 27-Ref-2. After purification, 61 mg of product 27-Ref-2 was obtained. Confirmed by ESI-MS (M+H + ): m/z calculated 658.3, founded 658.4.
Example 76
Synthesis of Compound 30a
[0316] Chemical SM-13a (5.4 g, 10 mmol), sulfonamide (SM-8a, 1.1 eq) and DMF (80 mL) were added into 250 mL flask reactor, followed by adding coupling reagent EDCI (1.3 eq) to keep the amidation at 55° C. until completed. The reaction mixture was worked out to obtain crude product 28a, followed by removing Boc group with HCl-THF solution to obtain 29a (3.7 g, yield: 83%), which was purified by precipitation in hexane-EtOAc and dried directly for next step. ESI-MS (M+H + ): m/z calculated 533.2, founded 533.2.
[0317] In the presence of coupling reagent HATU (1.3 eq) in DMF (1.0 mL), compound 29a (60 mg, 0.1 mmol) was reacted with another acid derivative SM-14a to obtain product 30a. After purification by flash column, 39 mg of 30a was obtained.
[0318] 1 H-NMR for the product 30a (CDCl 3 , 500 MHz): δ 9.98 (s, 1H), 9.39 (m, 1H), 8.77 (m, 1H), 8.56 (m, 1H), 8.19 (d, J=9.0 Hz, 1H), 7.32 (s, 1H), 6.89 (m, 1H), 6.71 (s, 1H), 6.67 (s, 1H), 5.95-5.96 (d, J=5.1 Hz, 2H), 5.72-5.81 (m, 1H), 5.26-5.30 (m, 1H), 5.13-5.16 (m, 1H), 5.40 (s, 1H), 4.63-4.70 (m, 2H), 4.52-4.60 (m, 3H), 4.43-4.48 (m, 2H), 4.20-4.22 (d, J=1.8 Hz, 1H), 3.88-3.91 (m, 1H), 2.81-2.86 (m, 1H), 2.35-2.38 (m, 1H), 2.06-2.13 (m, 1H), 2.04 (s, 1H), 1.95 (m, 2H), 1.87 (m, 1H), 1.61-1.73 (m, 6H), 1.46-1.50 (m, 1H), 1.24-1.31 (m, 4H), 0.99-1.06 (m, 12H). ESI-MS [(M+H) + ]: m/z calculated 891.4, founded 891.5
Example 77
Synthesis of Compound 30b
[0319] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30b. After purification, 46 mg of product 30b was obtained.
[0320] 1 H-NMR for the product 30b (CDCl 3 , 500 MHz): δ 9.99 (s, 1H), 9.39 (m, 1H), 8.76 (m, 1H), 8.55 (m, 1H), 8.19 (d, J=9.0 Hz, 1H), 7.24 (s, 1H), 6.87-6.89 (d, J=8.6 Hz, 1H), 6.72 (s, 1H), 6.67 (s, 1H), 5.95-5.96 (d, J=5.1 Hz, 2H), 5.40 (s, 1H), 4.64-4.70 (m, 2H), 4.53-4.59 (m, 3H), 4.44-4.49 (m, 2H), 4.18-4.20 (d, J=1.8 Hz, 1H), 3.86-3.89 (m, 1H), 2.96 (s, 1H), 2.88 (m, 1H), 2.04 (s, 1H), 1.95 (m, 2H), 1.85 (m, 1H), 1.53-1.73 (m, 9H), 1.17-1.35 (m, 6H), 0.96-1.03 (m, 12H). ESI-MS [(M+H) + ]: m/z calculated 893.4, founded 893.4
Example 78
Synthesis of Compound 30c
[0321] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30c. After purification, 41 mg of product 30c was obtained.
[0322] 1 H-NMR for the product 30e (CDCl 3 , 500 MHz): δ 10.37 (s, 1H), 9.26 (s, 1H), 8.74 (m, 1H), 8.57 (m, 1H), 8.34-8.36 (m, 1H), 7.31-7.32 (m, 1H), 6.76 (m, 1H), 6.79 (m, 1H), 5.92 (m, 1H), 5.39 (s, 1H), 5.30-5.33 (m, 1H), 5.13-5.15 (m, 2H), 4.72-4.74 (m, 1H), 4.61 (m, 2H), 4.49 (m, 2H), 4.40-4.43 (m, 2H), 4.25 (m, 4H), 2.87 (m, 1H), 2.47 (m, 1H), 2.25 (m, 2H), 1.89 (m, 4H), 1.78-1.80 (m, 4H), 1.65-1.67 (m, 1H), 1.44-1.48 (m, 2H), 1.13-1.21 (m, 8H), 1.02 (s, 9H). ESI-MS [(M+H) + ]: m/z calculated 905.4, founded 905.4
Example 79
Synthesis of Compound 30d
[0323] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30d. After purification, 38 mg of product 30d was obtained.
[0324] 1 H-NMR for the product 30d (CDCl 3 , 500 MHz): δ10.38 (s, 1H), 9.27 (s, 1H), 8.74 (m, 1H), 8.57 (m, 1H), 8.34-8.36 (m, 1H), 7.30-7.32 (m, 1H), 6.82 (m, 1H), 6.64-6.71 (m, 1H), 5.90 (m, 1H), 5.39 (s, 1H), 5.30-5.32 (m, 1H), 5.13-5.15 (m, 2H), 4.73-4.75 (m, 1H), 4.64 (m, 2H), 4.46-4.52 (m, 2H), 4.37-4.39 (m, 2H), 4.27-4.29 (m, 4H), 2.88 (m, 1H), 2.46 (m, 1H), 2.23 (m, 2H), 1.87-1.90 (m, 6H), 1.78-1.80 (m, 4H), 1.65-1.67 (m, 1H), 1.43-1.49 (m, 2H), 1.14-1.231 (m, 6H), 1.03 (s, 9H). ESI-MS [(M+H) + ]: m/z calculated 905.4, founded 905.4.
Example 80
Synthesis of Compound 30e
[0325] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30e. After purification, 43 mg of product 30e was obtained.
[0326] 1 H-NMR for the product 30e (CDCl 3 , 500 MHz): δ10.39 (s, 1H), 9.27 (s, 1H), 8.74 (m, 1H), 8.57 (m, 1H), 8.38 (m, 1H), 7.30-7.32 (m, 1H), 6.78 (m, 1H), 6.69-6.74 (m, 1H), 5.99 (s, 2H), 5.87-5.95 (m, 1H), 5.40 (s, 1H), 5.31-5.34 (m, 1H), 5.12-5.14 (m, 2H), 4.73-4.76 (m, 1H), 4.65-4.66 (m, 2H), 4.47-4.58 (m, 3H), 4.37-4.42 (m, 1H), 2.88 (m, 1H), 2.47 (m, 1H), 2.24 (m, 2H), 1.89 (m, 3H), 1.78-1.80 (m, 4H), 1.65-1.67 (m, 1H), 1.42-1.47 (m, 2H), 1.14-1.23 (m, 6H), 1.03 (s, 9H), 0.84-0.88 (m, 3H), ESI-MS [(M+H) + ]: m/z calculated 891.4, founded 891.4
Example 81
Synthesis of Compound 30f
[0327] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30f. After purification, 43 mg of product 30f was obtained.
[0328] 1 H-NMR for the product 30f (CDCl 3 , 500 MHz): δ9.97-9.99 (m, 1H), 9.40 (s, 1H), 8.76 (m, 1H), 8.55 (m, 1H), 8.19 (m, 1H), 7.32-7.35 (m, 1H), 7.00 (m, 1H), 6.65-6.77 (m, 2H), 5.92-5.97 (m, 2H), 5.41 (s, 1H), 4.47-4.76 (m, 7H), 4.21-4.26 (m, 1H), 3.88-3.90 (m, 1H), 2.84-2.91 (m, 1H), 2.33-2.40 (m, 2H), 2.21 (m, 3H), 1.83 (m, 1H), 1.55-1.65 (m, 9H), 1.12-1.42 (m, 6H), 0.96-1.03 (m, 13H). ESI-MS [(M+H) + ]: m/z calculated 893.4, founded 893.5
Example 82
Synthesis of Compound 30g
[0329] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30g. After purification, 26 mg of product 30g was obtained. Confirmed by ESI-MS [(M+H) + ]: m/z calculated 919.4, founded 919.4.
Example 83
Synthesis of Compound 30h
[0330] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30h. After purification, 43 mg of product 30h was obtained.
[0331] 1 H-NMR for the product 30h (CDCl 3 , 500 MHz): δ9.99 (s, 1H), 9.38 (m, 1H), 8.76 (m, 1H), 8.56 (m, 1H), 8.15-8.17 (m, 1H), 7.10 (s, 1H), 6.89 (s, 1H), 6.84 (s, 1H), 6.73-6.75 (m, 2H), 5.40 (s, 1H), 4.62-4.72 (m, 2H), 4.52-4.60 (m, 3H), 4.41-4.46 (m, 2H), 4.16-4.21 (m, 5H), 3.85-3.88 (m, 1H), 2.84-2.91 (m, 1H), 2.36-2.45 (m, 1H), 2.32-2.36 (m, 1H), 2.16-2.21 (m, 2H), 1.87 (m, 1H), 1.72-1.75 (m, 6H), 1.65-1.68 (m, 3H), 1.57-1.59 (m, 2H), 1.49-1.5 (m, 2H), 1.31-1.33 (m, 2H), 1.27 (m, 1H), 1.21-1.23 (m, 2H), 1.08-1.09 (m, 3H), 1.01 (s, 9H), 0.97-0.99 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 921.4, founded 921.4.
Example 84
Synthesis of Compound 30j
[0332] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30j. After purification, 43 mg of product 30j was obtained.
[0333] 1 H-NMR for the product 30j (CDCl 3 , 500 MHz): δ 9.98-10.02 (m, 1H), 9.40-9.41 (m, 1H), 8.75 (m, 1H), 8.52-8.55 (m, 1H), 8.18-8.21 (m, 1H), 7.09 (s, 1H), 6.89-6.92 (m, 1H), 6.79-6.81 (d, J=8.0 Hz, 1H), 6.74-6.75 (d, J=8.0 Hz, 1H), 5.42 (s, 1H), 4.67-4.76 (m, 2H), 4.54-4.61 (m, 3H), 4.42-4.49 (m, 2H), 4.24-4.26 (t, J=5.5 Hz, 2H), 4.16-4.20 (m, 3H), 3.87-3.93 (m, 1H), 2.84-2.91 (m, 1H), 2.40-2.46 (m, 1H), 2.30-2.36 (m, 1H), 2.18-2.23 (m, 2H), 1.88 (m, 1H), 1.80 (m, 3H), 1.63-1.71 (m, 5H), 1.57-1.61 (m, 3H), 1.36-1.41 (m, 1H), 1.30 (m, 2H), 1.18-1.26 (m, 2H), 1.08-1.10 (m, 2H), 1.02-1.04 (m, 2H), 0.99 (s, 9H), 0.96-0.98 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 921.4, founded 921.4.
Example 85
Synthesis of Compound 30k
[0334] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30k. After purification, 42 mg of product 30k was obtained.
[0335] 1 H-NMR for the product 30k (CDCl 3 , 500 MHz): δ10.36 (s, 1H), 9.27 (m, 1H), 8.74 (m, 1H), 8.57 (m, 1H), 8.34-8.37 (m, 1H), 7.30 (m, 1H), 7.08 (m, 1H), 6.98 (m, 2H), 5.92 (m, 1H), 5.41 (s, 1H), 5.30-5.33 (m, 1H), 5.13-5.15 (m, 2H), 4.75 (m, 3H), 4.65-4.68 (m, 1H), 4.59 (m, 1H), 4.47-4.51 (m, 1H), 4.38-4.42 (m, 1H), 2.87 (m, 1H), 2.49 (m, 1H), 2.37 (m, 1H), 2.23-2.26 (m, 1H), 1.89 (m, 1H), 1.79 (m, 4H), 1.67 (m, 2H), 1.42-1.45 (m, 2H), 1.26-1.31 (m, 4H), 1.14-1.19 (m, 4H), 1.01-1.06 (m, 12H). ESI-MS [(M+H) + ]: m/z calculated 865.4, founded 865.6
Example 86
Synthesis of Compound 30m
[0336] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30m. After purification, 43 mg of product 30m was obtained.
[0337] 1 H-NMR for the product 30m (CDCl 3 , 500 MHz): δ 10.02 (m, 1H), 7.20 (s, 1H), 6.71 (s, 1H), 6.64 (m, 2H), 5.95-5.97 (m, 2H), 5.38 (s, 1H), 4.82-4.83 (m, 1H), 4.62-4.69 (m, 2H), 4.45-4.51 (m, 4H), 4.17-4.20 (m, 1H), 3.83-3.85 (m, 2H), 2.93 (m, 1H), 2.48 (m, 1H), 2.29 (m, 1H), 1.89 (m, 1H), 1.63-1.72 (m, 5H), 1.53-1.60 (m, 5H), 1.49 (s, 9H), 1.34-1.37 (m, 3H), 1.16-1.21 (m, 2H), 1.04-1.06 (m, 4H), 1.00 (s, 9H), 0.97-0.99 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 887.4, founded 887.4.
Example 87
Synthesis of Compound 30n
[0338] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30n. After purification, 43 mg of product 30n was obtained.
[0339] 1 H-NMR for the product 30n (CDCl 3 , 500 MHz): δ 10.10 (s, 1H), 7.39 (s, 1H), 6.94 (m, 1H), 6.68 (s, 1H), 6.61 (m, 1H), 5.96 (s, 2H), 5.42 (s, 1H), 5.25 (br, 1H), 4.52-4.64 (m, 4H), 4.42-4.49 (m, 2H), 4.17-4.19 (m, 1H), 3.88-3.89 (m, 1H), 3.65 (m, 1H), 2.94 (m, 1H), 2.90 (s, 1H), 2.36-2.41 (m, 2H), 1.93 (m, 1H), 1.73 (m, 3H), 1.58-1.64 (m, 6H), 1.35 (m, 2H), 1.19-1.26 (m, 5H), 1.03-1.06 (m, 3H), 1.03 (s, 9H), 0.98-0.99 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 865.3, founded 865.4
Example 88
Synthesis of Compound 30p
[0340] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30p. After purification, 33 mg of product 30p was obtained.
[0341] 1 H-NMR for the product 30p (CDCl 3 , 500 MHz): δ 10.24 (s, 1H), 8.65 (m, 1H), 8.08 (m, 1H), 8.01 (m, 1H), 7.9 (m, 1H), 7.67 (m, 1H), 7.58 (m, 1H), 7.48 (m, 1H), 7.40 (m, 1H), 6.68 (m, 1H), 6.62 (s, 1H), 6.44 (s, 1H), 5.86-5.91 (m, 2H), 5.63 (s, 1H), 5.40 (s, 1H), 4.44-4.62 (m, 4H), 4.37-4.40 (m, 2H), 3.99-4.01 (m, 1H), 3.83 (m, 1H), 3.26 (m, 1H), 2.96 (m, 1H), 2.46 (m, 1H), 2.35 (m, 1H), 1.86 (m, 1H), 1.56-1.65 (m, 4H), 1.46-1.48 (m, 4H), 1.39-1.42 (m, 4H), 1.09 (m, 3H), 0.99-1.02 (m, 4H), 0.84 (s, 9H), 0.72 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 977.4, founded 977.4.
Example 89
Synthesis of Compound 30q
[0342] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30q. After purification, 39 mg of product 30q was obtained. Confirmed by ESI-MS [(M+H) + ]: m/z calculated 891.4, founded 891.5.
Example 90
Synthesis of Compound 30r
[0343] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30r. After purification, 44 mg of product 30r was obtained.
[0344] 1 H-NMR for the product 30r (CDCl 3 , 500 MHz): δ 10.51 (s, 1H), 7.65-7.67 (d, J=7.4 Hz, 2H), 7.47-7.51 (m, 2H), 7.34-7.37 (t, J=7.8 Hz, 2H), 6.98-6.99 (m, 1H), 6.54 (s, 1H), 6.30 (s, 1H), 5.87 (s, 1H), 5.81 (s, 2H), 5.45 (s, 1H), 4.55-4.63 (m, 3H), 4.46-4.49 (m, 1H), 4.19-4.26 (m, 2H), 4.05-4.07 (m, 1H), 3.85-3.87 (m, 1H), 3.18 (m, 1H), 2.96 (m, 1H), 2.68 (m, 1H), 2.42 (m, 1H), 1.84 (m, 1H), 1.65-1.67 (m, 2H), 1.51-1.55 (m, 9H), 1.25-1.37 (m, 5H), 1.08-1.13 (m, 5H), 0.99 (s, 9H), 0.85 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 927.4, founded 927.4.
Example 91
Synthesis of Compound 30s
[0345] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30s. After purification, 37 mg of product 30s was obtained.
[0346] 1 H-NMR for the product 30s (CDCl 3 , 500 MHz): δ 10.52 (s, 1H), 8.10 (m, 1H), 7.84-7.88 (t, J=9.0 Hz, 2H), 7.76-7.78 (m, 1H), 7.66-7.67 (m, 1H), 7.59-7.62 (m, 1H), 7.51-7.54 (m, 1H), 6.98 (m, 1H), 6.49 (s, 1H), 6.24 (s, 1H), 5.88-5.91 (m, 2H), 5.72 (s, 1H), 5.49 (s, 1H), 5.41 (s, 1H), 4.59-4.66 (m, 3H), 4.49-4.51 (m, 1H), 4.19-4.24 (m, 2H), 4.03-4.05 (m, 1H), 3.85-3.87 (m, 1H), 3.25 (m, 1H), 2.98 (m, 1H), 2.68 (m, 1H), 2.45 (m, 1H), 1.87 (m, 1H), 1.64-1.66 (m, 2H), 1.50-1.59 (m, 8H), 1.30-1.36 (m, 4H), 0.99-1.05 (m, 5H), 0.94 (s, 9H), 0.88 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 977.4, founded 977.4
Example 92
Synthesis of Compound 30t
[0347] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30t. After purification, 21 mg of product 30t was obtained.
[0348] 1 H-NMR for the product 30t (CDCl 3 , 500 MHz): δ 10.05 (m, 1H), 7.32 (s, 1H), 6.71 (m, 1H), 6.63 (m, 1H), 6.59 (m, 1H), 5.96 (m, 2H), 5.39 (s, 1H), 4.91 (m, 1H), 4.43-4.66 (m, 7H), 4.19 (m, 1H), 3.87-3.95 (m, 1H), 3.68-3.77 (m, 1H), 2.93 (m, 1H), 2.49 (m, 1H), 2.33 (m, 1H), 1.96 (s, 1H), 1.81 (m, 1H), 1.71 (m, 3H), 1.57-1.63 (m, 6H), 1.36 (m, 3H), 1.25 (s, 3H), 1.15 (s, 2H), 1.11 (s, 3H), 0.99-1.04 (m, 18H). ESI-MS [(M+H) + ]: m/z calculated 899.4, founded 899.4
Example 93
Synthesis of Compound 30v
[0349] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30v. After purification, 45 mg of product 30v was obtained.
[0350] 1 H-NMR for the product 30v (CDCl 3 , 500 MHz): δ 10.04 (s, 1H), 7.23 (s, 1H), 6.72 (s, 1H), 6.64 (m, 2H), 5.96-5.97 (m, 2H), 5.38 (s, 1H), 4.97-4.98 (m, 1H), 4.59-4.69 (m, 2H), 4.47-4.52 (m, 4H), 4.18-4.20 (m, 1H), 3.94 (m, 1H), 3.84 (m, 1H), 2.94 (m, 1H), 2.47 (m, 1H), 2.33 (m, 1H), 1.87 (m, 1H), 1.66-1.69 (m, 5H), 1.56-1.58 (m, 5H), 1.36 (m, 3H), 1.22-1.27 (m, 3H), 1.17-1.19 (m, 2H), 1.14-1.16 (m, 2H), 1.03-1.08 (m, 4H), 1.00 (s, 9H), 0.97-0.98 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 859.4, founded 859.4
Example 94
Synthesis of Compound 30w
[0351] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30w. After purification, 40 mg of product 30w was obtained.
[0352] 1 H-NMR for the product 30w (CDCl 3 , 500 MHz): δ 10.02 (m, 1H), 7.19 (s, 1H), 6.72 (s, 1H), 6.65 (m, 2H), 5.96-5.97 (m, 2H), 5.38 (s, 1H), 4.89 (m, 2H), 4.60-4.69 (m, 2H), 4.47-4.51 (m, 4H), 4.20-4.22 (m, 1H), 3.83-3.90 (m, 2H), 2.94 (m, 1H), 2.48 (m, 1H), 2.33 (m, 1H), 1.88 (m, 1H), 1.64-1.69 (m, 5H), 1.56-1.58 (m, 5H), 1.36-1.37 (m, 3H), 1.25 (s, 3H), 1.24 (s, 3H), 1.14-1.19 (m, 3H), 0.97-1.05 (m, 12H), 0.82-0.91 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 873.4, founded 873.5
Example 95
Synthesis of Compound 30x
[0353] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30x. After purification, 41 mg of product 30x was obtained.
[0354] 1 H-NMR for the product 30x (CDCl 3 , 500 MHz): δ 10.09 (s, 1H), 7.34 (br, 1H), 6.71 (s, 1H), 6.65 (m, 2H), 5.96-5.97 (m, 2H), 5.38 (s, 1H), 5.05 (m, 1H), 4.59-4.689 (m, 2H), 4.49-4.52 (m, 4H), 4.17-4.19 (m, 1H), 3.96 (m, 1H), 3.88 (m, 1H), 3.68 (s, 3H), 2.92 (m, 1H), 2.43 (m, 1H), 2.34 (m, 1H), 1.88 (m, 1H), 1.64-1.69 (m, 5H), 1.56-1.57 (m, 5H), 1.35 (m, 3H), 1.26 (m, 4H), 1.17-1.20 (m, 2H), 1.01 (s, 9H), 0.88-0.89 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 845.4, founded 845.4
Example 96
Synthesis of Compound 30y
[0355] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30y. After purification, 43 mg of product 30y was obtained. Confirmed by ESI-MS [(M+H) + ]: m/z calculated 921.4, founded 921.4
Example 97
Synthesis of Compound 30z
[0356] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30z. After purification, 31 mg of product 30z was obtained. Confirmed by ESI-MS [(M+H) + ]: m/z calculated 907.4, founded 907.5.
Example 98
Synthesis of Compound 30aa
[0357] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30aa. After purification, 31 mg of product 30aa was obtained.
[0358] 1 H-NMR for the product 30aa (CDCl 3 , 500 MHz): δ 10.00 (s, 1H), 7.76-7.78 (d, J=7.3 Hz, 2H), 7.58-7.62 (d, J=7.4 Hz, 2H), 7.38-7.42 (m, 2H), 7.30-7.34 (m, 2H), 7.03 (s, 1H), 6.69 (m, 2H), 6.65 (s, 1H), 5.93-5.96 (m, 2H), 5.38 (s, 1H), 5.13-5.15 (m, 1H), 4.59-4.69 (m, 2H), 4.52 (s, 2H), 4.39-4.48 (m, 4H), 4.17-4.20 (m, 1H), 3.95 (m, 1H), 3.83-3.87 (m, 1H), 2.91 (m, 1H), 2.43 (m, 1H), 2.30 (m, 1H), 1.86 (s, 1H), 1.68-1.73 (m, 2H), 1.61-1.64 (m, 3H), 1.53-1.58 (m, 3H), 1.33-1.36 (m, 2H), 1.26-1.30 (m, 2H), 1.15-1.20 (m, 3H), 0.97-1.03 (m, 15H). ESI-MS [(M+H) + ]: m/z calculated 1009.4, founded 1009.4
Example 99
Synthesis of Compound 30ab
[0359] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ab. After purification, 46 mg of product 30ab was obtained.
[0360] 1 H-NMR for the product 30ab (CDCl 3 , 500 MHz): δ 10.49 (brs, 1H), 7.40 (brs, 1H), 6.68 (s, 1H), 6.64 (m, 2H), 5.92-5.95 (m, 2H), 5.81 (brs, 1H), 5.43 (m, 1H), 5.28-5.30 (m, 1H), 5.11-5.19 (m, 1H), 4.87 (m, 1H), 4.55-4.64 (m, 3H), 4.25-4.51 (m, 3H), 4.19 (m, 1H), 3.92-4.04 (m, 2H), 2.83 (m, 1H), 2.28-2.39 (m, 2H), 2.20 (m, 1H), 1.98 (m, 1H), 1.67-1.81 (m, 3H), 1.41-1.62 (m, 5H), 1.30 (s, 9H), 1.12-1.26 (m, 3H), 1.07-1.09 (m, 3H), 1.03 (s, 9H), 0.86-0.99 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 884.4, founded 884.5
Example 100
Synthesis of Compound 30ac
[0361] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ac. After purification, 42 mg of product 30ac was obtained.
[0362] 1 H-NMR for the product 30ac (CDCl 3 , 500 MHz): δ 7.35 (brs, 1H), 6.63-6.68 (m, 2H), 5.93-5.95 (m, 2H), 5.39 (m, 1H), 4.89 (m, 1H), 4.33-4.59 (m, 6H), 4.16 (m, 1H), 3.92-4.00 (m, 2H), 2.85 (m, 1H), 2.32-2.39 (m, 3H), 1.67-1.80 (m, 5H), 1.52-1.62 (m, 5H), 1.40-1.48 (m, 3H), 1.30 (s, 9H), 1.13-1.26 (m, 4H), 1.05-1.10 (m, 3H), 1.04 (s, 9H), 0.89-0.99 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 886.4, founded 886.5.
Example 101
Synthesis of Compound 30ad
[0363] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ad. After purification, 31 mg of product 30ad was obtained.
[0364] 1 H-NMR for the product 30ad (CDCl 3 , 500 MHz): δ 10.03 (m, 1H), 7.20 (s, 1H), 6.88 (s, 1H), 6.81 (s, 1H), 6.72 (m, 1H), 5.38 (m, 1H), 4.85 (m, 1H), 4.59-4.68 (m, 2H), 4.43-4.51 (m, 4H), 4.18-4.20 (m, 5H), 3.85 (m, 2H), 2.86-2.96 (m, 2H), 2.42 (m, 1H), 2.34 (m, 1H), 2.19 (m, 2H), 1.60-1.70 (m, 5H), 1.51-1.58 (m, 5H), 1.44 (s, 9H), 1.36-1.39 (m, 3H), 1.13-1.21 (m, 2H), 1.04-1.07 (m, 4H), 1.01 (s, 9H), 0.97-0.99 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 915.5, founded 915.6.
Example 102
Synthesis of Compound 30ae
[0365] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ae. After purification, 31 mg of product 30ae was obtained.
[0366] 1 H-NMR for the product 30ae (CDCl 3 , 500 MHz): δ 10.03 (m, 1H), 7.19 (s, 1H), 6.88 (s, 1H), 6.80 (s, 1H), 6.64 (m, 1H), 5.38 (m, 1H), 5.07 (m, 1H), 4.89 (m, 1H), 4.60-4.69 (m, 2H), 4.45-4.54 (m, 4H), 4.20 (m, 5H), 3.86 (m, 2H), 2.91-2.96 (m, 1H), 2.44-2.49 (m, 1H), 2.32-2.34 (m, 1H), 2.17-2.21 (m, 2H), 1.81-1.90 (m, 4H), 1.64-1.71 (m, 8H), 1.52-1.57 (m, 7H), 1.33-1.36 (m, 2H), 1.05-1.28 (m, 7H), 1.01 (s, 9H), 0.93-0.99 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 927.5, founded 927.6
Example 103
Synthesis of Compound 30af
[0367] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30af. After purification, 31 mg of product 30af was obtained.
[0368] 1 H-NMR for the product 30af (CDCl 3 , 500 MHz): δ 10.03 (s, 1H), 7.20 (s, 1H), 6.70 (s, 1H), 6.58 (s, 1H), 5.97 (s, 2H), 5.74 (m, 1H), 5.40 (br, 1H), 5.21-5.28 (m, 2H), 5.14-5.16 (m, 1H), 4.66 (m, 2H), 4.44-4.55 (m, 3H), 4.21-4.23 (m, 2H), 3.87 (m, 1H), 2.89 (m, 1H), 2.37 (m, 2H), 2.08 (m, 1H), 1.94 (m, 1H), 1.78 (m, 1H), 1.40-1.48 (m, 2H), 1.34 (s, 9H), 1.07 (m, 2H), 1.02 (s, 9H). ESI-MS [(M+H) + ]: m/z calculated 746.3, founded 746.4
Example 104
Synthesis of Compound 30ag
[0369] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ag. After purification, 31 mg of product 30ag was obtained.
[0370] Confirmed by ESI-MS [(M+H) + ]: m/z calculated 748.3, founded 748.4.
Example 105
Synthesis of Compound 30ah
[0371] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ah. After purification, 31 mg of product 30ah was obtained.
[0372] 1 H-NMR for the product 30ah (CDCl 3 , 500 MHz): δ 10.02 (s, 1H), 7.16-7.18 (m, 1H), 6.76 (m, 1H), 6.62-6.72 (m, 1H), 5.98 (s, 1H), 5.97 (m, 1H), 5.76 (m, 1H), 5.41 (s, 1H), 5.29 (m, 1H), 5.21 (m, 1H), 5.14-5.16 (m, 1H), 4.66-4.69 (m, 2H), 4.53-4.58 (m, 2H), 4.46 (m, 1H), 4.20-4.25 (m, 2H), 3.85 (m, 1H), 2.92 (m, 1H), 2.37-2.43 (m, 2H), 2.08 (m, 1H), 1.96 (m, 1H), 1.71 (m, 1H), 1.44-1.48 (m, 2H), 1.30-1.33 (m, 9H), 1.04-1.05 (m, 2H), 1.02 (s, 9H). ESI-MS [(M+H) + ]: m/z calculated 746.3, founded 746.4
Example 106
Synthesis of Compound 30aj
[0373] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30aj. After purification, 23 mg of product 30aj was obtained.
[0374] Confirmed by ESI-MS [(M+H) + ]: m/z calculated 720.3, founded 720.4.
Example 107
Synthesis of Compound 30ak
[0375] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ak. After purification, 39 mg of product 30ak was obtained.
[0376] 1 H-NMR for the product 30ak (CDCl 3 , 500 MHz): δ 10.01 (s, 1H), 7.21 (s, 1H), 6.71 (s, 1H), 6.68 (s, 1H), 5.96 (m, 2H), 5.76 (m, 1H), 5.40 (s, 1H), 5.26-5.30 (m, 2H), 5.15-5.17 (m, 1H), 4.73 (br, 1H), 4.60-4.69 (m, 2H), 4.47-4.52 (m, 2H), 4.23 (m, 2H), 3.83 (m, 1H), 2.93 (m, 1H), 2.42 (m, 1H), 2.36 (m, 1H), 2.09 (m, 1H), 1.98 (m, 1H), 1.63-1.68 (m, 7H), 1.44-1.47 (m, 4H), 1.36 (m, 3H), 1.02 (s, 9H). ESI-MS [(M+H) + ]: m/z calculated 758.3, founded 758.4
Example 108
Synthesis of Compound 30am
[0377] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30am. After purification, 40 mg of product 30am was obtained.
[0378] Confirmed by ESI-MS [(M+H) + ]: m/z calculated 760.3,
Example 109
Synthesis of Compound 30an
[0379] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30an. After purification, 31 mg of product 30an was obtained.
[0380] 1 H-NMR for the product 30an (CDCl 3 , 500 MHz): δ 9.98 (s, 1H), 7.25 (s, 1H), 6.77 (m, 1H), 6.62-6.75 (m, 1H), 5.95 (m, 2H), 5.75 (m, 1H), 5.40 (s, 1H), 5.25-5.32 (m, 2H), 5.14-5.16 (m, 1H), 4.65-4.75 (m, 3H), 4.47-4.62 (m, 3H), 4.22-4.27 (m, 2H), 3.85 (m, 1H), 2.90 (m, 1H), 2.42 (m, 1H), 2.37 (m, 1H), 2.08 (m, 1H), 1.96 (m, 1H), 1.73 (m, 1H), 1.54-1.62 (m, 6H), 1.44 (m, 3H), 1.34 (m, 2H), 1.01-1.05 (m, 11H). ESI-MS [(M+H) + ]: m/z calculated 758.3, founded 758.4.
Example 110
Synthesis of Compound 30ap
[0381] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ap. After purification, 23 mg of product 30ap was obtained.
[0382] Confirmed by ESI-MS [(M+H) + ]: m/z calculated 762.3, founded 762.4.
Example 111
Synthesis of Compound 30aq
[0383] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30aq. After purification, 39 mg of product 30aq was obtained.
[0384] 1 H-NMR for the product 30aq (CDCl 3 , 500 MHz): δ 10.08 (s, 1H), 7.18 (brs, 1H), 6.69 (s, 1H), 6.58 (s, 1H), 5.96 (s, 2H), 5.40 (m, 1H), 4.47-4.64 (m, 4H), 4.3-4.44 (m, 2H), 4.29-4.31 (m, 1H), 3.89 (m, 1H), 2.92 (m, 1H), 2.34 (m, 2H), 1.58-1.68 (m, 3H), 1.36-1.43 (m, 2H), 1.28-1.33 (m, 1H), 1.26 (s, 9H), 1.05-1.07 (m, 3H), 1.01 (s, 9H), 0.95-0.98 (t, J=7.5 Hz, 1H). ESI-MS [(M+H) + ]: m/z calculated 747.4, founded 747.5
Example 112
Synthesis of Compound 30ar
[0385] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30ar. After purification, 33 mg of product 30ar was obtained.
[0386] 1 H-NMR for the product 30ar (CDCl 3 , 500 MHz): δ 10.18 (s, 1H), 7.11 (brs, 1H), 6.71 (s, 1H), 6.60 (s, 1H), 5.97 (s, 2H), 5.80-5.88 (m, 1H), 5.25-5.27 (d, J=9.5 Hz, 1H), 5.14-5.16 (d, J=10.5 Hz, 1H), 4.57-4.67 (m, 3H), 4.45-4.50 (m, 1H), 4.36-4.37 (m, 2H), 4.25-4.29 (m, 1H), 3.89 (m, 1H), 2.92 (m, 1H), 2.34-2.41 (m, 2H), 2.08-2.13 (m, 1H), 1.96-1.98 (m, 1H), 1.51-1.54 (m, 1H), 1.30-1.39 (m, 3H), 1.26 (s, 9H), 1.14-1.23 (m, 2H), 1.05 (m, 1H), 1.02 (s, 9H). ESI-MS [(M+H) + ]: m/z calculated 745.4, founded 745.5.
Example 113
Synthesis of Compound 30-Ref
[0387] The synthetic procedure was carried out as the same as in Example 76 for preparation of compound 30-Ref. After purification, 37 mg of product 30-Ref was obtained.
[0388] 1 H-NMR for the product 30-Ref (CDCl 3 , 500 MHz): δ 9.99 (s, 1H), 7.28 (s, 1H), 7.07 (m, 1H), 6.96 (m, 2H), 5.75 (m, 1H), 5.41 (s, 1H), 5.26-5.31 (m, 2H), 5.15-5.17 (m, 1H), 4.63-4.85 (m, 5H), 4.50-4.53 (m, 1H), 4.29-4.32 (m, 1H), 4.22-4.24 (m, 1H), 3.83 (m, 1H), 2.91 (m, 1H), 2.42 (m, 1H), 2.38 (m, 1H), 2.09 (m, 1H), 1.94 (m, 1H), 1.60 (m, 4H), 1.51 (m, 3H), 1.44 (m, 3H), 1.35 (m, 2H), 1.01-1.05 (m, 11H). ESI-MS [(M+H) + ]: m/z calculated 732.3, founded 732.4.
Example 114
Synthesis of Compound 33a
[0389] Chemical SM-15a (5.4 g, 10 mmol), SM-16 (1.1 eq) and DMF (80 mL) were added into 250 mL flask reactor, followed by adding coupling reagent EDCI (1.3 eq) to keep the amidation at 55° C. until completed. The reaction mixture was worked out to obtain crude product 31a, followed by removing Boc group with HCl-THF solution to obtain 32a (3.9 g, yield: 86%), which was purified by precipitation in hexane-EtOAc and dried directly for next step. ESI-MS (M+H + ): m/z calculated 487.2, founded 487.2.
[0390] In the presence of coupling reagent HATU (1.3 eq) in DMF (1.0 mL), compound 32a (60 mg, 0.1 mmol) was reacted with another acid derivative SM-14a to obtain product 33a. After purification by flash column, 41 mg of 33a was obtained.
[0391] 1 H-NMR for the product 33a (CDCl 3 , 500 MHz): δ 9.40 (s, 1H), 8.77 (s, 1H), 8.55 (s, 1H), 8.16-8.17 (m, 1H), 7.32-7.33 (m, 1H), 7.04 (m, 1H), 6.72 (s, 1H), 6.68 (s, 1H), 5.94-5.95 (m, 2H), 5.36 (m, 1H), 4.77-4.80 (m, 1H), 4.69-4.72 (m, 1H), 4.59-4.64 (m, 2H), 4.51-4.53 (m, 2H), 4.44-4.47 (m, 2H), 4.18-4.20 (m, 1H), 3.80-3.83 (m, 1H), 2.78 (m, 1H), 2.64 (m, 1H), 2.26 (m, 1H), 1.88-1.92 (m, 1H), 1.77-1.79 (m, 1H), 1.66-1.69 (m, 3H), 1.59-1.61 (m, 4H), 1.38-1.42 (m, 2H), 1.10-1.19 (m, 3H), 1.00-1.07 (m, 3H), 0.97-0.99 (m, 9H), 0.89-0.93 (m, 3H), 0.85-0.86 (m, 2H), 0.61 (m, 2H), ESI-MS [(M+H) + ]: m/z calculated 845.4, founded 845.4
Example 115
Synthesis of Compound 33b
[0392] The synthetic procedure was carried out as the same as in Example 114 for preparation of compound 33b. After purification, 41 mg of product 33b was obtained.
[0393] 1 H-NMR for the product 33b (CDCl 3 , 500 MHz): δ 9.39 (m, 1H), 8.77 (m, 1H), 8.57 (m, 1H), 8.33 (m, 1H), 7.75 (m, 1H), 6.76 (s, 2H), 6.69 (s, 1H), 6.62 (m, 1H), 6.06 (br, 1H), 5.70 (br, 1H), 4.86 (m, 1H), 4.54-4.66 (m, 3H), 4.44-4.51 (m, 2H), 4.25-4.41 (m, 1H), 4.25 (m, 4H), 4.09 (m, 1H), 2.82 (m, 1H), 2.58 (m, 1H), 2.22 (m, 1H), 1.97 (m, 2H), 2.19 (m, 2H), 1.78 (m, 4H), 1.68 (m, 2H), 1.25-1.29 (m, 6H), 1.05-1.16 (m, 4H), 1.05 (s, 9H), 0.84-0.85 (m, 2H), 0.76-0.79 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 859.4, founded 859.5
Example 116
Synthesis of Compound 33c
[0394] The synthetic procedure was carried out as the same as in Example 114 for preparation of compound 33c. After purification, 21 mg of product 33c was obtained.
[0395] 1 H-NMR for the product 33c (CDCl 3 , 500 MHz): δ 9.28 (s, 1H), 8.75 (s, 1H), 8.56 (m, 2H), 7.72 (m, 1H), 6.76-6.78 (m, 1H), 6.65-6.67 (m, 1H), 6.68 (s, 1H), 5.99 (m, 2H), 5.32 (s, 1H), 4.86 (m, 1H), 4.44-4.67 (m, 6H), 4.09 (m, 2H), 2.82 (m, 1H), 2.61 (m, 1H), 2.24 (m, 1H), 2.03 (m, 2H), 1.84-1.87 (m, 2H), 1.65-1.78 (m, 5H), 1.21-1.34 (m, 5H), 1.09-1.25 (m, 4H), 1.05-1.09 (m, 9H), 0.84-0.85 (m, 2H), 0.76 (m, 4H). ESI-MS [(M+H) + ]: m/z calculated 845.4, founded 845.4.
Example 117
Synthesis of Compound 33d
[0396] The synthetic procedure was carried out as the same as in Example 114 for preparation of compound 33d. After purification, 22 mg of product 33d was obtained.
[0397] 1 H-NMR for the product 33d (CDCl 3 , 500 MHz): δ 9.28 (m, 1H), 8.76 (m, 1H), 8.56 (m, 2H), 7.77 (m, 1H), 6.80 (m, 1H), 6.76 (m, 1H), 6.65 (m, 1H), 6.60 (br, 1H), 4.47-4.69 (m, 6H), 4.26 (m, 4H), 4.09 (m, 1H), 2.83 (m, 1H), 2.59 (m, 1H), 2.22 (m, 1H), 1.85-1.87 (m, 2H), 1.62-1.72 (m, 8H), 1.26 (m, 6H), 1.05-1.19 (m, 4H), 1.01-1.05 (m, 9H), 0.85-0.86 (m, 2H), 0.76-0.79 (m, 3H). ESI-MS [(M+H) + ]: m/z calculated 859.4, founded 859.5.
Example 118
Synthesis of Compound 33-Ref
[0398] The synthetic procedure was carried out as the same as in Example 114 for preparation of compound 33-Ref. After purification, 28 mg of product 33-Ref was obtained.
[0399] 1 H-NMR for the product 33-Ref (CDCl 3 , 500 MHz): δ 9.28 (m, 1H), 8.75 (s, 1H), 8.57 (m, 2H), 7.71 (m, 1H), 7.07 (m, 1H), 6.97-7.00 (m, 2H), 6.63 (m, 1H), 5.92 (m, 1H), 5.41 (s, 1H), 5.30-5.33 (m, 1H), 5.13-5.15 (m, 2H), 4.75 (m, 3H), 4.65-4.68 (m, 1H), 4.59 (m, 1H), 4.47-4.51 (m, 1H), 4.38-4.42 (m, 1H), 2.87 (m, 1H), 2.49 (m, 1H), 2.37 (m, 1H), 2.23-2.26 (m, 1H), 2.03 (m, 2H), 1.84-1.87 (m, 2H), 1.65-1.78 (m, 5H), 1.21-1.34 (m, 5H), 1.09-1.25 (m, 4H), 1.05-1.09 (m, 9H), 0.84-0.85 (m, 2H), 0.76 (m, 4H), ESI-MS [(M+H) + ]: m/z calculated 819.4, founded 819.4
[0400] This application claims priority to Chinese application No. CN 201010101403.7, filed on Jan. 27, 2010, and incorporated herein by reference. | The present invention discloses the structure, preparation methods and uses of a series of novel polyheterocyclic based compounds (Ia-Ib and IIa-IIb) that are highly effective for inhibiting hepatitis C virus (HCV):
where the structural variables are defined herein. The present invention is also provides a method of treating HCV infection by the polyheterocyclic based HCV inhibitory compounds, compositions and therapeutic methods. | 0 |
TECHNICAL FIELD
[0001] The present invention relates generally to thermostats, and more particularly, to thermostats for individuals with disabilities.
BACKGROUND
[0002] The regulation of indoor temperature, such as the interior of a home or office, is most commonly monitored and controlled by a thermostat. When an indoor temperature falls below or rises above a desired temperature setting (e.g., a thermostat setting), the thermostat activates a heating/cooling system to warm or cool the indoor temperature to the desired temperature setting.
[0003] A thermostat, in its simplest form, must be manually adjusted to change the indoor air temperature. For example, thermostats may be manually activated by turning a knob or positioning a lever to a desired temperature setting, which engages a heating/cooling system to increase or decrease interior temperature if the temperature changes from the desired setting.
[0004] More modern thermostats are digitally programmable and can automatically respond to changes in temperature and control heating/cooling in response thereto, to maintain a constant temperature. Most thermostats, whether manual or programmable, have a visible temperature display that shows the current temperature of an area in proximity to the thermostat and the temperature at which the thermostat is set.
[0005] Thermostats function in response to changes in ambient temperature in an environment. Therefore, to function properly, a home thermostat is typically located about 5 feet off the ground and about 2 feet away from an outside wall. It should not be exposed to any direct heat sources, such as, sunlight or other heating or cooling appliances. It is also best not to put a thermostat near a staircase or in a corner because they affect the circulation of air.
[0006] Because thermostats are for the most part manually operated and because there are limitations as to their placement in the home, challenges arise for certain individuals who may need to operate these important home devices. For example, because thermostats must be positioned high on a wall, they are out of reach for individuals confined to wheelchairs or with impaired mobility. Current thermostat models are also inaccessible to individuals with visual impairments because there is no way to adjust the temperature to the desired setting without the ability to view the temperature display.
[0007] There is lacking a thermostat that can be operated by individuals who are physically disabled or limited in their mobility or sight, which allows them the independence to control and achieve a comfortable home climate.
SUMMARY
[0008] An innovative thermostat having a handicap access mode is described. The thermostat accepts voice commands when in the handicap access mode. This feature is a particularly useful for the visually impaired, and individuals with limited mobility.
[0009] In a described implementation, the thermostat includes a controller operable in a direct input mode and/or a handicap access mode. When in the direct input mode, the controller receives user commands through mechanical actuation of an adjustment mechanism to adjust a thermostat setting. When in the handicap access mode the controller receives voice commands through a microphone to adjust a thermostat setting.
[0010] The handicap access mode may be actuated several different ways. In one embodiment, an elevation compensation actuator, directly or indirectly attached to the thermostat, allows a person to actuate the handicap access mode when the person moves the elevation compensation actuator. The elevation compensation actuator may be a flexible cord that when pulled down actuates the handicap mode. Alternatively, the elevation compensation actuator may be a rod that when pushed up, pulled down, or rotated along a longitudinal axis, actuates the handicap mode. The elevation compensation actuator is typically adjusted to compensate for a persons height if they are in a wheel chair or are too short to reach the thermostat on a wall.
[0011] In another embodiment, particular audible sounds received by the microphone, in part, trigger the selection of the handicap access mode. For instance, particular clapping patterns, words or phrases, bell sounds, or other audible sounds, when recognized by the thermostat invoke the handicap access mode.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] The detailed description is described with reference to the accompanying figures. In the figures, the left-most digit(s) of a reference number identifies the figure in which the reference number first appears. Reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
[0013] FIG. 1 illustrates various components of an exemplary thermostat that can be utilized to implement the inventive techniques described herein.
[0014] FIG. 2 is a flow diagram that illustrates an exemplary method of operation that may be used with the innovative thermostat described in FIG. 1 .
DETAILED DESCRIPTION
[0000] Exemplary Thermostat with Handicap Access Mode
[0015] FIG. 1 illustrates various components of an exemplary thermostat 100 that can be utilized to implement the inventive techniques described herein. Thermostat 100 utilizes voice recognition technology able to receive and recognize voice commands from an individual to control the operation of the thermostat. Thermostat 100 may also utilize speech response technology providing the ability for thermostat 100 to respond back to an individual verbally (or with other audible tones) in an interactive fashion.
[0016] In one implementation, thermostat 100 includes a display panel 102 , a manual adjustment mechanism 104 , a microphone 106 , a speaker 108 , an elevation compensation actuator 110 , a switch 112 , a controller 114 , and a memory module 116 .
[0017] Display panel 102 may enable a user to visually view thermostat settings, such as temperature settings or other programmable settings, such as but not limited to: time, date, temperature history, and average temperature. Display panel 102 , may be used by individuals without necessarily having to use voice recognition technology or voice response technology. Display panel 102 may be large enough to enable a person suffering from mild myopia to view content without the aid of corrective lenses. Additionally, magnifying materials (not shown) may be used in conjunction with display panel 102 to enlarge content displayed therein. Various types of display devices, sizes, and shapes may be chosen to implement display panel 102 including the possibility of touch-screen technology. Additionally, display panel may also be implemented with analog display devices. More than one display panel may be included on thermostat 100 and other elements may be used to display information such as audible indicators, lights and LEDs.
[0018] Manual adjustment mechanism 104 includes all types of input devices such as a keyboard, buttons, input pads, keypads, or other selectable controls that are manipulated by a user to enter information into thermostat 100 . Manual adjustment mechanism 104 may also include dials, levers, and other mechanisms found on thermostats to adjust thermostat settings.
[0019] Microphone 106 serves as another mechanism to receive audible information and commands from a user. Microphone 106 may receive voice commands from a user and/or other sounds produced by a user, such as clapping, the ringing of a bell, and other suitable sounds.
[0020] A speaker 108 disseminates audio content. The audio content may be in various forms, such as voice and/or tones, and may be disseminated to a user in conjunction with visual content on display panel 102 .
[0021] An elevation compensation actuator 110 may also be used in connection with thermostat 100 . An elevation compensation actuator 110 may include a pull cord, a rod, a remote activation device such as wireless device, and other suitable devices. In the form of a flexible cord or rod the elevation compensation actuator 110 is typically attached directly (as shown in FIG. 1 ) (although not required) to thermostat 100 and adjusted to hang down from thermostat 100 to compensate for an individual's height if the individual is in a wheel chair or is too short to reach thermostat 100 on a wall. By moving elevation compensation actuator 110 an individual triggers a switch (shown as block 112 ), which in turn, communicates with controller 114 (to be described), and activates a handicap access mode for thermostat 100 . As shall be explained, the handicap access mode facilitates a mode of operation for communicating with thermostat 100 in an interactive fashion, in which commands may be conveyed to and/or received from the thermostat 100 in an audible fashion.
[0022] When elevation compensation actuator 110 is implemented as a flexible cord, an individual may simply pull-down on the cord to activate switch 112 , and in turn, the handicap mode of operation. When elevation compensation actuator 110 is implemented as a rod, an individual may activate switch 112 by simply pushing up on the rod, pulling down on the rod, or rotating it along its longitudinal axis. It is also possible to implement elevation compensation actuator 110 as a remote device that is able to communicate with thermostat 100 .
[0023] Controller 114 processes various instructions to control the operation of thermostat 100 , and may communicate with other electronic and computing devices. Controller 114 may be implemented as one or more processors, microcontrollers, circuitry, logic, a combination of the aforementioned, or other computational resources configured to perform operational acts described herein.
[0024] Memory module 116 may include one or more memory components, examples of which include volatile memory (e.g., a random access memory (RAM) and the like), and a non-volatile memory (e.g., ROM, Flash, EPROM, EEPROM, a hard disk drive, any type of magnetic or optical storage device, and the like). The one or more memory components store computer-executable instructions in the form of program applications, routines, logic, modules and other applications. Additionally, various forms of information and/or data can be stored in volatile or non-volatile memory.
[0025] Alternative implementations of controller 114 and memory module 116 can include a range of processing and memory capabilities, and may include any number of memory components other than those illustrated in FIG. 1 . For example, full-resource thermostats can be implemented with substantial memory and processing resources, or low-resource thermostats can be implemented with limited processing and memory capabilities.
[0026] An operating system 118 , such as Windows® CE operating system from Microsoft® Corporation or other operating systems, and one or more program modules 120 may be resident in memory module 116 and execute on processor(s) (part of controller 114 ) to provide a runtime environment. A runtime environment facilitates extensibility of thermostat 100 by allowing various interfaces to be defined that, in turn, allow program modules 120 to interact with controller 114 . The program modules 120 can include off-the-shelf programs modules, or may be tailored programs.
[0027] Program modules 120 can also include one or more other programs configured to provide thermostat specific user interfaces including menus and information directed to users of thermostat 100 . These menus and information may be conveyed to a user in the form of display panel 102 and/or audibly through speaker 108 . For example, a voice recognition/response module 122 , generally facilitates operational aspects of thermostat to enable receipt of commands from an individual in an audible fashion. Voice recognition/response module 122 also enables conveyance of audible information to an individual in response to commands (including requests) made by the individual. For example, recognition/response module 122 may select one or more voice responses 140 from memory module 116 in response to commands received from a user of thermostat 100 .
[0028] Voice recognition/response module 122 may be implemented using rudimentary voice recognition technology or more sophisticated technology, such as a training mode to learn voice command patterns. For example, in a training mode a user can tailor a list of predefined commands in the user's own voice. Voice recognition/response module 122 may save the specific commands 142 pronounced by the voice of a user in memory module 116 and/or the commands 142 may be predefined without the need for user input.
[0029] Handicap access mode may be triggered several different ways. As described above, elevation compensation actuator 110 may be used to activate the handicap access mode, and the launching of voice recognition/response module 122 .
[0030] Handicap access mode may also be triggered (e.g. selected), when thermostat 100 receives particular audible sounds from microphone 106 . That is, microphone 106 receives certain volume sounds and transmits them to controller 114 . Voice recognition/response module 122 , analyzes the received sounds and determines whether they match one or more sound patterns stored in memory module 116 associated with activating the handicap access mode (referred to as Trigger Sounds 144 ). The particular audible sounds may be predetermined and saved in memory module 116 or saved by the user. Examples of particular audible sounds that may trigger the handicap access mode include, but are not limited to, one or more of a series of hand claps, a particular word, a phrase, a ringing of a bell, a blowing of a horn, or various other tones.
[0031] Once the system is trained (or if the system has a pre-saved verbal commands), a user can launch the handicap access mode by emitting a particular trigger sound 144 . Once the handicap access mode is activated, a user can issue a verbal command to thermostat 100 , to change system settings associated with heating or air-conditioning, or program the thermostat. For example, assuming the handicap access mode is selected, a user may issue a request such as, “what is the temperature?”
[0032] Voice synthesizing technology may be included as part of Voice recognition/response module 122 to convey verbal information and sounds from the thermostat to an individual. So in response to the temperature question, voice recognition/response module 122 may convey an answer, such as “it is 68 degrees.” Again, the responses may be selected from a set of potential voice responses 140 stored in memory module 116 .
[0033] Although not shown in FIG. 1 , it is appreciated that voice recognition/response module 122 and controller 114 may utilize well known filters, and a A/D converter technology to convert information received from microphone 106 into a digital format for processing by controller 114 , or to convert information into an analog format from the controller 114 , for transmission to a user via speaker 108 . Additionally, although not shown, a system bus as well as other well known interconnect technology may be used to connect the various components within thermostat 100 .
[0034] It is also noted that program modules 120 , such as voice recognition/response module 122 , may execute on processor(s) or other computational devices, and can be stored as computer-executable instructions in memory module 116 . Although the program modules 120 are illustrated and described as single applications or module(s), each can be implemented as one or more combined components. For purposes of illustration, programs, modules and other executable program or logical components are illustrated herein as discrete blocks, although it is recognized that such programs and components reside at various times in different storage components and may be executed by one or more processors that are not necessarily part of thermostat 100 .
[0035] It is to be appreciated that additional components (not shown) can be included in thermostat 100 and some components illustrated in thermostat 100 above need not be included. For example, additional processors or storage devices, additional interfaces, and so forth may be included in thermostat 100 , or a display panel may not be included.
[0036] It is also to be appreciated that the components and processes described herein can be implemented in software, firmware, hardware, or combinations thereof. By way of example, a programmable logic device (PLD) or application specific integrated circuit (ASIC) could be configured or designed to implement various components and/or processes discussed herein.
[0000] Exemplary Methods of Operation
[0037] Methods of operation for thermostat 100 may be described in the general context of computer-executable instructions. Generally, computer-executable instructions include routines, logic, programs, objects, components, data structures, etc. and the like that perform particular functions or implement particular abstract data types. The described method may also be practiced in distributed computing environments where functions are performed by remote processing devices that are linked through a communications network. In a distributed computing environment, computer-executable instructions may be located in both local and remote storage media, including memory storage devices.
[0038] FIG. 2 is a flow diagram that illustrates an exemplary method 200 of operation associated with thermostat 100 . The order in which the method is described is not intended to be construed as a limitation, and any number of the described method blocks can be combined in any order to implement the method. Each of the operations and blocks may be optional and do not necessarily have to be implemented. Furthermore, the method can be implemented in any suitable hardware, software, firmware, logic, or combination thereof. Exemplary method 200 includes blocks 202 through 208 .
[0039] In block 202 , a determination is made whether a direct-input-mode or handicap access mode is selected (e.g., triggered)? The direct input mode may be triggered when a user attempts to adjust a thermostat setting by directly touching a manual adjustment mechanism, such as a manual adjustment mechanism 104 ( FIG. 1 ).
[0040] The handicap access mode may be triggered several different ways. For instance, the triggering impetus may be received from movement of an elevation compensation actuator 110 ( FIG. 1 ) in communication with the thermostat's controller 114 ( FIG. 1 ). For example, a user may pull down on a pull-cord which enables a switch 112 ( FIG. 1 ) to send an activation signal to controller 114 , thereby selecting a handicap access mode of operation.
[0041] The triggering impetus may also be received in the form of a sound, such as a key word, phrase, clap(s), bell, horn, etc. For example, microphone 106 receives sounds and sends them to controller 114 . Voice recognition/response module 122 ( FIG. 1 ) in conjunction with controller 114 , analyzes the received sounds and determines whether they match one of a set of sound patterns stored in memory module 116 associated with activating the handicap access mode.
[0042] Once a determination is made in block 202 whether the direct input mode or handicap access mode is selected, process 200 proceeds to either block 204 or 206 . For instance, if the direct input mode is selected in block 202 , process 200 proceeds to block 204 . If the handicap access mode is selected in block 202 , process 200 proceeds to block 206 .
[0043] In block 204 , the direct input mode is activated and thermostat receives commands through one or more manual adjustment mechanisms.
[0044] In block 206 the handicap access mode is activated. At this point, voice recognition/response module 122 ( FIG. 1 ) in conjunction with controller 114 , listen for a command to adjust a thermostat setting which includes responding to requests for information, such as the current temperature setting, the temperature in a room, and so forth. For example, a command, such as “set the heater to 68 degrees” is received by microphone 106 and converted into a digital format and compared with a list of stored commands in memory module 116 .
[0045] In block 208 , it is possible for the thermostat to reply to the use in an interactive fashion each time it receives requests or commands using speaker 108 . If the controller 114 and voice recognition/response module 122 ( FIG. 1 ) does not recognize a command, thermostat may prompt the user to repeat the command or query the user with yes/no questions to determine what the user was attempting to say. Additionally, at any point in process 200 , thermostat may transmit audio responses through speaker 108 back to the user, even if the user is using the direct input mode of operation. For examples of how the thermostat may provide audible outputs, please see U.S. Pat. No. 5,690,277 entitled Audible Thermostat to Flood, incorporated herein by reference.
[0046] In block 210 , controller 114 uses the command(s) received in either direct input mode or handicap access mode to invoke an action such as sending a signal to a increase/decrease heating, or some other suitable action, such as changing a temperature setting, a program setting (such as program interval heating/cooling periods), setting a time setting and so forth.
[0047] It is noted that whether in the direct input mode or handicap access mode, a timer is typically set for allowing a maximum time to receive commands either through a mechanical adjustment mechanism 104 ( FIG. 1 ) or through voice commands or other tones. If the thermostat does not receive the commands within a predetermined time period, the thermostat “times out” (i.e., resets) and process 200 returns back to block 202 . For example, controller 114 allows the user to perform any number of supported actions using the display panel 102 ( FIG. 1 ) and/or mechanical adjustment mechanism 104 ( FIG. 1 ) within a predetermined period of time. Otherwise, process 200 will reset. Likewise, if the thermostat does not receive audible commands within the predetermined time period, the thermostat “times out” (i.e., resets) and process 200 returns back to block 202 .
[0048] Additionally, at any point in process 200 , thermostat 200 allows for manual intervention through display panel 102 or manual adjustment mechanism 104 .
[0049] The described embodiments are to be considered in all respects only as exemplary and not restrictive. The scope of the invention is, therefore, indicated by the appended claims rather 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. | An innovative thermostat having a handicap access mode is described. When the handicap access mode is triggered, the thermostat accepts voice commands to control thermostat settings. This innovative thermostat is a particularly convenient feature for the visually impaired, and individuals with limited mobility. In one exemplary embodiment, the thermostat includes a controller operable in a direct input mode and/or a handicap access mode. When in the direct input mode, the controller receives user commands through mechanical actuation of an adjustment mechanism to adjust a thermostat setting. When in the handicap access mode the controller receives voice commands through a microphone to adjust a thermostat setting. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application Ser. No. 60/884,246, filed on Jan. 10, 2007; U.S. Provisional Application Ser. No. 60/884,268, filed on Jan. 10, 2007; and U.S. Provisional Application Ser. No. 60/908,488, filed on Mar. 28, 2007, herein incorporated by reference in its entirety.
FIELD OF THE INVENTION
The present invention relates to several improvements in a bolt-action firearm and its method of assembly. More particularly, it relates to a firearm having a two-piece bolt, an improved takedown assembly, an improved scope mount, and a buttonless stop. In addition, the present invention relates more specifically to a method of assembling a bolt-action rifle in which the proper headspace can be determined, adjusted, and fixed without disassembling the rifle.
BACKGROUND OF THE INVENTION
Bolt-action firearms are well known in the art. Typically, a cartridge is fed into the receiver from an internal magazine by the forward movement of a bolt. After the shot is fired, the bolt is retracted, which removes the spent casing. The rearward movement of the bolt is limited by a stop machined into the bolt.
However, current bolt designs have several limitations. Primarily, the extension is typically brazed on and encompasses only a small portion of the circumference of the bolt. Both of these factors limit the bolt's strength. In an effort to overcome this problem, attempts have been made to manufacture a one-piece bolt with the extension. This solution suffers from rendering the bolt extremely expensive given the amount of machining required to fabricate the bolt.
Another issue with current bolt designs is the takedown assembly. Known designs make it awkward to remove the bolt. In addition, current scope mounts do not have the unique features of the present invention.
The headspace of a bolt-action rifle is the distance between the face of the closed rifle bolt to the surface in the chamber on which the cartridge case seats.
Headspace ranges are established by industry advisory bodies, government bodies, or by individual manufacturers. In the United States, the primary advisory body is the Small Arms and Ammunition Manufacturers Institute.
In the manufacture of bolt-action rifles, headspace is measured after the firearm has been assembled. If the headspace is not within the specified range, the firearm must in many cases be disassembled and the headspace then adjusted. This process is laborious, time consuming, and slows the production of such rifles.
In view of the above, there is a need for an improved bolt design and scope mounts for a bolt-action firearm as well as a method of assembling a bolt-action rifle where the headspace may be determined, adjusted, and fixed prior to disassembling the rifle. The present invention fulfills these needs and more.
SUMMARY OF THE INVENTION
An object of the present invention is to provide a bolt-action firearm in which the bolt is machined as a rearward part that has an outwardly extending handle and an interior part that is axially displaceable. Then, in its finished form, the bolt is brazed as a single piece.
Another object of the present invention is to increase the strength of the joint between the bolt handle and the bolt.
Still another object of the present invention is to decrease the fabrication cost and assembly time of an improved bolt.
Yet another object of the present invention is to have a takedown assembly, which allows a bolt to be easily removed without any parts being misplaced.
Yet another object of the present invention is to provide a scope mount with a superior design that allows it to be mounted over a receiver without blocking the opening for the cartridge feed.
It is another object of the present invention to provide a method of assembling a firearm in which the proper headspace can be determined, adjusted, and fixed without disassembling the firearm.
It is another object of the present invention to provide a method of assembling a bolt-action firearm in which the proper headspace can be determined, adjusted, and fixed without disassembling the firearm.
It is yet another object of the present invention to provide a buttonless stop for a bolt-action firearm.
It is another object of the present invention to provide a simplified bolt stop with fewer components than known bolt stops.
It is an additional object the present invention to decrease fabrication costs and assembly time associated with known bolt stops.
It is yet another object of the present invention to provide a simplified bolt stop and to decrease the fabrication cost and assembly time associated with known bolt stops by providing a buttonless stop.
It is a further object of the present invention to provide a buttonless stop in which a bolt may be retracted and removed from a firearm through the interaction between a channel machined in the bolt and a sear surface of the firearm.
According to one embodiment of the present invention, a bolt for a bolt-action firearm includes a main body with a bolt front end, an opposing end, and an outer surface. The main body has an interior flange at the opposing end that is recessed from the outer surface of the main body and stands proud from the opposing end. A supplemental body is joined to the main body by a joint between the interior flange and a corresponding recess on the supplemental body. The supplemental body also has an integrally formed bolt handle.
According to another embodiment of the present invention, a takedown system for a bolt-action firearm includes a bolt having a circumference enclosed within a receiver of the firearm and a rod operably mounted within the receiver and in substantial touching relationship with the bolt. A pin is mounted to the receiver and connected to the rod with a spring attached to an end of the rod. The rod contains a recessed area that matches the circumference of the bolt so that the bolt can be rearwardly removed from the receiver when the rod is depressed and remains in place when the spring is in a relaxed position.
According to yet another embodiment of the present invention, a scope mount for a bolt-action firearm, where the firearm has a receiver with a top surface adapted to receive the scope mount and an ejection port substantially on a side of the receiver, includes a base having an attachment means for removably affixing to the receiver of the firearm. The base has two ends astride of the ejection port and a central region in substantial registration with the ejection port. The central region has a geometry configured to allow a cartridge to be inserted into and ejected from the ejection port.
According to still another embodiment of the present invention, a bolt-action firearm includes a receiver adapted to be received by a firearm stock and having a threaded portion. A barrel is affixed at a forward end of the receiver and has a corresponding threaded portion. A crush washer is located between the barrel and the receiver so that the barrel is threadedly adjustable about the crush washer.
According to another embodiment of the present invention, a method of assembling a firearm includes the steps of: (1) providing a barrel with a threaded portion at one end and a barrel chamber capable of seating a cartridge, (2) fitting a crush washer over the threaded portion of the barrel, (3) inserting the threaded portion of the barrel into a corresponding threaded portion of a receiver, wherein a bolt with a face is enclosed within the receiver and is adapted to travel in an open and closed position within the receiver, and (4) adjusting the barrel about the crush washer until a desired headspace is achieved, wherein the headspace is the distance between the face of the bolt in a closed position and the barrel chamber on which the cartridge seats.
According to another embodiment of the present invention, a bolt with a buttonless stop for a bolt-action firearm, where the bolt has an outer surface, includes a bolt enclosed within a receiver of the firearm and the bolt has a first channel section, a second channel section, and a third channel section on the outer surface of the bolt. An upper portion of a sear of the firearm engages the channel sections to guide the movement of the bolt. The first channel section is generally perpendicular to a bolt axis of the firearm and terminates in a stop. The second channel section is connected to the first channel section and is generally perpendicular to the first channel section. The third channel section is connected to the second channel section, is generally perpendicular to the second channel section, is generally parallel to the first channel section, and does not have a stop.
According to another embodiment of the present invention, a bolt-action firearm includes a stock, a receiver mounted in the stock, a trigger assembly mounted in the receiver, a barrel located at a forward end of the receiver, and a bolt enclosed within the receiver and adapted to travel forward and rearward within the receiver. The bolt includes a main body with a bolt front end, an opposing end, and an outer surface. The main body has an interior flange at the opposing end that is recessed from the outer surface of the main body and stands proud from the opposing end. A supplemental body is joined to the main body by a joint between the interior flange and a corresponding recess on the supplemental body. The supplemental body also has an integrally formed bolt handle.
According to another embodiment of the present invention, a bolt-action firearm includes a stock, a receiver mounted in the stock, a trigger assembly mounted in the receiver, a barrel located at a forward end of the receiver, and a bolt with an outer surface enclosed within the receiver and adapted to travel forward and rearward within the receiver. The bolt has a first channel section, a second channel section, and a third channel section on the outer surface of the bolt. An upper portion of a sear of the firearm engages the channel sections to guide the movement of the bolt. The first channel section is generally perpendicular to a bolt axis of the firearm and terminates in a stop. The second channel section is connected to the first channel section and is generally perpendicular to the first channel section. The third channel section is connected to the second channel section, is generally perpendicular to the second channel section, is generally parallel to the first channel section, and does not have a stop.
These and other objects of the present invention, and their preferred embodiments, shall become clear by consideration of the specification, claims, and drawings taken as a whole.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a cut away view of a prior art bolt-action rifle illustrating the headspace of the rifle.
FIG. 2 is a perspective view of a barrel and receiver assembled according to a method of the present invention.
FIG. 3 is an exploded view of the barrel of FIG. 2 illustrating a washer of the present invention.
FIG. 4 is a simplified schematic side view of a two-piece bolt provided in accordance with the present invention.
FIG. 5 is a simplified schematic exploded side view of the bolt of FIG. 4 .
FIG. 6 is a simplified schematic end view of the second member of the bolt of FIG. 4 .
FIG. 7 is a simplified schematic illustration of the second member of the bolt of FIG. 4 .
FIG. 8 is a simplified schematic side view of a takedown assembly provided in accordance with the present invention.
FIG. 9 is a simplified schematic side view of the takedown assembly of FIG. 8 .
FIGS. 10 and 10A are simplified schematic views of a bolt and rod engagement of the takedown assembly of FIG. 8 .
FIG. 11 is a simplified schematic exploded side view of the takedown assembly of FIG. 8 .
FIG. 12 is a simplified schematic side view of a scope mount provided in accordance with the present invention.
FIG. 13 is a simplified schematic top view of the scope mount of FIG. 12 .
FIG. 14 is a simplified schematic exploded side view of the scope mount of FIG. 12 .
FIG. 15 is a perspective view of a bolt and receiver equipped with a buttonless stop in accordance with an embodiment of the present invention.
FIG. 16 is a simplified perspective view of the buttonless stop of FIG. 15 .
FIG. 17 is a partially exploded rear perspective view of the buttonless stop of FIG. 15 .
FIG. 18 is an exploded side view of the buttonless stop of FIG. 15 depicting individual components of a sear assembly.
FIG. 19 is a simplified perspective bottom view of the buttonless stop of FIG. 18 illustrating the interaction between the sear and a channel of the bolt.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A typical bolt-action firearm includes a stock, a receiver mounted in the stock, a trigger assembly mounted in the receiver, a barrel located at a forward end of the receiver, and a bolt enclosed within the receiver and adapted to travel forward and rearward within the receiver.
FIG. 1 illustrates the interaction of the various components that create the headspace of a prior art bolt-action rifle. More specifically, FIG. 1 shows a bolt 2 in a closed position, a receiver 4 , and a barrel chamber 6 with a cartridge 8 seated in the chamber. The headspace 10 is the distance between the face of the bolt 2 and the portion of the barrel chamber 6 on which the cartridge case 8 seats. As mentioned above, when such rifles are assembled, the headspace is measured and then, if adjustments are necessary, the rifles are disassembled to modify the distance the barrel extends into the receiver. As will be appreciated, this process is not particularly efficient since it requires multiple assemblies of the rifle.
Turning to FIG. 2 , the preferred embodiment of the present method addresses this problem through the addition of a crush washer 14 . The crush washer 14 is placed between a barrel 12 and a receiver 16 . During assembly, the barrel 12 is threaded into the receiver 16 . After a bolt is assembled, the headspace is measured. If the headspace needs adjustment, the barrel 12 may be tightened or loosened about the crush washer 14 , thereby varying the distance between the face of the bolt and the face of the barrel 12 chamber in which a cartridge seats.
The crush washer 14 is an important aspect of the present invention as it allows the headspace to be adjusted without disassembling the rifle. This in turn reduces the amount of time required to assemble a bolt-action rifle and increases the efficiency of the manufacturing process.
FIG. 3 shows the individual components of the inventive method. As shown, the barrel 12 has an end with a threaded portion 20 . The crush washer 14 fits over the threaded end 20 of the barrel 12 . The threaded end of the barrel 12 is then inserted into a corresponding threaded portion of the receiver 16 . In a preferred embodiment, the crush washer 14 has a recoil lug 18 , which extends from a bottom portion of the washer 14 . The recoil lug 18 reduces the movement of the barrel 12 and receiver 16 in the stock of the rifle upon discharge.
FIG. 4 shows one embodiment of the present invention in a simplified schematic form. Specifically, it shows a two-piece bolt. In FIG. 4 , a bolt 110 has a first member (or main body) 112 and a second member (or supplemental body) 114 . The first member 112 has a bolt front end 116 and an opposing end 118 . The second member 114 has a bolt handle 120 .
As shown in FIG. 5 , an interior flange 122 is located at the opposing end 118 of the first member 112 . The interior flange 122 fits inside a corresponding recess 124 of the second member 114 (shown in FIG. 7 ). The interior flange 122 is recessed from the outer surface of the main body 112 and also stands proud from the opposing end 118 .
The interior flange 122 of the first member 112 is brazed to the corresponding recess 124 of the second member 114 . This design allows for a full 360-degree brazed joint. In contrast, prior multi-piece bolts had a separate brazed handle. The brazed handle was joined to only a portion of the circumference of the bolt. For example, FIG. 6 shows the second member 114 of the present invention, which is machined out of a single piece so that the extension 120 does not have to be brazed onto the bolt. However, prior art bolts have a brazed handle, which would only be attached to a partial circumference of the bolt (shown as the small circumference between dashed lines α and β in FIG. 6 ). In contrast, the brazed joint of the present invention is the full circumference of the interior flange 122 and its corresponding recess 124 , which creates a stronger bolt 110 .
As will be readily appreciated, the bolt 110 moves axially and translates about an axis of the bolt 110 . By using a brazed joint over the full circumference of the interior flange 122 and its corresponding recess 124 , which are also configured centrally about an axis of the bolt 110 , the amount of torque applied to the brazed joint is significantly reduced when compared to known brazed joints on bolts where the bolt handle is attached over only a portion of the circumference of the bolt. The strength of the bolt is also increased since the supplemental body engages the main body over three separate surfaces. Specifically, the three surfaces are the outer surface of the interior flange 122 , the end surface of the opposing end 118 , and the end surface of the interior flange 122 .
Creating the second member 114 with the bolt handle 120 creates a stronger handle. The brazed joint now covers the full circumference of the bolt 110 around interior flange 120 . In contrast, previous attempts only had a brazed joint that covered a fraction of the circumference of the bolt, which resulted in the forces on the brazed joint being magnified from the axial forces exerted on the handle. These forces are not present on the brazed joint when it is located over the entire circumference of the bolt 110 .
It is therefore an important aspect of the present invention that the bolt consists of two separate pieces. With this configuration, the bolt is less expensive to manufacture and has a stronger extension handle.
FIGS. 8 , 9 , and 11 show another embodiment of the present invention in a simplified schematic form. Specifically, it shows components for a takedown assembly. In FIG. 8 , a bolt 210 with a bolt handle 220 is enclosed within a receiver 130 and is adapted to slide forward and rearward within the receiver 130 .
The receiver 130 contains two holes, which operably mount a rod 132 and a pin 134 . The pin 134 keeps the rod 132 in place. The rod 132 operably engages with the bolt 210 .
As shown in FIG. 10 , the rod 132 is spring mounted on its lower end by spring 136 . The pin 134 keeps the rod 132 in its proper position. When the spring 136 is in its relaxed position, the recessed area 138 is slightly displaced from the bolt 210 so as to prevent the bolt 210 from being removed. As shown in FIG. 10A , when the user depresses the rod 132 downward, the spring 136 is forced down and the recessed area 138 now matches the circumference of the bolt 210 so that the bolt 210 can be removed from the receiver 130 .
The present invention allows the bolt 210 to be rearwardly removable from a firearm by simply pressing the rod 132 on the side of the receiver 130 . Current designs provide a pin, which keeps the bolt in place. However, this pin can be difficult to remove and replace and is easily misplaced. The present invention overcomes these disadvantages by featuring a rod 132 , which allows the bolt 210 to be easily removed, as well as the rod 132 with the pin 134 and the spring 136 to always be contained within the receiver 130 .
It is therefore an important aspect of the present invention that the bolt-action firearm has a rearwardly removable bolt that can be completely removed from the firearm by simply pressing a rod on the side of the receiver.
Although the takedown assembly has mostly been described using a standard bolt 210 , FIG. 11 further illustrates that the takedown assembly can be equally applied to the two-piece bolt 110 as described above.
FIG. 12 shows another embodiment of the present invention in a simplified schematic form. Specifically, it shows a scope mount 142 . In FIG. 12 , the scope mount 142 is removedly affixed to the top surface of the receiver 230 by an attachment means. As shown in FIGS. 13 and 14 , the scope mount 142 is attached to the receiver 230 by nuts 144 .
As can best be seen in FIG. 13 , the scope mount 142 substantially covers the top surface of the receiver 230 . The central region of the scope mount 142 is narrowed so that the ejection port of the receiver 230 is not significantly blocked in order to allow a cartridge to be easily fed into the receiver 230 . In other words, the central region is in substantial registration with the ejection port. The geometry of the central region of the scope mount 142 is configured to allow a cartridge to be inserted into and ejected from the ejection port, which is located substantially on one side of the receiver 230 .
FIG. 15 is a perspective view of a bolt 302 equipped with a buttonless stop according to an embodiment of the present invention. As shown, the bolt 302 is located in the receiver 304 of the firearm and is shown in a retracted position. A portion of the trigger mechanism 306 and the sear (not shown) are also located within the receiver 304 as illustrated in the figure. The bolt 302 has a groove or channel 308 machined into its surface, which allows the bolt 302 to be urged forward to load a cartridge into the receiver 304 and be retracted to remove a spent cartridge. Significantly, the channel 308 also allows the bolt 302 to be completely removed from the receiver 304 and the firearm (not shown).
While FIG. 15 , and the other figures, depicts a two-piece bolt as described above, it will be readily apparent that the present invention can be used with one-piece bolts as well.
Turning now to FIG. 16 , the channel 308 has several connected sections. Specifically, the channel 308 has a first channel section 310 that is generally perpendicular to bolt axis b of the firearm. The first channel section 310 terminates in an abutment surface or stop 312 . The stop 312 limits the rearward travel of the bolt 302 when it is retracted to remove a cartridge. Further, channel 308 has a second channel section 314 that is connected to the first channel section 310 . The second channel section 314 is generally perpendicular to the first channel section 310 . The second channel section 314 allows the bolt 302 to be rotated so that it may subsequently be removed. Finally, the second channel section 314 is connected with a third channel section 316 which is generally perpendicular to the second section 314 and parallel to the first section 310 . The third channel section 316 does not terminate in a stop and allows the bolt 302 to be slidably removed from the receiver.
As will be appreciated, the channel 308 and its sections 310 , 314 , and 316 are important aspects of the present invention. The channel 308 allows the bolt 302 to be urged forward and rearward to load and remove a cartridge respectively. The second channel section 314 also allows the bolt 302 to be rotated about bolt axis b and then be removed from the firearm via the third channel section 316 . As discussed in greater detail below, the specific configuration and orientation of the channel 308 eliminates the need for a button or lever to remove the bolt 302 .
Turning to FIGS. 17-19 , an upper portion 320 of the firearm sear 318 engages the channel sections 310 , 314 , 316 and guides the movement of the bolt 302 . As shown in FIG. 17 , an upper sear portion 320 protrudes slightly into the receiver 304 and into the channel (not shown). The engagement of the upper sear portion 320 and the channel sections 310 , 314 , 316 is illustrated in FIG. 19 , which is a simplified perspective view of the inventive bolt 302 and sear 318 . As will be appreciated, the bolt 302 slides rearward and forward, relative to the firearm, about the upper sear portion 320 when the portion 320 is in channel sections 310 and 316 . The bolt can also be rotated about the bolt axis b when the upper sear portion 320 travels in the second channel section 314 .
To remove the bolt 302 , a user retracts the bolt 302 via the bolt handle or extension 322 until the upper sear portion 320 contacts the stop 312 at the end of the first channel section 310 . The bolt 302 is then urged forward slightly until the second channel portion 314 is aligned with the upper sear portion 320 . Once aligned, the bolt 302 may then be rotated about bolt axis b in direction d until the upper sear portion 320 is aligned with the third channel portion 316 . As stated, the third channel portion 316 does not have a stop or abutment surface at its terminal end and allows the bolt 302 to be completely removed from the sear 318 and the receiver (not shown).
As will be readily apparent, the channel 308 and upper sear portion 320 are important aspects of the present invention as they allow the bolt 302 to be removed without the need for a button or lever. The inventive buttonless stop thereby reduces manufacturing and assembly costs, as additional components, machining, and assembly are not required. Moreover, the inventive stop does not require the stocking of replacement parts, e.g., levers or biasing means, as none are needed apart from the actual bolt 302 and sear 318 .
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various obvious changes may be made, and equivalents may be substituted for elements thereof, without departing from the essential scope of the present invention. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed, but that the invention includes all embodiments falling within the scope of the appended claims. | Several improvements to the components and assembly method of a bolt-action firearm are disclosed. An improved bolt includes two separate members, which makes the bolt less expensive to manufacture while having a stronger extension handle. An improved takedown system and buttonless stop provide two easy ways to remove a bolt from a receiver when desired without misplacing any parts. An improved scope mount has a base connected to a receiver with two ends that substantially cover the top surface of the receiver and a middle portion that is narrowed over an opening to the receiver to accommodate a cartridge. A method of assembling a firearm involves providing a barrel with a threaded portion, fitting a crush washer over the threaded portion, inserting the threaded portion into a corresponding threaded portion of a receiver, and adjusting the barrel about the crush washer until a proper headspace is achieved. | 5 |
FIELD OF THE DISCLOSURE
[0001] The present disclosure relates to methods for improving recovery of hydrocarbons from subterranean formations. More specifically, the disclosure relates to a method of controlling the fluid interface level above a horizontal producer well to effect the inflow of oil-bearing production fluids from the reservoir and to avoid breakthrough of gases into the producer well.
BACKGROUND
[0002] Gravity drainage processes are used for extracting highly viscous oil (“heavy oil”) from subterranean formations or bitumen from oil sand formations. For purposes of this patent specification, the general term “oil” will be used with reference to liquid petroleum substances recovered from subterranean formations, and is to be understood as including conventional crude oil, heavy oil, or bitumen, as the context may allow or require.
[0003] For heavy oil or bitumen to drain from a subterranean formation by gravity, its viscosity must first be reduced. The Steam-Assisted Gravity Drainage (SAGD) process uses steam to increase the temperature of the oil and thus reduce its viscosity. Other known gravity drainage processes use solvents or heat from in-situ combustion to reduce oil viscosity.
[0004] SAGD uses pairs of horizontal wells arranged such that one of the horizontal wells, called the producer, is located vertically below a second well, called an injector. The vertical distance between the injector and producer wells is typically 5 meters (5 m). The horizontal section of a SAGD well is typically 700 m to 1500 m long. For SAGD projects in the Athabasca oil sands in Alberta, Canada, the depth of the horizontal section is typically between 100 m and 500 m from the surface. Bitumen recovery from the oil sands is accomplished by injecting steam into the injector wellbore. Steam is injected from the injector wellbore into the hydrocarbon-bearing formation, typically through slots or other types of orifices in the injector wellbore liner. The steam permeates the formation within a region of the formation adjacent to the injector well; this steam-permeated region is referred to as a steam chamber. As steam is continuously injected into the formation, it migrates to the edges of the steam chamber and condenses at the interface between the steam chamber and the adjacent region of the bitumen-bearing formation. As the steam condenses, it transfers energy to the bitumen, increasing its temperature and thus decreasing its viscosity, ultimately to the stage where the bitumen becomes flowable, whereupon the mobile bitumen and condensed water flow down the edges of the steam chamber, accumulating as a “liquid inventory” in a lower region of the steam chamber and flowing into the producer wellbore. The fluid mixture of flowable bitumen and water that enters the producer well is then produced to the surface.
[0005] A significant challenge encountered by operators of SAGD well pairs is controlling the inflow distribution of oil and water over the horizontal length of the producer well, or the outflow distribution of steam, solvents, or combustion gases from the horizontal injector well. In many cases, inflow distributions or steam outflow distributions are biased towards one part of the well—for example, the region near the heel of the well (i.e., where the horizontal producer well transitions to a vertical well to the surface) or the region near the toe of the well. This results in less favourable well economics due to ineffective use of injection fluid (i.e., steam), poor bitumen recovery rates, and low recovery factors (i.e., when parts of the reservoir are not produced). The inflow/outflow biasing is influenced by the reservoir geology, which is largely outside the control of the well operator.
[0006] Another important factor influencing inflow and outflow distributions is the sand face pressure distribution along the length of the injector or producer well resulting from wellbore hydraulics. In this context, “sand face” refers to the point where flow emerges from the sand pack. In oil sands, the sand packs around the liner and flow emerges from the point where the sand is retained by the liner and flows into the gaps of the sand screen. The well operator has some control over this factor by means of the well completion design. For a typical injector well injecting steam into the formation through a slotted liner, wellbore steam pressures are highest near the heel and decrease towards the toe due to fluid friction pressure losses in the axial direction of the wellbore. Where wellbore pressures are higher at the heel, greater outflows of steam, solvent, or other injected gas are present. To equalize or create preferential outflow distributions, Dall'Acqua et al. have proposed (in International Application No. PCT/CA2008/000135) an injector completion with a tubing string run inside a liner, whereby the tubing string has ports located along its length that are sized and positioned to create a uniform or preferential sand face pressure distribution over the length of the injector well. The pressure distribution could be customized to achieve preferential outflow distributions into reservoirs with varying mobility (due to varying formation permeability, for example).
[0007] The experience of SAGD well operators in Alberta has shown that the performance of gravity drainage wells is affected by both injector and producer completion designs. In some cases, the producer completion has been shown to have a more significant effect on well performance. A method of controlling inflow distributions over the length of a long horizontal producer well is needed. Producer well design requires consideration of additional complexities that are not factors for injector well design. The fluid interface level relative to the producer needs to be managed carefully to both maximize production rates and to protect the producer well from breakthrough of injection gases. Breakthrough of steam into the producer will damage the well and/or related facilities, and breakthrough of other injection gases (e.g., light hydrocarbons such as propane and butane) reduces the efficiency of their function to mobilize bitumen.
[0008] The fluid interface (i.e., the interface between the liquid inventory and the overlying steam chamber) is characterized by a density contrast between the injection fluid (typically steam) and the produced oil and water. For purposes of this patent specification, the fluid interface level will be alternatively referred to as the “liquid level”. It is preferred to let the liquid level sit a short distance above the producer well to act as a seal preventing steam from entering the producer well. If steam is allowed to enter the producer, the steam is not being used for heating bitumen and the process becomes less efficient. Steam entering the producer well can also carry sand particles at high speeds and cause erosion of the steel liners and tubing strings in the wellbore.
[0009] To evaluate the economics of an oil recovery project, an estimate of the recovery rate is required. For conventional oil wells, an inflow performance relationship (IPR) is used to predict the oil recovery rate for the reservoir pressure and bottom hole pressure conditions expected. In this sense, conventional oil production is driven by pressure not gravity. Therefore, IPRs as used for conventional oil wells cannot be applied to gravity drainage projects, so a gravity drainage inflow performance relationship (GIPR) is needed to estimate the economics of the process.
[0010] “Thermal Recovery of Oil and Bitumen” (R. Butler, 1997, 3 rd edition, printed by GravDrain Inc., ISBN 0-9682563-0-9) presents formulas for predicting SAGD recovery rates for a given liquid head, or difference in height between the top of the steam chamber and the producer well. The calculation is based on a two-dimensional cross-section of the well and reservoir. Two other factors will affect SAGD production rates that are not covered in these calculations. Firstly, Butler's calculation assumes that the liquid level contacts the top of the producer well. In actuality, it is typical for liquid levels to sit above the producer wellbore forming a liquid “trap” that the producer wellbore is submersed in. As bitumen and water flow through the liquid trap to the producer well, pressure loss will occur. Many SAGD operators have observed significant pressure losses in this region, with resultant reduction in actual production rates relative to predicted rates. While exact causes for these pressure losses are not fully known, they are sometime attributed to two-phase flow (relative permeability) effects, plugging of slotted liners, fines migration, or other causes.
[0011] Another important consideration for predicting SAGD production rates is that wellbore pressures and temperatures vary along the length of a long horizontal well. This will cause liquid levels, and thus the depth of the liquid trap, to also vary along the length of the well, which in turn will affect the total production rate from the well. Near-wellbore reservoir heterogeneities (i.e., permeability variations close to the wellbore) will also contribute to inflow variations along the length of the well.
BRIEF SUMMARY OF THE DISCLOSURE
[0012] The present disclosure teaches methods for predicting or characterizing an inflow relationship that relates the vertical position of the liquid level to the position of a producer well. This inflow relationship is applied to producer completion design to select wellbore tubular and flow control equipment that will influence the pressure profile along the length of the producer well, which will affect liquid levels. The inflow relationship considers a number of parameters to arrive at a liquid level prediction; these parameters include injection pressure and temperature, pressures in the producer wellbore, subcool (i.e., cooling of liquid below its saturation temperature) at the heel of the producer, and the vertical temperature gradient (i.e., due to heat loss rate to the underburden, or formation below the production zone). These parameters can be measured directly or indirectly by temperature and pressure sensors placed in the injector and producer wellbores.
[0013] The permeability of a heavy oil or oil sands reservoir is non-uniform, or “heterogeneous”. Areas with high permeability will tend to allow steam and oil to flow more easily through them; thus these areas are more likely to be depleted sooner than areas with low permeability. Commonly used producer completion strategies provide little restriction to inflow from high permeability areas, so it is likely that reservoirs will be depleted non-uniformly over the length of the well. This could lead to ineffective placement or distribution of steam during the life of the well, which would reduce the overall efficiency of the process. The ideal case is for the reservoir to be depleted uniformly.
[0014] The present disclosure teaches methods facilitating the design or selection of means to limit liquid inflow into the producer well from high permeability areas and to control flow from areas with different permeabilities based on liquid level to match reservoir delivery rate. For example, methods in accordance with the disclosure can be used:
To determine the liquid level required in areas of different permeabilities so that they will produce uniformly; To determine the fluid level required to match production to different reservoir delivery rates in a homogeneous reservoir; To compare the production distribution for a measured fluid level distribution (for example, by temperature monitoring or logs) with the reservoir delivery distribution to determine the transient behaviour of the fluid level; and/or To determine the transient production distribution based on changes in the temperature distribution.
[0019] According to one embodiment of methods in accordance with the present disclosure, wellbore flows can be designed to match reservoir delivery. Using this method to determine production rate provides a basis for confirming the completion design and adjusting the design to maintain the production distribution. In this way, growth of the steam chamber can be promoted to be uniform. Alternatively, custom growth patterns can be promoted to accommodate specific geological settings for optimal recovery. Depleting the reservoir uniformly will promote uniform steam chamber growth. This is particularly beneficial for wells with water or gas caps that “rob” steam from the steam chamber rather than allowing the steam to be used as intended (i.e., for heating bitumen at the edge of the steam chamber).
[0020] Liquid level is a function of a number of parameters including injector pressure, formation heat loss rate, production rate, permeability, and producer wellbore pressure. Injector pressures are set by the well operator to be higher than the original reservoir pressure to allow for steam to enter the pore spaces within the formation. Injection pressures are limited by the fracture pressure of the formation, which is a function of well depth and overburden geology. Higher injection pressures allow for higher steam chamber temperatures. The pressure acting down on the liquid at the liquid-steam interface is expected and presumed to be close to the injector wellbore pressure.
[0021] Formation heat loss rates are governed by the heat conductivity of the underburden geology below the producer well. For a reservoir with bottom water below the producer well, heat losses may be higher and therefore the vertical temperature gradients will be higher.
[0022] Producer wellbore pressure and production rates are linked. As production rates are increased, wellbore pressures will decrease. Pressure losses of oil and water will occur as they travel downwards through the liquid trap. Pressure losses are associated with flow through porous media, typically calculated in accordance with Darcy's Law. Additional pressure losses in the liquid trap can occur due to flow convergence from the liquid trap into the openings on the horizontal liner of the producer, from plugging of openings in the horizontal liner, fines migration, relative permeability effects, or other causes.
[0023] The rates at which these temperatures and pressures decrease are generally outside the control of the well designer. However, the well designer can control the wellbore pressures through design of the producer well completion. For example, a conventional producer completion may use 88.9 mm tubing landed at the toe of the well. If this tubing diameter is increased to 139.7 mm, then pressure losses through the tubing will be lower. Wells are often controlled to a subcool at the heel of the well, which is typically between 5° C. to 20° C. Subcool at the sand face will be higher as pressure loss through the tubing results in higher pressures at the sand face. For a well with 88.9 mm tubing higher tubing pressure losses will occur, which will result in higher liquid levels. By contrast, a wellbore with 139.7 mm tubing will have less pressure loss and therefore a lower subcool at the sand face.
[0024] The preceding example demonstrates the effect of wellbore pressure on sand face subcool and consequently on liquid level. The same principles can be applied to more complicated wellbores with flow control devices mounted on the tubing string or on the liner. The sizing and positioning of flow control devices in the wellbore will affect the direction and magnitude of flow at different points in the wellbore, thus affecting the wellbore pressures.
[0025] To maximize production, liquid levels can be designed to be as close to the producer wellbore as possible without causing steam breakthrough. Lower liquid levels will provide greater head pressure in the steam chamber to drive gravity drainage to the sump (liquid inventory).
[0026] An iterative method can be applied to predict the liquid level height for an expected pressure and temperature gradient through the liquid zone and a known production rate and injector-producer pressure differential. This calculation can be applied over the well length to determine a liquid level distribution for different completion scenarios. Producer wellbore completions can be optimized to raise liquid levels in areas where production needs to be restricted, and completions can be designed to lower liquid levels in areas where production needs to be increased.
Gravity IPR
[0027] The Gravity IPR (Inflow Performance Relationship) relates the pressure difference between the steam chamber and the production wellbore to the flow rate into the production wellbore. Developing or characterizing the Gravity IPR involves using temperature measurements from the field to define an analysis boundary encompassing the production wellbore and part of the liquid inventory (i.e., sump or steam trap) surrounding the wellbore. The relationship between pressure difference and inflow rate is then determined using numerical or analytical methods. The Gravity IPR has several unique features when compared to a conventional IPR:
By using temperature measurements to define the analysis boundary, the Gravity IPR couples the drainage radius to the temperature of the fluid entering the wellbore (inflow temperature) such that a higher inflow temperature corresponds to a smaller drainage radius, and a lower inflow temperature corresponds to a larger drainage radius. The Gravity IPR accounts for the viscosity gradient in the liquid inventory surrounding the wellbore, providing a better approximation of the flow resistance in the near-wellbore region. The Gravity IPR accounts for the effect of gravity, allowing a stable range of inflow temperatures to be identified, within which the liquid inventory will move towards an equilibrium state where the inflow rate matches the rate at which liquid is delivered to the inventory (delivery rate).
[0031] Accordingly, in one aspect the present disclosure teaches a method for characterizing an inflow performance relationship relating the vertical position of the liquid level of a liquid inventory in a steam chamber in a petroleum-bearing formation relative to a horizontal producer well disposed within the formation, comprising the steps of:
measuring temperatures within the steam chamber; measure the vertical temperature gradient in the liquid inventory; defining the temperature drawdown as the difference between the steam chamber temperature and the temperature of liquids flowing into the producer well; defining an analysis boundary in a plane perpendicular to the producer well, such that the analysis boundary encompasses the producer wellbore and contacts the fluid interface between the liquid inventory and the overlying steam chamber; mapping the measured steam chamber temperature and vertical temperature gradient onto the area enclosed by the analysis boundary; defining the pressure drawdown as the difference between the steam chamber pressure and the wellbore pressure; and determining the relationship between the pressure drawdown and the flow rate into wellbore, using known numerical or analytical methods.
[0039] In one embodiment of the method, the temperature at the fluid interface is assumed to equal the steam chamber temperature, and the temperatures at locations within the analysis boundary are calculated from the vertical temperature gradient and the distance below the fluid interface.
[0040] In another embodiment, the pressure at the fluid interface is assumed to equal the steam chamber pressure, and the sum of the pressure head and the elevation head is assumed to be constant along the analysis boundary.
[0041] In a further embodiment, the steam chamber pressure is assumed to equal the saturation pressure corresponding to the measured steam chamber temperature.
[0042] The analysis boundary may be assumed to be a cylindrical boundary centred on the producer wellbore and touching the lowest part of the fluid interface. However, methods in accordance with the present disclosure are not limited to this assumption, and alternative embodiments of the method may assume a different shape for the analysis boundary.
[0043] The methods may include the additional steps of determining the relationship between the pressure drawdown and the inflow rate at a plurality of temperature drawdowns, and then plotting the inflow rate as a function of inflow temperature for a constant pressure drawdown.
Axial Flow Relationship
[0044] In addition to flowing radially from the fluid interface to the producer well, liquid may flow axially (i.e, parallel to the producer well) through the near-wellbore reservoir. For purposes of this patent specification, axial flow through the near-wellbore reservoir will be alternatively referred to as “crossflow”. The steps comprising the characterization of the gravity IPR—namely, temperature measurements, analysis boundary definition, temperature mapping, and numerical or analytical analysis—also enable accurate calculation of the axial hydraulic conductivity of the liquid inventory and, in turn, the axial flow rate.
[0045] Accordingly, in another aspect the present disclosure teaches a method for characterizing an axial flow relationship relating the conditions at two axial locations along a horizontal producer well disposed within a petroleum-bearing formation to the axial flow rate through a liquid inventory surrounding the producer well, comprising the steps of:
characterizing the gravity IPR at two axial locations along the producer well; evaluating the axial hydraulic conductivity of the liquid inventory at both locations; interpolating to approximate the axial hydraulic conductivity of the liquid inventory between the two locations; and calculating the axial flow rate through the liquid inventory as the product of the axial hydraulic conductivity, effective axial hydraulic gradient, and mean flow area.
[0050] In one embodiment of the method, the axial hydraulic conductivity of the liquid inventory between the two locations is taken as the average of the axial hydraulic conductivity at the first location and the axial hydraulic conductivity at the second location.
[0051] In another embodiment, when conditions other than the liquid level are approximately equal at the two locations, the axial hydraulic conductivity of the liquid inventory at the first location is assumed to equal the axial hydraulic conductivity at the second location and, in turn, the axial hydraulic conductivity between the two locations.
[0052] In another embodiment, the effective axial hydraulic gradient between the two locations is taken as the difference between the liquid level at the first location and the liquid level at the second location, divided by the axial distance between the two locations.
[0053] In a further embodiment, the gravity IPR is characterized at plurality of axial locations along the producer well, and an axial flow relationship is characterized for each pair of adjacent locations to create a system of axial flow relationships.
BRIEF DESCRIPTION OF THE DRAWINGS
[0054] Embodiments of the invention will now be described with reference to the accompanying figures, in which numerical references denote like parts, and in which:
[0055] FIG. 1 is a schematic cross-section through a steam chamber within a subterranean oil sands reservoir, in conjunction with a horizontal steam injection well and a horizontal production well.
[0056] FIG. 2 is an enlarged cross-section through a production well and adjacent regions as in FIG. 1 .
[0057] FIG. 3 is a flow chart illustrating steps in one embodiment of a method for establishing an inflow performance relationship for a production wellbore in accordance with the present disclosure.
[0058] FIG. 4 is a graph illustrating the variability of inflow rate into a production well with changes in inflow temperature.
[0059] FIG. 5 is a flow chart illustrating steps in one embodiment of a method for establishing an axial flow relationship for a liquid inventory surrounding a production wellbore in accordance with the present disclosure.
DETAILED DESCRIPTION
[0060] FIG. 1 schematically illustrates a horizontal well pair (i.e., injector and producer) in a typical SAGD bitumen recovery installation in a bitumen-laden subterranean oil sands formation 30 underlying an overburden layer 20 extending to the ground surface 10 , and overlying an underburden formation 40 , all in accordance with prior art knowledge and well within the understanding of persons of ordinary skill in the art. Steam under high pressure is introduced into injector well 50 from a connecting well leg (not shown) extending to ground surface 10 . Injector 50 has a slotted or orificed liner such that steam exits injector 50 through the liner slots or orifices and permeates oil sands formation 30 to create a steam chamber 70 within formation 30 . In this context, the term “steam chamber” may be understood to mean a volume within formation 30 in which steam remains present and mobile, at least for so long as steam injection into formation 30 continues. For analytical purposes, it is assumed that regions of formation 30 outside steam chamber 70 are essentially uninfluenced by the steam injected through injector 50 .
[0061] The pattern of steam migration within formation 30 , and thus the configuration of steam chamber 70 , will vary with a variety of factors including formation characteristics and steam injection parameters. However, as represented by the idealized configuration shown in FIG. 1 , a typical steam chamber 70 for a SAGD well can be considered or modeled as being generally wedge-shaped in cross-section, surrounding injector well 50 , with a “roofline” 72 and sloping side boundaries 74 converging downward toward a lower limit 76 . Steam migrating to steam chamber side boundaries 74 condenses due to the lower temperature of the surrounding region of formation 30 . As the steam condenses, it transfers energy to the bitumen, increasing its temperature and thus decreasing its viscosity such that it becomes flowable, whereupon the mobile bitumen and condensate flow downward and accumulate as a liquid inventory 80 within a lower region of steam chamber 70 , below injector 50 . A fluid interface 85 is thus formed between liquid inventory 80 and the overlying region of steam chamber 70 . Based on theory and field observation, the level of fluid interface 85 is assumed for analytical purposes to be lowest (i.e., closest to producer 60 ) at a point 85 X directly above producer 60 .
[0062] A producer well 60 is installed at a selected depth below and generally parallel to injector 50 , such that it can be expected to lie within the zone of liquid inventory 80 upon formation of steam chamber 70 . Producer well 60 has slots or other suitable orifices to allow the bitumen/condensate mix in liquid inventory 80 to enter producer 60 for production to the surface 10 . For this purpose, producer well 60 typically has a liner with narrow slots or other orifices that allow liquid flow into producer 60 while substantially preventing sand or other contaminants from entering producer 60 or clogging the slots or orifices in the liner.
[0063] FIG. 2 provides an enlarged illustration of liquid inventory 80 and producer well 60 within a lower region of steam chamber 70 . Also indicated in FIG. 2 is an analysis boundary 90 surrounding producer well 60 , with analysis boundary 90 being an empirically defined or selected parameter for purposes of predictive methods in accordance with the present disclosure. In accordance with a preferred embodiment of these predictive methods, analysis boundary 90 is assumed to be circular in cross-section and centered around producer well 60 , with a radius corresponding the distance from the center of producer 60 to point 85 X on fluid interface 85 . However, alternative configurations of analysis boundary 90 may be appropriate to satisfy case-specific physical and/or analytical constraints.
Gravity Inflow Performance Relationship (Gravity IPR)
[0064] FIG. 3 schematically illustrates one embodiment of a procedure for developing a “gravity IPR” for use in evaluating the stability of liquid inventory 80 . In this context, the stability of liquid inventory 80 relates to the stability of the vertical distance from producer 60 to point 85 X on fluid interface 85 at given points along the horizontal length of producer 60 (which for purposes of FIG. 2 corresponds to the radius of circular analysis boundary 90 ). Procedural and analytical steps shown in FIG. 3 are summarized below:
Stage 101 —Temperature Measurements:
[0000]
Measure temperatures within steam chamber 70 and the vertical temperature gradient in liquid inventory 80 .
Define the temperature drawdown to be the difference between the steam chamber temperature and the inflow temperature (i.e., temperature of produced fluids flowing into producer well 60 ). For this purpose:
[0000] Temperature drawdown=steam chamber temperature−inflow temperature.
Stage 102 —Define Analysis Boundary:
[0000]
Consider a cross-section of producer wellbore 60 and the surrounding liquid inventory 80 in a plane perpendicular to the axis of the wellbore. Define analysis boundary 90 such that it encompasses producer wellbore 60 and contacts fluid interface 85 between liquid inventory 80 and the overlying steam chamber 70 . The distance between producer wellbore 60 and fluid interface 85 (i.e., the liquid level) is given by the temperature drawdown and the vertical temperature gradient. For this purpose:
[0000] Liquid level=temperature drawdown/vertical temperature gradient.
Stage 103 —Temperature Mapping:
[0000]
Map the measured steam chamber temperature and vertical temperature gradient onto the area enclosed by analysis boundary 90 . For this purpose:
The temperature at liquid-vapor interface 85 is assumed to equal the steam temperature. The temperature at locations within analysis boundary 90 is calculated from the vertical temperature gradient and the distance below the liquid-vapor interface 85 .
Stage 104 —Solution:
[0000]
Specify the pressure conditions at analysis boundary 90 and producer wellbore 60 . Define the pressure drawdown to be the difference between the steam chamber pressure and the wellbore pressure. Using numerical or analytical methods known to persons of ordinary skill in the art, determine the relationship between the pressure drawdown and the flow rate into wellbore 60 . For this purpose:
The pressure at liquid-vapor interface 85 is assumed to equal the pressure within steam chamber 70 (which is taken to be the saturation pressure corresponding to the measured steam chamber temperature). The total head (i.e., the sum of the pressure head and the elevation head) is assumed to be constant along analysis boundary 90 . A skin factor is included to account for near-wellbore pressure losses that are measured in the field but not captured by conventional equations for flow through porous media (e.g., Darcy's Law). “Skin factor” in this context is a term well understood in the field (see, for example, the definition of skin factor in the Schlumberger Oilfield Glossary: www.glossary.oilfield.slb.com).
Flow chart blocks 110 and 120 in FIG. 3 represent additional criteria taken into consideration in the solution stage 104 :
Block 110 —The analysis boundary represents a uniform head (i.e., a flow isobar), and flow normal to the boundary integrated around the perimeter of the boundary defines the inflow to the wellbore. In its simplest form, it is a cylindrical boundary centered on the producer wellbore and touching the lowest part of the fluid interface. Other shapes for the analysis boundary can be incorporated to reflect better conformance to a different fluid level interface, if additional refinement to reflect a changing steam chamber shape with time is desired. Block 120 —Reservoir and fluid properties are calculated over the range of temperatures considered inside the analysis boundary. Relative permeability properties are incorporated and in combination with the temperature field and fluid portions in determining the pressure gradients that are integrated to arrive at the inflow characterization.
Stage 105 —Stability Assessment:
[0000]
Determine the relationship between the pressure drawdown and inflow rate at various temperature drawdowns. Plot inflow rate as a function of inflow temperature for a constant pressure drawdown, as shown in FIG. 4 . The slope of the plotted curve(s) is negative in the stable range of inflow temperatures.
Within the stable range of inflow temperatures, an increase in liquid level (resulting when the delivery rate into liquid inventory 80 exceeds the inflow rate into producer well 60 ) will cause the inflow rate to increase. The liquid level will rise until it reaches an equilibrium position at which the inflow rate matches the delivery rate. A decrease in liquid level (resulting when the inflow rate exceeds the delivery rate) causes the inflow rate to decrease. The liquid level will drop until it reaches an equilibrium position at which the inflow rate matches the delivery rate. Outside the stable range of inflow temperatures, an increase in liquid level will cause the inflow rate to decrease, allowing the liquid level to “run away.” For certain combinations of pressure drawdown, fluid properties, and reservoir properties, the slope of the curve(s) will be positive for all inflow temperatures, indicating that there is no stable range of inflow temperatures. A decrease in liquid level will cause the inflow rate to increase, potentially leading to steam breakthrough into producer 60 .
Practical Application of Gravity IPR
[0082] When coupled to a wellbore hydraulic model, the gravity IPR enables the performance of a production well to be evaluated by measuring the inflow temperature along the well to determine when the liquid level is reaching critical levels (i.e., when fluid level rise in portions of the well compromises production efficiency, or when fluid level drop in portions of the well compromises well integrity). More specifically, the gravity IPR provides a basis for:
Configuring producer well completions to deliver a pressure distribution that is within the range of self-balancing performance over the life of the well. Evaluating how pump intake subcool should be controlled to maintain hydraulic conditions within the self-balancing range of operation over the entire well. Evaluating production rate capacities for specific completion options and field applications. Using inflow temperature distributions for evaluating completion configuration changes to match reservoir variations and maintain performance within the self-balancing range over the entire well. Using temperature fall-off logs for evaluating completion configuration changes to match reservoir variations and maintain performance within the self-balancing range over the entire well. Using temperature measurements to set “smart well” controls for production wells and maintain performance within the self-balancing range over the entire well. Positioning or repositioning tubing intake points to maintain performance within the self-balancing range over the entire well. Adjusting chokes on gas lift tubing based on intake temperature to maintain performance within the self-balancing range over the entire well. Determining where fluid conditions approach water saturation, leading to flashing, which in turns chokes flow to automatically regulate inflow. By using flow conditions in the GIPR assessment, determining locations where pore throat water flashing may produce scaling and inflow restrictions.
[0093] The gravity IPR also provides a basis for determining reservoir delivery distribution over the length of the steam chamber:
For producer wells operating in the self-balancing range, the delivery distribution can be calculated from temperature fall-off logs and inflow distributions using distributed temperature measurements under static inflow conditions. For wells operating in the dynamic range, the reservoir delivery distribution can be calculated from the inflow rate to the well and the transient behaviour of the fluid level. Transient plugging development (for example, plugging of slots/orifices in the liner, or plugging in the formation itself by way or pore throat plugging) can be determined using temperature measurements and the gravity IPR. Producer well configuration updates can be evaluated to:
Assess the likelihood of maintaining the well in the self-balancing performance envelope and the reconfiguration requirements to maintain stability. Determine a production intervention schedule to maintain an efficient production distribution under dynamic fluid level control.
[0099] Other analytical methods for describing the inflow performance of the SAGD or any other gravity process can be calibrated using methods in accordance with the present disclosure. For example a conventional IPR inflow performance relationship can be calibrated by determining the drainage radius in the basic IPR equation as a function of inflow temperature. This can provide an even simpler basis for evaluating SAGD inflow performance. One example of such an application would be wellbore hydraulics programs used for analyzing and optimizing completions for SAGD production.
Axial Flow Relationship
[0100] FIG. 5 schematically illustrates one embodiment of a procedure for developing an axial flow relationship for use in predicting the axial flow rate through liquid inventory 80 . In FIG. 5 , reference numbers 101 - 105 , 110 , and 120 correspond to the same reference numbers in FIG. 3 , specifically in the context of a first location along a producer well. Reference numbers 201 - 205 , 210 , and 220 similarly correspond to flow chart blocks 101 - 105 , 110 , and 120 in the context of a second location along the producer well. Procedural and analytical steps shown in FIG. 5 are summarized below:
Characterization of Gravity IPR at Two Axial Locations:
[0000]
Characterize the gravity IPR at two axial locations along producer well 60 :
Measured or estimated conditions at the two locations (for example, steam chamber temperature, vertical temperature gradient, fluid properties, or reservoir properties) will be used to approximate conditions in the liquid inventory between the two locations. The greater the distance between the two locations, the greater the uncertainty in this approximation. An analysis boundary suitable for characterization of the gravity IPR may not be appropriate for characterization of the axial flow relationship. When liquid flows radially from fluid interface 85 to producer well 60 , the pressure gradient is largest near producer well 60 , where the flow area is smallest and the fluid viscosity is highest (because the temperature decreases from fluid interface 85 to producer well 60 ). Consequently, conditions in the part of liquid inventory 80 near producer well 60 will have a greater influence on the gravity IPR than conditions in other parts of liquid inventory 80 . By contrast, the axial flow relationship will be most strongly influenced by conditions in the part of liquid inventory 80 near fluid interface 85 , where the temperature is highest and the fluid is most mobile. Therefore, for characterization of the axial flow relationship, analysis boundary 90 should be expanded to include the part of liquid inventory 80 near fluid interface 85 . For purposes of characterizing an axial flow relationship, the axial hydraulic conductivity may be calculated at numerous points in liquid inventory 80 and analysis boundary 90 defined according to an axial hydraulic conductivity criterion. For example, the analysis boundary may be drawn along a contour of constant axial hydraulic conductivity to encompass only the part of the liquid inventory where the axial hydraulic conductivity is greater than a specified minimum value. The axial hydraulic conductivity criterion may alternatively be expressed in terms of an axial hydraulic conductivity ratio—for example, the ratio of the local axial hydraulic conductivity to the maximum axial hydraulic conductivity.
Evaluation of Axial Hydraulic Conductivity of Liquid Inventory—Block 300 :
[0000]
Evaluate the axial hydraulic conductivity of the part of liquid inventory 80 enclosed by analysis boundary 90 at both axial locations, using numerical or analytical methods known to persons of ordinary skill in the art. The axial hydraulic conductivity is the proportionality constant relating the axial flow velocity and the axial hydraulic gradient.
Interpolate to approximate the axial hydraulic conductivity of liquid inventory 80 between the two axial locations. For this purpose:
The axial hydraulic conductivity of liquid inventory 80 between the two axial locations is taken as the average of the axial hydraulic conductivity at the first location and the axial hydraulic conductivity at the second location. When conditions other than the liquid level (for example, the steam chamber temperature, vertical temperature gradient, fluid properties, and reservoir properties) are approximately equal at the two locations, the axial hydraulic conductivity of liquid inventory 80 at the first location may be assumed to equal the axial hydraulic conductivity at the second location and, in turn, the axial hydraulic conductivity between the two locations. By extension, when conditions other than the liquid level are approximately uniform along producer well 60 , the axial hydraulic conductivity of liquid inventory 80 need only be evaluated at one axial location. Variations in the liquid level will shift the mobile part of liquid inventory 80 vertically but will not significantly affect the axial hydraulic conductivity.
Calculation of Axial Flow Rate—Block 310 :
[0000]
Calculate the axial flow rate through liquid inventory 80 as the product of the axial hydraulic conductivity, effective axial hydraulic gradient, and mean flow area. For this purpose:
The effective axial hydraulic gradient between the two locations is taken as the difference between the liquid level at the first location and the liquid level at the second location, divided by the axial distance between the two locations. The effective axial hydraulic gradient may account for variations in the axial hydraulic gradient with distance from producer well 60 due to radial flow from fluid interface 85 to producer well 60 . The mean flow area is taken as the average of the areas enclosed by analysis boundary 90 at the two locations.
Practical Application of Gravity IPR with Crossflow
[0113] The gravity IPR may be characterized at a plurality of axial locations along the producer well and axial flow relationships developed for each pair of adjacent locations to create a system of axial flow relationships, or axial flow “network”. When included in a wellbore hydraulic model coupled with the gravity IPR, an axial flow network enables improved estimation of liquid level variations over time, based not only on an imbalance between the inflow distribution and delivery distribution, but also on the axial redistribution of liquid from locations with a higher liquid level to locations with a lower liquid level.
[0114] Practical applications of an axial flow network include:
estimation of the liquid level above blank (i.e., unslotted or unscreened) sections of the producer liner, where liquid must flow axially through the liquid inventory before flowing radially into a slotted section of the liner; and estimation of the liquid level above locations of formation damage, where a reduction in the near-wellbore permeability causes liquid to flow preferentially in the axial direction.
[0117] It will be readily appreciated by those skilled in the art that various modifications of methods in accordance with the present disclosure may be devised without departing from the scope and teaching of the present invention. It is to be especially understood that the subject methods are not intended to be limited to any described or illustrated embodiment, and that the substitution of a variant of a claimed element or feature, without any substantial resultant change in the working of the methods, will not constitute a departure from the scope of the invention.
[0118] In this patent document, any form of the word “comprise” is to be understood in its non-limiting sense to mean that any item following such word is included, but items not specifically mentioned are not excluded. A reference to an element by the indefinite article “a” does not exclude the possibility that more than one of the element is present, unless the context clearly requires that there be one and only one such element.
[0119] Relational terms such as “parallel”, “horizontal”, and “perpendicular” are not intended to denote or require absolute mathematical or geometric precision. Accordingly, such terms are to be understood in a general rather than precise sense (e.g., “generally parallel” or “substantially parallel”) unless the context clearly requires otherwise.
[0120] Wherever used in this document, the terms “typical” and “typically” are to be interpreted in the sense of representative or common usage or practice, and are not to be understood as implying invariability or essentiality. | In a method for controlling interface level between a liquid inventory and an overlying steam chamber in a subterranean petroleum-bearing formation, an inflow relationship is developed to predict the vertical position in a gravity field of the interface between the two fluids (liquid and steam) with a density contrast relative to a horizontal producer well. The inflow relationship is applied to producer well completions by designing the completion to raise or lower sand face pressures according to mobility variations over the horizontal length of the well. This pressure distribution will affect liquid levels according to the inflow relationship. The completion can include tubing-conveyed or liner-conveyed flow control devices to create flow network that provides a customized sand face pressure distribution. Axial flow relationships between adjacent locations along the producer well may be modeled in order to develop an axial flow network to facilitate estimation of liquid levels at selected locations. | 4 |
FIELD OF THE INVENTION
[0001] The invention relates generally to oilfield equipment, including reciprocating pump fluid ends and down-hole equipment for well service. Particularly demanding applications include high-pressure hydraulic stimulation on intervals along horizontal wellbores in ultralow-permeability (unconventional) formations.
INTRODUCTION
[0002] New designs described herein incorporate innovative applications of well-known technical principles for improved stimulation system performance. Both adverse and beneficial aspects of the technical principles are well-represented in relationships between mechanical shocks and their associated vibration spectra. Adverse aspects of these relationships are strikingly manifest, for example, in the troubling failure rates of even the most modern conventional high-pressure well-stimulation pumps. While analogous relationships can alternatively be beneficially employed to increase pump reliability and enhance well productivity through more efficient and localized stimulation.
[0003] Specific examples are cited in the following paragraphs to illustrate how reliability improvements have evolved from a better understanding of causes and effects of shock and vibration in fluid ends. First, remarkably strong and repetitive mechanical shocks commonly originate in fluid ends. Second, the intensity of mechanical shocks that occur with normal closure of conventional fluid end check valves can be reduced through innovative design changes. Third, without such design changes, fatigue-related damage is exacerbated, predisposing fluid ends to premature failures.
[0004] It is frequently observed that premature fluid end failures are more common now than they have been in the past. This is true even though the underlying failure mechanisms have remained unchanged in some aspects. One such unchanged aspect is the fact that a mechanical shock is created each time a fluid end check valve closes on a valve seat. But these mechanical shocks are generally much stronger now than they have been in the past. The reason for a strong valve-closing shock is high back pressure, and peak back pressures are much higher now than they have been in the past. ***And each strong valve-closing shock inevitably generates high-energy broad-spectrum vibration that propagates throughout the fluid end.***
[0005] Broad vibration spectra, in turn, excite a range of destructive resonances in the fluid end or the pump as a whole, predisposing various parts to fatigue-related cracking and ultimate failure. A variety of designs shown and described in the following materials explain how these damaging vibration resonances can be controlled (e.g., suppressed) using a hierarchy of tunable systems, tunable subsystems, tunable components and design elements. Controlling destructive resonance excitation, in turn, limits vibration-induced cracking.
[0006] But resonance vibration excitation shouldn't always be limited in well stimulation systems; sometimes it should be enhanced! Specifically, vibration spectra originating in tunable down-hole stimulators can be tailored (i.e., their frequency spectra can be shifted) to maximize stimulation efficiency. Directing such (tuned) stimulation vibration to geologic material adjacent to a wellbore, in the presence of high down-hole hydraulic pressures, typically increases rock fracturing. The combination of high hydraulic pressures plus tuned stimulation vibration thus tends to both: (1) open geologic channels, and (2) prop them open, for improved well production. To optimize these complementary functions, the extent of geologic fracturing (with its associated geologic fragmentation) is periodically assessed in near-real time. Such analysis proceeds continuously as feedback data from the geologic material are processed in programmable controllers running empirically-derived software algorithms (broadly termed herein: frac diagnostics).
[0007] The above geologic feedback data, in the form of backscatter vibration, thus allow closed-loop control of geologic stimulation. That is, closed-loop stimulation control incorporates feedback of a portion of the controlled-system output (i.e., stimulated geologic material) to the controlled-system input (i.e., tuned stimulation vibration). Feedback data are used to guide re-tuning of stimulation vibration as needed, with quick convergence on optimal stimulation levels. This process is accomplished in tunable down-hole stimulation systems via closed-loop control of mechanical shocks, the shocks originating in one or more tunable down-hole stimulators.
[0008] Closed-loop control of mechanical shocks implies control of the kinetic energy impulses corresponding to a moving hammer (or mass) element striking, and rebounding from, a fluid interface in a tunable vibration generator. At least one such generator resides within each tunable down-hole stimulator. And at least a portion of a generator's initial kinetic energy for each hammer strike is converted to broad-spectrum vibration energy. So with each hammer strike and rebound, the vibration spectrum's power spectral density (PSD) can be detected and adjusted as desired under closed-loop control.
[0009] Closed-loop PSD control for tunable down-hole stimulation systems means that transmitted vibration spectra from a tunable vibration generator are tuned at their source (e.g., by altering the rebound cycle time for each hammer element strike). Such tuning effectively shapes a transmitted vibration spectrum's PSD to concentrate stimulation vibration power in predetermined frequency ranges. The predetermined frequency ranges for any stage of stimulation are those that maximize transmission of vibration resonance excitation power to the adjacent geologic materials.
[0010] The geologic materials themselves then (after a short time delay) report their actual levels of resonance excitation in the form of backscatter vibration feedback data. Calculated control signals based on the feedback data then close the loop in closed-loop shock control. The control signals are calculated using a programmable controller running frac diagnostic software, and the signals are then applied (e.g., via feedback control link) to one or more tunable stimulation vibration generators to optimize stimulation in near-real time.
[0011] Note that evaluation of backscatter vibration data detected in one or more down-hole stimulators may optionally be enhanced in light of corresponding down-hole temperature and/or hydraulic pressure data sensed at one or more down-hole stimulators. Such enhanced evaluation may be carried out, e.g., via frac diagnostics in a programmable controller for the relevant tunable down-hole stimulation system.
[0012] An example benefit of such enhanced evaluation relates to estimating the effects of down-hole hydraulic pressure changes on fluid flow (e.g., liquid hydrocarbons) from stimulated geologic material. As stimulation proceeds, channels for such fluid flow are opened, but flow may be blocked by relatively higher down-hole hydraulic pressure. If the hydraulic pressure is sufficiently (temporarily) lowered, fluid flow from the stimulated geologic material ensues, carrying with it, e.g., small particulates that may alter backscatter vibration. The vibration alteration(s), in turn, may include Doppler shifts secondary to the velocity of the flowing particulates, such velocity being an early indicator of the wellbore stage's productivity potential.
[0013] To acquire the benefits of backscatter vibration as described above, tunable down-hole stimulators transmit shock-generated stimulation vibration to geologic materials adjacent to their wellbore stages or location(s). Access is via, e.g., casing perforations and/or slots (i.e., ports or access openings). (See, e.g., U.S. patent application number 2014/0000909 A1, incorporated by reference). Since maximum resonance excitation frequencies necessarily change as stimulation progresses, closed-loop shock control in the stimulator(s) causes the PSD of stimulation vibration energy to be correspondingly shifted in near-real time to optimize stimulation, and thus generate the corresponding backscatter vibration, of individual producing zones or stages within a wellbore. (See, e.g., U.S. patent application number 2014/0041876 A1, incorporated by reference). ***Optimization thus means more effective stimulation (i.e., more productive wells) achieved with higher energy efficiency in less time.***
[0014] The following background materials discuss the vibration spectrum of an impulse in greater detail, highlighting its importance with examples of the deleterious effects of mechanical shock and vibration in conventional applications. Analogous-in-part vibration-related issues in the automotive industry are also described to illustrate that ***positive or negative aspects of vibration in mechanical systems may become economically important, or even evident, only at certain frequencies and/or above certain energy levels.*** Building on this background, subsequent sections describe selected alternative designs for high-pressure pump components (e.g., check valves and vibration dampers) and associated well-stimulation equipment (including, e.g., tunable down-hole stimulators) which address current operational issues of reliability, efficiency, and efficacy in well stimulation.
BACKGROUND
[0015] The necessity for modified designs (e.g., as described herein and in related patents) may be better appreciated after first considering: (1) the remarkably high failure rates of conventional reciprocating high-pressure pumps (especially fluid ends), and (2) the substantial uncertainties (e.g., in cost/benefit analysis and technical complexity/reproducibility) associated with multistage well stimulation in unconventional formations. Pump-related issues will be considered initially.
[0016] Frac pumps (also commonly called fracking or well-service 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).
[0017] 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 cyclically close upon a (relatively stationary) valve seat to achieve substantially unidirectional bulk fluid flow through the valve.
[0018] Pulsatile fluid flow results from cyclical pressurization of the pumping chamber by a reciprocating plunger or piston strokes 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.
[0019] 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).
[0020] 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). A portion of total check-valve closure impulse 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 energy impulse (i.e., a mechanical shock). As described below, each such mechanical shock is associated with transmission of broad-spectrum vibration energy, the range of vibration spectrum frequencies being an inverse function of valve-closure energy impulse duration.
[0021] Repeated application of dual valve-closure shocks with each pump cycle (i.e., one shock from the suction valve and another shock from the discharge valve) predisposes each check valve, and the pump as a whole, to vibration-induced (e.g., fatigue) damage. Cumulative valve-closure shocks thus significantly degrade frac pump reliability, proportional in part to the rigidity and weight of each check valve body.
[0022] The increasing importance of fatigue-related frac pump reliability issues has paralleled the inexorable rise of peak pumped-fluid pressures in new fracking applications. And insight into fatigue-related failure modes has been 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 and in the frequency domain, and also in terms of its effects 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 ).
[0023] References to time and frequency domains appear frequently in descriptions of acquisition and analysis of shock and vibration data. And these domains are mathematically represented on opposite sides of equations generally termed Fourier transforms. Further, 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).
[0024] Digital representations of time and frequency domain data play important roles in computer-assisted shock and vibration studies. 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 movement of a check valve body is abruptly stopped by a valve seat. Relatively high acceleration values and broad vibration spectra are prominent, because each valve-closure impulse response primarily represents a violent conversion of a portion of kinetic energy (of the moving valve body and fluid) to other energy forms.
[0025] 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, a portion of that energy is necessarily transmitted to the pump housing in the form of broad-spectrum vibration energy. This relationship of (frequency domain) vibration energy to (time domain) kinetic energy, is mathematically represented by a Fourier transform. Such transforms are well-known to those skilled in the art of shock and vibration mechanics. For others, a graphical representation (i.e., plots) rather than a mathematical representation (i.e., equations) may be preferable.
[0026] For example, 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 relatively broad-spectrum band of high-amplitude vibration. ***The breadth of the vibration spectrum is generally inversely proportional to the impulse duration.***
[0027] Thus, as noted above, a portion of the check valve's cyclical valve-closure kinetic energy is converted to relatively broad-spectrum vibration energy. The overall effect of cyclical check valve closures may therefore be compared to the mechanical shocks that would result from repeatedly striking the valve seat 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).
[0028] 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 energy impulse. The difference is that impulse-generated (e.g., valve-generated) vibration occurs in bursts having relatively broad spectra (i.e., simultaneously containing many vibration frequencies) ranging from a few Hz to several thousand Hz (kHz).
[0029] In conventional frac pumps then, nearly all of the (relatively broad-spectrum) valve-generated vibration energy must be transmitted to proximate areas of the fluid end or pump housing because vibration energy cannot be efficiently dissipated in the (relatively rigid) valves themselves. Based on extensive shock and vibration test data (see Harris ) 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 vibration 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).
[0030] Opportunities to limit fluid end damage can reasonably begin with experiment-based redesign to control vibration-induced fatigue. For example, a spectrum of vibration frequencies initially applied in the form of a test shock can reveal structural resonance frequencies likely to cause trouble in a particular pump. These revealed frequencies are herein termed critical frequencies. For example, a test shock may comprise a half-sine impulse of duration one millisecond, which has predominant spectral content up to about 2 kHz (see Harris , p. 11.22). This spectral content likely overlaps, and thus will excite, a plurality of the pump's structural resonance (i.e., critical) frequencies. Excited critical frequencies are then readily identified with appropriate instrumentation, so attention can be directed to limiting operational vibration at those critical frequencies.
[0031] Limiting vibration at critical frequencies through use of the above shock tests can be particularly beneficial in blocking progressive fatigue cracking in a structure. If vibration is not appropriately limited, fatigue cracks may grow to a point where fatigue crack size is no longer limited (i.e., the structure experiences catastrophic fracture). The size of cracks just before the point of fracture has been termed the critical crack size. 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 (with consequent earlier progression to catastrophic fracture). (See Harris , p. 33.23).
[0032] 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 fatigue-related 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 among the valves most commonly 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.
[0033] 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.
[0034] 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 the 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 eventually 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.
[0035] 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, meaning that at least a portion of the total vibration energy is converted to heat energy and dissipated (i.e., the heat is rejected to the surroundings). A reduction in total vibration energy results in reduced 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.
[0036] Further, when considering vibration in well stimulation systems comprising frac pumps together with down-hole equipment, additional opportunities for increased efficiency 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 vibration energy to well-specific geologic parameters contributes to operational flexibility, efficiency, and efficacy.
SUMMARY OF THE INVENTION
[0037] Tunable down-hole stimulation system design includes closed-loop control of (generally truck-mounted) pumps and tunable down-hole stimulators. Tunable down-hole stimulators hydraulically transmit broad vibration spectra tuned for maximum resonance excitation and fracturing of targeted geologic materials adjacent to the wellbore. Frequencies and amplitudes of both transmitted stimulation vibration and backscatter vibration data are acquired by one or more detectors in each tunable down-hole stimulator. Closed-loop control of stimulation vibration is exercised using feedback data relevant to progress of the stimulation process, the feedback data including backscatter vibration originating in stimulated geologic material.
[0038] For initial (stimulation-induced) geologic fracturing, which is associated with relatively large fragment sizes, the power spectral density (PSD) of tunable down-hole stimulator vibration energy is down-shifted. That is, PSD is tuned to shift the distribution of vibration power toward relatively lower frequencies. A PSD down-shift thus tends to match stimulation vibration frequencies with the relatively-lower resonant frequencies of large geologic fragments. As stimulation progresses to smaller-size fragments, corresponding (higher frequency) backscatter vibration data are fed back (in a closed-loop) to a programmable controller. The controller then creates at least one control signal and transmits it to at least one stimulator to cause progressive up-shifting of the stimulator's transmitted vibration energy. That is, the PSD of the stimulator's transmitted vibration energy is changed by shifting the distribution of vibration power toward relatively higher frequencies). ***Stimulator power requirements are minimized because available stimulation vibration energy is efficiently shifted toward (and concentrated in) the bands of resonant frequencies to which the geologic material is most susceptible at every stage of stimulation.*** Thus, progressive geologic fragmentation at minimum energy levels is optimized, with inherent production of self-generated proppant as geologic fragments are progressively, and controllably, reduced to proppant-size.
[0039] Self-generated proppant may be of considerable importance if it reduces the need for pumping of exogenous proppant (e.g., sand shipped to the drilling site from Wisconsin). And the geologic fragmentation associated with self-generated proppant contributes to wellbore stimulation for increased productivity. Both geologic stimulation and proppant generation are closely related to the manner in which a closed-loop stimulation system generates and modifies broad-spectrum vibration energy within a wellbore.
[0040] Stimulation vibration energy is generated and modified in the wellbore to minimize transmission losses as the energy travels to adjacent geologic material. On striking the material, the energy immediately excites resonant vibrations which lead to vibration-induced geologic fractures and fragmentation. Backscatter vibration data originating from the stimulated geologic materials is subsequently captured by detectors on one or more tunable down-hole stimulators. Analysis of this backscatter vibration data in near-real time then ensures that stimulation vibration energy remains efficiently concentrated (i.e., via feedback-controlled PSD's) for creating specific geologic responses (i.e., fractures and fragmentation), rather than being dissipated as wasteful heat. Beneficial geologic stimulation is thus obtained using a combination of minimum applied vibration energy, plus resonance vibration effects assessed via detection of backscatter vibration from the stimulated geologic material.
[0041] Note that plasma sources (e.g., an electric arc) are also described as producing wide-band stimulation vibration energy. But such plasma sources do not incorporate the feedback-control of stimulation vibration, and thus the associated benefits of stimulation vibration energy concentration, as described herein.
[0042] The size range of geologic fragmentation encountered throughout the above stimulation process is broad, including large chunks through smaller fragments to proppant-sized particles. Efficient stimulation over the entire range therefore requires current feedback data regarding fragment or particle sizes within the geologic material. (See, e.g., U.S. Pat. Nos. 8,535,250 B2 and 8,731,848 B2, incorporated by reference). And various embodiments of the present invention provide for such data to be extracted substantially from band-limited backscatter vibration originating in the geologic fragments themselves.
[0043] But the composition of geologic fragments demonstrates wide variations. So supplemental data may usefully be extracted (e.g., via empirically-derived frac diagnostics) from parameters in addition to backscatter vibration, such as ambient (down-hole) pressure and temperature. It is particularly difficult to obtain an accurate description of shale reservoirs, which are substantially different from conventional and other types of unconventional reservoirs. (See, e.g., U.S. Pat. No. 8,731,889 B2, incorporated by reference). Thus various embodiments of the present invention reflect a variety of different functional relationships among the parameters that may bear on necessarily time-dependent modifications of (initially broad-spectrum) stimulation vibration. The manner in which each functional relationship among parameters bears on vibration modifications is determined, as noted above, by one or more frac diagnostic tools (i.e., software) residing in a programmable controller for each tunable down-hole stimulation system.
[0044] Frac diagnostics reflect not only different stimulation approaches needed for various types of geologic reservoirs, but also for different configurations of tunable down-hole stimulation systems. Pertinent system parameters include, for example: (1) the number and type of pumps, (2) the presence of optional pressure and/or temperature sensors in tunable down-hole stimulators, and (3) the number of tunable down-hole stimulators present. Notwithstanding differences among the variety of system embodiments however, they all reflect applications of similar technical principles (relating to, e.g., the vibration spectrum of an impulse) to the objective of efficient delivery of effective down-hole stimulation vibration.
[0045] Regarding differences mentioned above in the number and type of pumps, certain embodiments of tunable down-hole stimulation systems include one or more pumps comprising a tunable fluid end. In such pumps, valve-generated vibration spectra are suppressed using tunable components to limit fatigue-related fracturing of pump structures aggravated by destructive excitation of pump resonances. Vibration suppression, as described herein, includes damping (i.e., dissipation as heat) and/or shifting of the vibration's PSD. The desired effect in each case is to decrease the amount of vibration power present at a pump's critical frequencies.
[0046] Further, certain tunable down-hole stimulation system embodiments may comprise one or more relatively higher-pressure pumps for fluid (e.g., plain water) that contains no proppant (schematically illustrated and labeled herein as frac pumps). One or more such frac pumps may be combined with one or more relatively lower-pressure pumps for fluid containing exogenous proppant (schematically illustrated and labeled herein as proppant pumps). Such system embodiments facilitate pulsed proppant placement or PPP (see below) in previously fractured geologic material.
[0047] In an example scenario for initial geologic fracturing (e.g., initially comprising relatively large rock fragments), one or more frac pumps provide relatively high hydraulic down-hole pressure. Simultaneously, the PSD of broad-spectrum tunable down-hole stimulator vibration is down-shifted (i.e., PSD is pre-tuned to shift the distribution of stimulation vibration power toward relatively lower frequencies). The pre-tuned vibration provides relatively lower vibration frequencies for synergistic combination with relatively high pumped-fluid (hydraulic down-hole) pressures to optimize initial stimulation. As stimulation progresses, up-shifting is carried out (i.e., PSD is re-tuned to shift the distribution of stimulation vibration power toward relatively higher frequencies). Such higher frequencies are needed to maintain progressive stimulation as fracturing proceeds to smaller rock fragments (e.g., fragments approaching proppant particles in size).
[0048] As noted above, the extent of geologic fragmentation is periodically assessed in real time via analysis in programmable controllers running empirically-derived algorithms (broadly termed herein: frac diagnostics). The diagnostics operate on data including band-limited backscatter vibration energy from the rock fragments themselves, as well as optionally-sensed down-hole pressure, temperature, and/or related parameters. The degree of rock fragmentation for each stimulation stage is thus periodically assessed for optimized flowback (e.g., through substantial flow equalization within a cluster of analogous stages).
[0049] Preplanned stimulation of each fracture stage for self-generation of proppant-sized particles is thus individually controlled via adjustment of: (1) down-hole hydraulic pressures, and/or (2) the magnitudes and frequencies of transmitted tunable down-hole stimulator resonance excitation vibrations. Inherent production of self-generated proppant from the stimulated geologic material is thus facilitated to support long-term stable productivity of each stage and cluster. Effectiveness of proppant placement, including the potential need for supplemental exogenous proppant, are assessed via comparison of transmitted stimulation vibration with its corresponding (time-displaced) backscatter vibration, in combination with associated (conventional) well logging data.
[0050] Such combined data may be used to guide intermittent (e.g., pulsed) addition of exogenous proppant to a wellbore (typically under reduced pressure), between proppant-free fracs (under relatively higher pressures). Pulsed-proppant additions minimize the total amount of exogenous proppant needed to supplement in situ or self-generated proppant resulting from tunable down-hole stimulation. Thus, the task of stimulation (including proppant placement) is simplified. The overall frac process thus becomes a series of quickly-executed incremental steps under closed-loop control for fast convergence on an optimal end point.
[0051] Note certain differences between pulsed-proppant placement (or PPP) as described herein and the industry practice of pumping different types of slurries or fluids in discrete intervals, that is, as slugs or stages. (See, e.g., U.S. Pat. No. 8,540,024 B2, incorporated by reference). First, proppant addition in PPP is under closed-loop control; it is a function, in part, of backscatter vibration sensed down-hole in near-real time by one or more detectors on each tunable down-hole stimulator. Second, proppant-laden fluid may be injected into a wellbore (via a separate proppant pump) at lower pressures than those associated with the frac pump(s) which otherwise feed the wellbore with a proppant-free fluid stream. And Third, proppant provided via the PPP closed-loop system is supplemental to self-generated proppant which is created anew through stimulation vibration transmitted by one or more tunable down-hole stimulators.
[0052] A tunable down-hole stimulation system embodiment to accomplish such PPP is schematically illustrated herein to emphasize certain advantages stemming from separation of the relatively high-pressure frac pump from the (optionally) relatively lower-pressure proppant pump. The absence of proppant in the relatively high-pressure fluid end means longer life for high-pressure valves, with resultant improvements in fluid end reliability. Even in proppant pumps, valve life-cycles and fluid-end reliability would improve because the valves would (optionally) be operating at relatively lower pressures, thereby producing relatively less-energetic valve-generated vibration with narrowed (and less damaging) vibration spectra.
[0053] As described herein, control of vibration spectra (particularly their power spectral densities or PSD's) guides the design and operation of both tunable fluid ends and tunable down-hole stimulators. These subsystems, in turn, contribute to the increased reliability and productivity of tunable down-hole stimulation systems. Fundamental principles are invoked throughout this description to explain major benefits of improved vibration suppression (in tunable fluid ends) and improved vibration generation, transmission and analysis (via tunable down-hole stimulators and programmable system controllers).
[0054] In the following paragraphs, both generation of broad-spectrum vibration in tunable down-hole stimulators, and incorporation of the stimulators in tunable down-hole stimulation systems, are considered before control of valve-generated vibration in tunable fluid ends. This is to emphasize the role of induced resonance excitation vibration in geologic materials for maximizing well productivity.
[0055] Suppression of resonance excitation in tunable fluid ends, on the other hand, limits the destructive effects of valve-generated vibration (for maximizing fluid end reliability). Comparisons will be noted between the related-in-part techniques for inducing or suppressing a desired range of resonance-related power spectral densities in systems comprising both tunable down-hole stimulators and (optionally) tunable fluid ends.
[0056] The desirability of tunable down-hole stimulators in tunable down-hole stimulation systems stems from the well-known vertical and horizontal heterogeneity of unconventional reservoirs. Wide variability of geologic materials adjacent to wellbores is common, meaning that consistently-beneficial stimulation design has been difficult to achieve. In current practice, some fracture stages are typically found to be substantially more productive than others, while the cost of fracking varies little from stage-to-stage. Thus, stimulation design currently reflects compromises between the efficiency of a single customized fracture stage and the degraded performance of multiple one-size-fits-all stages that include a variety of geologic materials having different productive potentials.
[0057] Such currently unavoidable inefficiencies are substantially reduced by the advent of new tunable down-hole stimulation systems as described herein. With the new systems, progressive series of customized fracture stages can be realized in near-real time through productive integration of: (1) pumps (optionally having tunable fluid ends), (2) tunable down-hole stimulators, and (3) programmable controllers. Each fracture stage is electively customized in turn, through use of near-real time frac diagnostics. Relatively productive stages can be readily identified for optimal stimulation, followed by combination of such stages into strategically important productive clusters.
[0058] And the twin keys to creation of productive clusters in horizontal wellbores are (1) gathering backscatter vibration data generated in different portions of a tunable down-hole stimulation system and (2) processing these and related data (e.g., pressure and/or temperature) in the system's programmable controller to create control signals. Control signals, in turn, optimize stimulation; they can also facilitate accurate placement and adjustment of inflow control devices within a tunable down-hole stimulation system.
[0059] Embodiments of tunable down-hole systems may comprise a plurality of tunable subsystems, e.g., (optionally) tunable fluid ends and/or tunable down-hole stimulators. And each subsystem may comprise tunable components, e.g., tunable valves, tunable valve seats, and/or tunable vibration generators. Functions of tunable subsystems are coordinated via control elements including, for example, down-hole pressure and/or temperature sensors, detectors for both transmitted and backscatter vibration, and programmable computers running various frac diagnostic software programs. Communication pathways (e.g., the control links schematically illustrated herein) connect control elements, as well as tunable components and subsystems.
[0060] Control links carry information (e.g., data, electronic signals for analog or digital encoded variables, and parameters such as frequency, time, amplitude, pressure values, and/or temperature values). Communication pathways include, e.g., mechanical links, electrical cables, wireless links, and/or fluid-filled spaces. While example embodiments of tunable subsystems, tunable components, control elements and control links are described and schematically illustrated herein, the following examples are intended to be merely representative of certain functional groupings to enhance the clarity of overall system description.
[0061] One such functional grouping concerns detection, analysis and modification of vibration. In either closed-loop or open-loop embodiments, a single (wide dynamic range) accelerometer can function as a detector of vibration, whether transmitted as broad-spectrum stimulation energy or received in the form of band-limited backscatter vibration energy. But since the typical energy levels of (relatively high-energy) transmitted vibration and (relatively low-energy) backscatter vibration may differ substantially, two or more separate accelerometers may be preferred for greater accuracy. Regardless of their arrangement in a tunable down-hole stimulation system, one or more vibration detectors initiate the flow of feedback information necessary for closed-loop control.
[0062] An illustration of such closed-loop control is seen in a first embodiment of a tunable down-hole stimulation system. The system comprises at least one frac pump for creating down-hole hydraulic pressure, together with at least one tunable down-hole stimulator, each stimulator comprising a tunable vibration generator for transmitting vibration hydraulically. The system further comprises a programmable controller for creating a plurality of control signals and transmitting at least one control signal to each frac pump and each tunable down-hole stimulator. Additionally, each tunable down-hole stimulator comprises at least one accelerometer for sensing vibration and for transmitting an electrical signal derived therefrom (i.e., for transmitting an electrical signal which is a function of the vibration as sensed by the accelerometer through change in one or more accelerometer electrical parameters such as capacitance, inductance and/or capacitance). And the programmable controller is responsive to that electrical signal (i.e., the programmable controller creates at least one control signal as a function of that electrical signal).
[0063] Each tunable down-hole stimulator comprises a hammer element longitudinally movable within a hollow cylindrical housing having a longitudinal axis, a first end, and a second end, the first end being closed by a fluid interface, and the second end being closed by a driver element. The driver element comprises at least one field emission structure for moving the hammer element to strike, and rebound from, the fluid interface to generate broad-spectrum vibration.
[0064] Each of the above field emission structures is responsive to at least one control signal, and the generated broad-spectrum vibration has a predetermined power spectral density responsive to at least one control signal. Additionally, each tunable vibration generator has a characteristic rebound frequency, and each accelerometer is responsive to that characteristic rebound frequency.
[0065] The characteristic rebound frequency is substantially influenced by the driver element. And each driver element may comprise one or more magnetic field emission structures and/or one or more electric field emission structures. A hammer element (i.e., a mass) is longitudinally movable within the cylindrical housing between the driver element and the fluid interface. Such movement is influenced (i.e., controlled in an open-loop or closed-loop manner) by forces exerted on the hammer via the magnetic and/or electrical fields of the field emission structure(s). (See, e.g., U.S. Pat. No. 8,760,252 B2, incorporated by reference). To facilitate hammer element movement, the hammer element may comprise, e.g., one or more permanent magnets, and the driver element's field emission structure(s) may comprise, e.g., one or more electromagnets, at least one with reversible polarity and variable field strength. See the '252 patent for other examples of field emission structures.
[0066] By design, the hammer element periodically moves toward impact on the fluid interface (analogous in part to the impact of a fluid end valve closure), followed by movement away from the fluid interface (i.e., rebounding from the impact). More specifically, the hammer element moves (under the influence of the driver element's electric and/or magnetic fields) to strike, and rebound from, the fluid interface, thus generating broad-spectrum vibration. In other words, the cylindrical housing, driver element, hammer element, and fluid interface function together as a tunable vibration generator for stimulation.
[0067] Note that the hammer element is responsive to the driver element both for striking, and rebounding from, the fluid interface. Responsiveness of the hammer element may be achieved via open-loop control (using empirically-derived predictions of hammer element direction and velocity based, e.g., on field emission strength) or closed-loop control (using, e.g., feedback data on hammer element position to calculate direction and velocity of hammer element movement). The latter data may be obtained, e.g., via an electric field sensor on the fluid interface interacting with an electret electric field emission structure on the hammer element.
[0068] Note further that a block diagram of a tunable down-hole stimulator is schematically illustrated herein as having an internal stimulator interconnect which connects two sections: (1) a section comprising an optional down-hole pressure sensor with a tunable vibration generator as described above and (2) a section comprising one or more optional temperature sensors combined with one or more detectors for transmitted and backscatter vibration. The separate (and more numerous) functions of these two sections with their detectors and optional sensors may be compared with the internal structural features shown in the separate schematic illustration of a tunable hydraulic stimulator. Taken together, the two schematic illustrations and the written description herein explain how the relatively less-complex tunable hydraulic stimulator might be used in a relatively-simple open-loop system, while the functionally more-complex tunable down-hole stimulator is adapted to the greater demands of a closed-loop feedback control system.
[0069] Regardless of a stimulator's configuration, stimulation vibration energy may preferably be transmitted from down-hole stimulators in relatively short bursts that are spaced apart in time. Time-delayed backscatter vibration energy may then be sensed at the same or different down-hole stimulators in the periods between bursts of transmitted vibration. But both transmitted and backscatter vibration energy can be detected at the fluid interface because they will be present at different times. Thus, one or more accelerometers may provide data on both transmitted and backscatter vibration energy, as well as on the delay time inherent in backscatter vibration.
[0070] Delay time, in turn, may be interpreted (e.g., using frac diagnostics) to indicate the stimulation depth or total distance traveled by the backscatter vibration energy. Further, changes in the backscatter vibration's power spectral density (see below) may also (again using frac diagnostics) be used to characterize the geologic material along a wellbore. Thus, vibration information detected by one or more detectors at a fluid interface, as well as estimates of related parameters (e.g., Doppler shift) that can be extracted therefrom, may be particularly useful when determining the preferred directions, depths and lengths of multiple wellbores to be placed in a relatively confined geologic space.
[0071] The importance of vibration information is reflected in the schematic illustration herein of a tunable down-hole stimulation system. The illustration includes a block-diagram of a tunable down-hole stimulator, the diagram clearly separating the function of transmitting broad-spectrum vibration for stimulation from the functions of detecting both transmitted vibration energy and band-limited (and time-shifted) backscatter vibration energy. The separated functions emphasize, for example, that changes in backscatter vibration's frequency band limits are reflected as shifts in the vibration energy's power spectral density (or PSD) plot. That is, an up-shift in PSD will reveal that relatively lower frequencies represent a smaller fraction of the plot's total vibration energy. And relatively higher frequencies will be seen to represent a greater portion of the plot's total vibration energy. Such an up-shift could occur naturally as stimulation of geologic material progresses, with backscatter vibration arising in ever-smaller stimulated particles having relatively higher resonant frequencies.
[0072] Since backscatter vibration emanates from particles experiencing vibration resonance excitation (i.e., stimulation), changes in the backscatter vibration's PSD can reveal changes in the particles' resonance frequencies. And since particles' resonance frequencies are functions of, among other things, particle size and composition (e.g., hardness), analysis of PSD data can directly indicate the local effects of stimulation. In other words, frac diagnostics applied during the stimulation process can provide near real-time information on the changing nature of the stimulated geologic material. ***Specifically, the extent and range of stimulation-generated fragmentation can be estimated through analysis of sequential PSD shifts in band-limited backscatter vibration energy.***
[0073] Note that the influence of absolute power levels on backscatter vibration calculations may be substantially reduced through scaling of power measurements (including PSD) to local maxima.
[0074] Note also that periodic estimates of the degree of shift in PSD may be used to estimate progress (in near-real time) toward a desired end point for stimulation. Thus, stimulation may be optimized via control of vibration energy to achieve a predetermined degree of fragmentation. If more fragmentation is desired, one may up-shift (or re-tune) the power spectral density of the originally-transmitted vibration to make more total high-frequency stimulation energy available. A tunable down-hole stimulator facilitates this up-shift through responsiveness of its hammer element's rebound cycle time to its driver element's field emission structure(s).
[0075] Responsiveness of a hammer element to a driver element of a tunable down-hole stimulator may be achieved via, e.g., a field emission structure comprising an electromagnet/controller having programmable magnetic field polarity reversal and variable magnetic field strength, as seen, e.g., in linear reversible motors. Control of magnetic field strength is optionally via open-loop and/or closed-loop networks associated with the electromagnet/controller. Note that such magnetic field strength control allows the driver to influence hammer element movement before, during and after each impact via attractive or repelling spatial forces. See. e.g., the '252 patent for a discussion of spatial forces.
[0076] In practice, cyclical changes in magnetic field strength may be characterized by a polarity reversal frequency responsive to the accelerometer signal mentioned earlier and/or to a signal from a tunable down-hole stimulator system controller. Longitudinal movement of the hammer element is thus responsive in part (e.g., via electromagnetic attraction and repulsion) to the driver element's cyclical magnetic polarity reversal. For example, 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.
[0077] Thus, 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 of the driver element's magnetic field polarity and strength. The duration of the hammer element's entire flexure-rebound cycle is thus controllable; it 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 (e.g., cycles per second) and is termed “characteristic rebound frequency” herein.
[0078] Each hammer strike & rebound applies a mechanical shock to the fluid interface which generates a (relatively-broad) spectrum of stimulation vibration frequencies that are transmitted hydraulically via the fluid interface (and the surrounding down-hole fluid) to the adjacent geologic material. (See the Background section above). The breadth of the generated stimulation vibration spectrum is a reflection of a mechanical shock's duration (i.e., the rebound cycle time). Shortening the rebound cycle time broadens the generated-vibration spectrum (i.e., the spectrum extends to include relatively higher frequencies). The power spectral density is therefore up-shifted, meaning that more of the total power of the transmitted spectrum is represented in the higher frequencies. In this manner, additional stimulation energy (i.e., rock-fracturing energy) may be directed to relatively smaller rock fragments because these fragments have resonances at the relatively-higher stimulation vibration frequencies. Thus, a tunable down-hole stimulator's transmitted stimulation vibration energy may be controlled so as to encourage continued geologic fragmentation to a predetermined fragment size (e.g., to a size for effective function as a proppant).
[0079] Summarizing, hammer rebound movement may be either augmented or impeded by the driver element's magnetic field polarity and strength, thereby changing hammer rebound cycle time and thus changing the character of stimulation vibration spectra generated. That is, the driver element's field emission structure comprising an electromagnet/controller can effectively, and in near-real time, tune each stimulation vibration spectrum transmitted by the fluid interface for application to geologic material adjacent to a wellbore. Such tuning may comprise, for example, altering a transmitted vibration spectrum's bandwidth and/or changing the relative magnitudes of the vibration spectrum's frequency components (i.e., changing the spectrum's power spectral density). In other words, stimulation energy in the form of vibration spectra transmitted by a tunable down-hole stimulator's fluid interface may be subject (in near-real time) to alterations in response to ongoing results of frac diagnostic calculations operating on feedback data inherent in backscatter vibration.
[0080] Note that alternative embodiments of a down-hole stimulation vibration generator may be described as having the form of a linear electrical motor, the hammer element acting as an armature. One such form is seen in railguns, with the armature providing the conducting connection between (parallel) rails. In this case, opposing currents in the rails (and thus the hammer movement) would be controlled by the driver to achieve the desired characteristic rebound frequency. (See, e.g., U.S. Pat. Nos. 8,371,205 B2 and 8,677,877 B2, both incorporated by reference).
[0081] Progressive alterations in the character of stimulation vibration energy applied to down-hole geologic material may include, for example, changes in vibration frequencies present, changes in relative energy levels of vibration frequency components, and/or changes in the total power of a pulse of stimulation vibration. Such changes may be desirable while stimulation proceeds through a continuum of fracturing of the geologic material. Progress of stimulation is reflected in backscatter vibration, the character of which changes with continued fracturing and/or fragmentation of the geologic material. That is, the geologic material's absorption of stimulation vibration energy, and its radiation of backscatter vibration, changes in a time-varying manner. Changes in absorbed stimulation energy, in turn, cause changes in backscatter vibration that may be detected (e.g., by an accelerometer) at the fluid interface. The resulting accelerometer signal may then be fed back to the driver (e.g., by cable or wireless link) as described herein.
[0082] The invention thus facilitates a form of closed-loop (feedback) control of the stimulation process that may be optimized (i.e., to yield better results from less stimulation). One might choose, for example, to emphasize relatively higher down-hole pressure and lower frequency stimulation vibration energy initially. One might then choose to adaptively decrease the down-hole pressure and increase relatively higher frequency stimulation vibration spectrum components as stimulation progresses. Individual tunable down-hole stimulators of the invention can support such an optimization strategy inherently because they naturally produce relatively broad vibration spectra (rather than substantially single-frequency vibration like an aviation black-box pinger). Should a greater frequency range be desired than that obtainable from a single tunable down-hole stimulator, a plurality of such stimulators may be interconnected in a ***tunable down-hole stimulator array***. Operation of such an array may be controlled via, for example, a programmable controller as part of a tunable down-hole stimulation system, the controller having one or more control links to the driver of each stimulator of a tunable down-hole stimulator array. Such an array may reveal location dependent resonances through cross PSD calculations in the programmable controller. (See, e.g., U.S. Pat. No. 8,571,829 B2, incorporated by reference).
[0083] In such a tunable down-hole stimulator array, the driver element polarity reversal frequency of each down-hole stimulator may be made responsive to a band-limited portion of backscatter vibration represented in one accelerometer signal. Alternatively or additionally, stimulation vibration of the array may be subject to control via programmable devices elsewhere in a wellbore and/or at the wellhead.
[0084] A second embodiment of tunable down-hole stimulation system is similar in several respects to the above first embodiment, comprising at least one frac pump for creating down-hole hydraulic pressure. But the second embodiment differs in that at least one frac pump is combined with at least one proppant pump connected in parallel with the frac pump for adding exogenous proppant. The system further comprises at least one tunable down-hole stimulator, each stimulator comprising a tunable vibration generator having a characteristic rebound frequency. A programmable controller is included for creating a plurality of control signals and transmitting at least one control signal to each frac pump, each proppant pump, and each tunable down-hole stimulator. Each tunable down-hole stimulator comprises at least one accelerometer for sensing vibration and for transmitting an electrical signal derived therefrom (i.e., for transmitting an electrical signal which is a function of the vibration as sensed by the accelerometer through change in one or more accelerometer electrical parameters such as capacitance, inductance and/or resistance). And each accelerometer is responsive to the characteristic rebound frequency (i.e., the accelerometer transmits at least one electrical signal which is a function of the characteristic rebound frequency). Finally, the programmable controller is responsive to the electrical signal (i.e., the programmable controller creates at least one control signal as a function of that electrical signal). Further, longitudinal hammer element movement, as noted above, is associated with the tunable vibration generator's characteristic rebound frequency. In certain embodiments, the characteristic rebound frequency may be similar to the magnetic field's polarity reversal frequency to aid control of the hammer's longitudinal displacement.
[0085] A third embodiment of a tunable down-hole stimulation system differs from the above first and second embodiments in part because it comprises a wellbore which itself comprises a vertical wellbore, a kickoff point, a heel, and a toe. At least one frac pump creates down-hole hydraulic pressure in the wellbore, and at least one tunable down-hole stimulator is located within the wellbore (and between the heel and toe). Each stimulator comprises a tunable vibration generator, and a programmable controller creates a plurality of control signals and transmits at least one control signal to each frac pump and each tunable down-hole stimulator. Each tunable down-hole stimulator comprises at least one accelerometer for sensing vibration and for transmitting an electrical signal derived therefrom, and the programmable controller is responsive to the electrical signal.
[0086] As noted above, part of the vibration sensed at the fluid interface typically includes time-delayed backscatter vibration. It also may contain temperature data related to the degree of rock fracturing and/or fragmentation, including the size of rock fragments. Fracturing-related temperature changes may be induced in part by mechanical inefficiencies secondary to vibration earlier transmitted from the fluid interface. (See U.S. Pat. No. 8,535,250 B2, incorporated by reference). Hence, temperature-related well-stimulation data can be used to augment control of fracturing resulting from transmitted stimulation vibration.
[0087] Note also that the driver element's polarity and field strength may also or alternatively be directly responsive (e.g., via integrated control electronics and windings of the electromagnet) to the magnetic field strength at the fluid interface. Such responsiveness may be mediated by changes in the magnetic field permeability sensed by the control electronics, the permeability changes being in part functions of the amplitude and frequency of backscatter vibration received by the fluid interface. Reception of the backscatter vibration thus allows (by at least two mechanisms) near-real-time estimation of the degree of stimulation imposed by the tunable down-hole stimulator.
[0088] 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 spectra. For convenience, alternate hammer embodiments may comprise one or a plurality of interchangeable striking faces, each having a single value within a predetermined range of modulus choices. Choice of that range will facilitate tuning of the down-hole stimulator to predetermined stimulation vibration spectra, of course, and the range of vibration spectra parameters (e.g., frequency and magnitude) will also be influenced by the fluid interface's modulus of elasticity and the design criteria vibration spectrum frequency range.
[0089] The spectra of stimulation vibration desired for a particular application will generally be chosen to encompass one or more of the (estimated) 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 (1) one or more programmable microprocessors in the tunable down-hole stimulator and/or (2) one or more programmable microprocessors in the tunable down-hole stimulation system controller. Such estimates may be based in part, e.g., on the portion(s) of the backscatter vibration energy from stimulated porous media.
[0090] Note that a tunable down-hole stimulator is intended for down-hole use within a fluid environment maintained in the wellbore via (1) fluids collected through explosively-formed perforations or preformed slots in the wellbore casing 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 either the tunable down-hole stimulator or the tunable hydraulic stimulator can be completely sealed from internal contact with surrounding fluid, use of either embodiment is not subject to dielectric strength and conductivity limitations (e.g., “compensation dielectric liquid” required in U.S. patent publication number 2014/0027110 A1 cited above) that are common in pulsed power apparatus. (See also U.S. Pat. No. 8,616,302 B2, incorporated by reference).
[0091] Note also that tunable resilient circumferential seals are electively provided to isolate predetermined explosively-formed perforations or preformed slots in portions of the wellbore casing (analogous in part to swell packers). (See, e.g., U.S. patent application number 2014/0051612 A1, incorporated by reference). Such tunable seals can provide a tuned coupling of the stimulator to the wellbore casing. The circumferential seal comprises a circular tubular area which may contain at least one shear-thickening fluid to assist tuning to a preferred frequency range. And the fluid may further comprise nanoparticles which, in conjunction with the shear-thickening fluid, also facilitate tuning of the seal as well as heat scavenging.
[0092] Having summarized certain improvements in new tunable down-hole stimulation systems as a whole, this description now focuses on subsystems and components (e.g., structures and functions of the frac pump's fluid end and down-hole stimulators). While a tunable down-hole 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 fluid end failures.
[0093] 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.
[0094] 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.
[0095] 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 materials 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).
[0096] 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. 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).
[0097] 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 “characteristic rebound 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.
[0098] 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.
[0099] 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.
[0100] 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 ).
[0101] 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).
[0102] 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).
[0103] 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.
[0104] 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.
[0105] 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.
[0106] 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.
[0107] 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.
[0108] 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.
[0109] 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 structure 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 structures 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.
[0110] 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.
[0111] 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.
[0112] 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.
[0113] 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.
[0114] Flexibility in the choice of tunable valve 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
[0115] 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 characteristic rebound 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.
[0116] 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 characteristic rebound frequency), and vibration attenuation.
[0117] 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.
[0118] 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.
[0119] 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.
[0120] 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).
[0121] 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).
[0122] 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).
[0123] 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.
[0124] 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).
[0125] 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.
[0126] 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.
[0127] 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.
[0128] 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.
[0129] 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).
[0130] 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.
[0131] 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.
[0132] 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.
[0133] 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.
[0134] 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.
[0135] 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.
[0136] 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.
[0137] 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.
[0138] 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.
[0139] 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.
[0140] 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).
[0141] 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).
[0142] 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.
[0143] 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.
[0144] 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.
[0145] 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.
[0146] 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).
[0147] 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.
[0148] 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.
[0149] 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.
[0150] 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.
[0151] 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.
[0152] 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.
[0153] 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.
[0154] 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.
[0155] 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.
[0156] 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.
[0157] 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.
[0158] 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.
[0159] 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 characteristic rebound frequency.
[0160] Lowered characteristic rebound 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).
[0161] 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.
[0162] 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/rebound, 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).
[0163] 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).
[0164] 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).
[0165] 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 (e.g. cycle time and peak pressure 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.
[0166] 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.
[0167] 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.
[0168] 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.
[0169] 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
[0170] 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.
[0171] 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.
[0172] 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.
[0173] 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.
[0174] 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.
[0175] 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.
[0176] 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 ).
[0177] 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.
[0178] 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).
[0179] 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.
[0180] 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.
[0181] 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.
[0182] 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.
[0183] 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.
[0184] 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.
[0185] 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.
[0186] FIG. 17 schematically illustrates a 2-dimensional view of major components, subsystems, and interconnections of a tunable down-hole stimulation system, together with brief explanatory comments on component and subsystem functions. As aids to orientation, a schematic wellbore is shown, as are control link pathways for communication among pumps, tunable down-hole stimulator(s) and a tunable down-hole stimulation system controller. Schematic pathways are shown for stimulation vibration energy directed toward down-hole geologic material adjacent to the wellbore, and for backscatter vibration energy emanating from the geologic material.
DETAILED DESCRIPTION
[0187] Tunable equipment associated with high-pressure well-stimulation comprises a first family of tunable down-hole stimulators (plus associated controllers, power supplies, etc.), a second family of (frac) pumps optionally comprising tunable fluid ends (which include but are not limited to, e.g., tunable valve assemblies and/or vibration dampers), and a third family of closed-loop tunable down-hole stimulation systems. An example tunable down-hole stimulation system comprises at least one frac pump, at least one tunable down-hole stimulator, and at least one tunable down-hole stimulation system programmable controller. The controller has control links to at least one frac pump and at least one tunable down-hole stimulator. Note that each frac pump in a tunable down-hole stimulation system may optionally comprise one or more components of a tunable fluid end.
[0188] The above three equipment families have strikingly different operational characteristics. In the first family, tunable down-hole stimulators operate within the wellbore, generating and transmitting vibration tailored to enhance stimulation of geologic materials for higher hydrocarbon yields. In contrast, fluid ends of the second family may 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. The third family of closed-loop tunable down-hole stimulation systems includes system controllers plus elaborations of the first family's tunable hydraulic stimulators, with optional inclusion of the second family's tunable fluid ends. Structures related to the first and second families are shown in FIGS. 1-16 , while FIG. 17 schematically illustrates various structures and functions of third-family systems.
[0189] 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.
[0190] 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.
[0191] 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 .
[0192] 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 .
[0193] 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.
[0194] 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.
[0195] 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 .
[0196] 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).
[0197] 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.
[0198] 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.
[0199] 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.
[0200] 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.
[0201] 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.
[0202] 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).
[0203] 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.
[0204] 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.
[0205] 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 .
[0206] 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.
[0207] 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 .
[0208] 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 characteristic rebound frequency) through increase of rebound cycle time, and selective vibration attenuation through energy dissipation (i.e., via redistribution) at predetermined assembly resonant frequencies.
[0209] 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.
[0210] 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 characteristic rebound frequency.
[0211] 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.
[0212] 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.
[0213] 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.
[0214] 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 .
[0215] 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 .
[0216] 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.
[0217] 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.
[0218] 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.
[0219] 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.
[0220] 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 ″.
[0221] 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.
[0222] 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).
[0223] 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).
[0224] 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).
[0225] 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 .
[0226] 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.
[0227] 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.
[0228] 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 nonlinearly 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.
[0229] 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.
[0230] 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 characteristic rebound frequency as described above.
[0231] 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 electrical signal (i.e., an accelerometer-generated feedback signal) representing vibration transmitted and received via fluid interface 520 .
[0232] Driver element 560 (comprising a field emission structure which itself comprises electromagnet/controller 564 / 562 ) reversibly seals second end 592 , and hammer (or movable mass) element 540 is longitudinally movable within housing 590 between driver element 560 and fluid interface 520 . In some embodiments, hammer element 540 may itself be a field emission structure consisting of a permanent magnet (or consisting of a plurality of permanent magnets). Polarity of any such permanent magnets is not specified because it would be assigned in light of the electromagnet/controller 564 / 562 . Alternatively, hammer element 540 may be analogous in part to the armature of a linear electric motor, as in a railgun. (See, e.g., the '205 and '877 patents noted above). Note that the above accelerometer-generated feedback electrical signal may be augmented by, or replaced by, sensorless control means (e.g., controlling operating parameters of electromagnet 564 such as magnetic field strength and polarity) in free piston embodiments of the tunable hydraulic stimulator. (See, e.g., U.S. Pat. No. 6,883,333 B2, incorporated by reference).
[0233] Thus, hammer element 540 is responsive to the magnetic field emitted by 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 “characteristic rebound 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 .
[0234] Fluid interface 520 transmits vibration spectra generated by hammer impacts on fluid interface 520 as well as receiving backscatter 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).
[0235] 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).
[0236] 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.
[0237] FIG. 16 also schematically illustrates a first electrical cable 516 for carrying accelerometer electrical signals (schematically representing vibration data 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 (to form a tunable hydraulic stimulator array) and/or for connecting one or more down-hole tunable hydraulic stimulators to related equipment (e.g., a programmable controller as shown in FIG. 17 ) proximal in a wellbore and/or adjacent to the wellhead. Accelerometer electrical signals provide feedback on transmitted vibration and also on received backscatter vibration to driver element 560 .
[0238] 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.
[0239] In certain embodiments, frac diagnostic software and data to implement sensorless control via operating parameters (e.g., magnetic field strength and polarity) 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.
[0240] 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., vibration characterized by predetermined magnitude and/or frequency and/or PSD) 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 or control link, (see FIGS. 16 and 17 ) may extend to other hydraulic stimulators and/or to wellhead or other auxiliary equipment (see, e.g., FIG. 17 ) that may 1) power the hydraulic stimulator, 2) receive and transmit stimulation-related data, 3) coordinate stimulator operation (e.g. vibration phase, frequency, amplitude and/or PSD) with related equipment, and/or 4 ) modify driver-related frac diagnostic software programs affecting tunable hydraulic stimulator operations.
[0241] 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 or stage 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.
[0242] 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 a field emission structure comprising an electromagnet/controller 564 / 562 having cyclical magnetic polarity reversal characterized by a variable polarity reversal frequency; 2) longitudinal movement of hammer (or movable mass) 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 accelerometer 518 's electrical signal (and thus responsive to vibration sensed by accelerometer 518 ; 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 characteristic rebound frequency which is the inverse of the hammer rebound cycle time; 7) the hammer may rebound in phase with polarity reversal and; 8) the hammer rebound cycle time is a function of i) the cyclical magnetic polarity of driver element 560 and/or; ii) the moduli of elasticity of hammer element 540 and fluid interface 520 .
[0243] FIG. 17 schematically illustrates a 2-dimensional view of major components and interconnections of a tunable down-hole stimulation system 699 , together with brief explanatory labels and comments on component functions. As aids to orientation, a schematic wellbore is shown, including surface pipe connections with pumps. Hydraulic pathways are illustrated for transmitting broad-spectrum vibration to, and receiving band-limited backscatter vibration from, down-hole geologic material adjacent to the wellbore. The hydraulic pathways are shown passing to and from geologic material via, e.g., a preformed casing slot or an explosively-formed casing perforation.
[0244] The tunable down-hole stimulation system 699 schematically illustrated in FIG. 17 is relatively sophisticated, employing several structures, functions and interactions that may appear in different invention embodiments (but that need not appear in all invention embodiments) and are described in greater detail below. To improve clarity, certain structures and functions inherent in the system of FIG. 17 are schematically represented in FIGS. 15-16 . For example, references to specific elements (e.g., hammer element 540 or fluid interface 520 ) should be understood with reference to FIGS. 15-16 . Further, the illustration of tunable down-hole stimulator 638 in FIG. 17 should be understood as including a tunable vibration generator (labeled as such) which is analogous to the illustrated tunable hydraulic stimulator 599 in FIGS. 15-16 . So while a portion of tunable down-hole stimulator 638 should be understood as schematically analogous to tunable hydraulic stimulator 599 , it should also be recognized that stimulator 638 represents a different (expanded in part) subset of structures and functions not represented in stimulator 599 .
[0245] A first example of a tunable down-hole stimulation system is one of the embodiments schematically illustrated in portions of FIGS. 15-17 . The embodiment comprises at least one frac pump 688 for creating down-hole hydraulic pressure, together with at least one tunable down-hole stimulator 638 . Each stimulator 638 comprises a tunable vibration generator (labeled in FIG. 17 ) for transmitting vibration hydraulically, as well as a programmable controller 650 for creating a plurality of control signals and transmitting at least one control signal to each said frac pump 688 and each said tunable down-hole stimulator 638 . Additionally, each tunable down-hole stimulator 638 comprises at least one accelerometer 518 for sensing vibration and for transmitting an electrical signal derived therefrom. And the programmable controller 650 is responsive to accelerometer 518 via the electrical signal derived therefrom.
[0246] A second example of a tunable down-hole stimulation system is one of the embodiments schematically illustrated in portions of FIGS. 15-17 . The embodiment comprises at least one frac pump 688 for creating down-hole hydraulic pressure, together with at least one proppant pump 618 connected in parallel with at least one frac pump 688 for adding exogenous proppant. The system further comprises at least one tunable down-hole stimulator 638 , each stimulator 638 comprising a tunable vibration generator (labeled in FIG. 17 ) having a characteristic rebound frequency. A programmable controller 650 is included for creating a plurality of control signals and transmitting at least one control signal to each frac pump 688 , each proppant pump 618 , and each tunable down-hole stimulator 638 . Each tunable down-hole stimulator 638 comprises at least one accelerometer 518 for detecting vibration and for transmitting an electrical signal derived therefrom, and each accelerometer 518 is responsive to the characteristic rebound frequency. Finally, the programmable controller 650 is responsive to accelerometer 518 via the electrical signal.
[0247] A third example of a tunable down-hole stimulation system is one of the embodiments schematically illustrated in portions of FIGS. 15-17 . The embodiment comprises a wellbore comprising a vertical wellbore, a kickoff point, a heel, and a toe (all portions labeled in FIG. 17 ). At least one frac pump 688 creates down-hole hydraulic pressure in the wellbore, and at least one tunable down-hole stimulator 638 is located within the wellbore (and between the heel and toe as labeled in FIG. 17 ). Each stimulator comprises a tunable vibration generator (labeled in FIG. 17 ), and a programmable controller 650 creates a plurality of control signals and transmits at least one control signal to each frac pump 688 and each tunable down-hole stimulator 638 . Each tunable down-hole stimulator 638 comprises at least one accelerometer 518 for sensing vibration and for transmitting an electrical signal derived therefrom, and the programmable controller 650 is responsive to accelerometer 518 via the electrical signal.
[0248] An alternative embodiment included in the tunable down-hole stimulation system 699 of FIG. 17 , for example, comprises at least one frac pump 688 for creating down-hole hydraulic pressure. System 699 further comprises at least one down-hole tunable hydraulic stimulator 638 for generation and transmission of broad-spectrum vibration, and for detection of backscatter vibration, stimulator 638 being hydraulically pressurized by frac pump 688 . A programmable controller 650 is linked to at least one frac pump 688 and at least one tunable hydraulic stimulator 638 for controlling down-hole hydraulic pressure and vibration generation as functions of backscatter vibration sensed by one or more detectors on at least one tunable hydraulic stimulator 638 . Each tunable hydraulic stimulator 638 comprises a movable mass or hammer element 540 (see FIGS. 15-16 ) which is movable via a field emission structure in the form of an electromagnet/controller 562 / 564 to strike, and rebound from, a fluid interface 520 (see FIGS. 15-16 ) for generating broad-spectrum vibration (see FIG. 17 ). At least one tunable hydraulic stimulator 638 detects the backscatter vibration via an accelerometer 518 coupled to fluid interface 520 (see FIGS. 15-16 ). An electric signal derived from accelerometer 518 is carried via link 516 , link 514 and at least one additional link 654 (labeled in FIG. 17 ) to programmable controller 650 . The broad-spectrum vibration indicated in FIG. 17 is characterized by a vibration spectrum having a predetermined power spectral density, and programmable controller 650 (see FIG. 17 ) alters the predetermined power spectral density during the course of stimulation as a function of the backscatter vibration.
[0249] The alternative embodiment of the tunable stimulation system 699 described above may be further described as follows: tunable down-hole hydraulic stimulator 638 comprises a hollow cylindrical housing 590 having a longitudinal axis, a first end 594 , and a second end 592 , first end 594 being closed by fluid interface 520 for transmitting and receiving vibration, and fluid interface 520 comprising at least one accelerometer 518 for producing an accelerometer signal representing vibration transmitted and received by fluid interface 520 . A driver element 560 reversibly seals second end 592 , and driver element 560 comprises a field emission structure comprising an electromagnet/controller 562 / 564 having cyclical magnetic polarity reversal characterized by a variable polarity reversal frequency.
[0250] The alternative embodiment of the tunable stimulation system 699 may additionally comprise at least one temperature sensor (labeled in FIG. 17 ). Down-hole hydraulic pressure may be sensed (as labeled in FIG. 17 ) and transmitted as a pressure signal derived therefrom. Programmable controller 650 (through change in one or more of the control signals it produces) is responsive to the pressure signal when present. Pressure may analogously be controlled as a function-in-part of both temperature and backscatter vibration sensed at tunable down-hole stimulator 638 . And predetermined power spectral density may similarly be altered as a function-in-part of both temperature and backscatter vibration sensed at tunable down-hole stimulator 638 .
[0251] In the above embodiments, a field emission structure may be responsive to at least one control signal. Such responsiveness to at least one control signal is achieved, e.g., by emitting one or more electric and/or magnetic fields which are functions of at least one control signal as sensed by the field emission structure through change in one or more field emission structure electrical parameters. Thus, a tunable vibration generator may have a predetermined PSD which is dependent-in-part on one or more field emission structures that are themselves responsive to at least one control signal. | Tunable down-hole stimulation systems feature closed-loop control of pumps and tunable down-hole stimulators. Stimulators generate and hydraulically transmit broad vibration spectra tuned for resonance excitation and fracturing of geologic materials adjacent to the wellbore. Feedback data for controlling stimulation includes backscatter vibration originating in stimulated geologic material and detected at the stimulator(s). For initial fracturing with relatively large particle sizes, the power spectral density (PSD) of each stimulator output is down-shifted toward the lower resonant frequencies of large particles. As fracturing proceeds to smaller (proppant-sized) fragments having higher resonant frequencies, backscatter vibration guides progressive up-shifting of stimulator PSD to higher vibration frequencies. Stimulator power requirements are minimized by concentrating vibration energy efficiently in frequency bands to which geologic materials are most sensitive at every stage of stimulation. Geologic fragmentation efficiency is thus optimized, with inherent potential for plain-water fracs completed with self-generated proppant. | 4 |
This invention was made with Government support under Contract No. DE-AC04-94AL85000 awarded by the Department of Energy. The Government has certain rights in the invention.
BACKGROUND OF THE INVENTION
This invention relates to an apparatus and method for determining the penetration of the weld created from pulsed laser welding, and more particularly, to an apparatus and method of utilizing an optical technique to monitor the weld vaporization plume velocity to determine the depth of penetration.
Laser processing of metals is widely used in many industries, with the capability to monitor and control the depth of the weld into the metal crucial in many applications, such as nuclear safety critical welds.
In a laser welding process, the laser radiation first heats the metal surface. Melting occurs next, producing a plume of vaporized metal atoms and ions above the surface of the weld pool. When the laser energy input into the metal is sufficient, vaporization becomes sufficiently intense so that a void volume, or keyhole, is opened in the weld pool due to the recoil pressure generated by vaporization. During intense vaporization, a recoil pressure is developed due to the momentum change that occurs when metal atoms leave the surface of the weld pool. This recoil pressure is sufficient to cause a depression of the weld pool surface. As the laser intensity increases, this depression forms a void in the weld pool and allows for further penetration of the incident laser into the metal, leading to deep penetration welding. We refer to the regime of laser welding in which a void is formed and maintained in the weld pool during some fraction of the laser pulse as penetration, or keyhole, welding. In a pulsed laser welding process, the laser energy is delivered to the workpiece or part in short time intervals of approximately of 4-20 milliseconds. During each pulse, a vaporization plume is generated directly above the keyhole.
Several techniques, both non-optical and optical, have been disclosed for determining the state of penetration of a weld pool. Leong and Hunter, in U.S. Pat. No. 5,674,415 issued on Oct. 7, 1997, disclose a non-optical technique where an infrared signature emitted by a hot weld surface during welding is detected and the signature compared with a signature emitted during steady state conditions. This result in correlated with weld penetration.
Ortiz and Schneiter, in U.S. Pat. No. 5,045,669, issued on Sep. 3, 1991, disclose a laser apparatus that includes an optical sensor on the root side of the weld joint with a means for acoustically monitoring the processing. This technique requires accessibility to the root side of the joint.
Maram and Smith, in U.S. Pat. No. 4,767,911, issued on Aug. 30, 1988, disclose an apparatus that utilizes a photo-position detector to monitor the reflection angle of a beam of light specularly reflected from the weld pool to determine the state of penetration.
SUMMARY OF THE INVENTION
The general object of the invention is to determine the depth of penetration of a weld pool in solid metal during the welding process. More particularly, this invention provides an apparatus and method to determine weld penetration depth utilizing measurement of the vaporization plume velocity above the weld pool.
In accordance with the present invention, it is an object of the invention to provide an apparatus for real-time determination of the depth of penetration of the weld, comprising means for applying a pulsed laser beam to a workpiece to form a weld, means to generate a measurement light beam at a known distance above the weld, said light beam being attenuated by the presence of a rising vaporization plume above the weld, means to detect said light beam for measuring a change in light intensity caused by the plume and generating an electrical output signal, means for analyzing said electrical output signal to determine the velocity of said vaporization plume, said velocity being function of the depth of penetration of the weld.
Another object of the invention is the additional means for controlling the welding process based upon the determined state of penetration of the weld pool.
Another object of the invention is to provide a method for real-time determination of the depth of penetration of the weld, comprising the steps of applying a pulsed laser beam to a workpiece to form a weld, generating a measurement light beam at a known distance above the weld, said light beam being attenuated by the presence of a rising vaporization plume above the weld, detecting said light beam to measure a change in light intensity caused by the plume and generating an electrical output signal, and analyzing said electrical output signal to determine the velocity of said vaporization plume, said velocity being a function of the depth of penetration of the weld.
Utilization of the optical apparatus and method of the present invention to determine the vaporization plume velocities and subsequently the depth of weld penetration provides an easy and efficient real-time, optical monitoring sensor for pulsed laser welding without the need for complicated techniques involved with prior art weld penetration monitoring methods.
Other objects, advantages and novel features of the present invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic of the system arrangement of the present invention.
FIG. 2 shows typical results from Nd:YAG spot welds on an iron-nickel alloy.
FIG. 3 shows simulated detector response output to the data acquisition system.
FIG. 4 shows typical results of weld depth as a function of vaporization plume velocity.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 of the drawings shows a laser 10, such as a flash lamp pumped laser. Preferred is a Nd:YAG or CO 2 pumped laser. Flash lamp pumped lasers are preferred because they have a high energy density, a large depth of field that does not require refocusing between pulses, and a high beam quality. Laser 10 is focused on a workpiece 12. The beam from the laser may be focused directly on the workpiece or may be transmitted through an optical fiber to the workpiece. The laser radiation first heats the metal surface. Melting occurs next, producing a plume of vaporized metal atoms and ions above the surface of the weld pool. When the laser energy input into the metal is sufficient, vaporization becomes sufficiently intense so that a void volume, or keyhole, is opened in the weld pool.
A light source 20, preferably a laser, produces a directed light beam 21 through the rising vaporization plume directly (usually between 0 to about 4 centimeters) above the weld and keyhole of the workpiece 12. As the light beam 21 from the light source 20, for example a helium-neon laser or diode laser, passes through the rising vaporization plume, the light beam is deviated due to the refractive index gradients in the vaporization plume and the sheath of air surrounding the plume, producing a change in light intensity and a deviated light beam 30. An optical fiber input coupler 31 is utilized to couple the light beam 30 into an optical fiber 32. The optical fiber 32 is coupled to an optical fiber output coupler 33 to direct the light beam 30 to a detecting means 34, for example a silicon photodiode, infrared detector, photomultiplier tube, or imaging detector such as a charge coupled device, to measure the deviated intensity of the light source. The detecting means 34 produces an output voltage proportional to the intensity of the beam 30 to a digital or analog data acquisition system 40.
Laser 10 is connected to a trigger 13 which is connected to the detecting means 34. When the laser 10 delivers energy to the workpiece 12, the trigger 13 is activated and provides an output signal to the detecting means 34. The detecting means 34 is activated by this output signal, detecting initially the intensity of the beam 30 before the formation of the vaporization plume and then detecting, after some time interval, the change in intensity of the beam 30 as the vaporization plume forms and rises above the weld.
The detecting means 34 is connected to a digital or analog data acquisition system 40. One function of the data acquisition system 40 is to determine the time interval between the initiation of the laser pulse on the workpiece 12 as signaled by the detecting means 34 and the time in a step change in the intensity of the light beam 30 as indicated by the detecting means 34. By dividing the distance of the light beam 21 above the workpiece 12 by this time interval, the velocity of the vaporization plume is calculated by the data acquisition system 40.
The depth of the keyhole is related to the velocity of the vaporization plume by the energy balance equation. The energy balance equation shows that the weld radius and depth is proportional to the plume velocity. This equation is given by
(c.sub.1 A.sub.1 /V.sub.p).sup.1/2 =a+bv (1)
where a and b are constants, V p is the volume of the keyhole void, A 1 is related to the area of the weld and v is the plume velocity. Therefore, measurement of the plume velocity provides information on the weld depth.
In one embodiment of the invention, a pulse from a Nd:YAG laser 10 initiates the trigger 13, with the signal simultaneously sent to the data acquisition system 40 to fix the time of weld initiation. The triggered laser pulse results in weld penetration of the workpiece 12 and production and increased depth of a keyhole. A light source 20, in this embodiment a helium-neon laser, directs a light beam 21 through the vaporization plume directly over the workpiece 12 and formed keyhole. The light beam 21 intersects the vaporization plume a measured distance directly over the keyhole, and preferably within 0 to about 4 centimeters from the workpiece 12. Compared to the time period prior to initiation of the laser pulse, the intensity of the light beam 21 is changed, or deviated, because of vaporization plume containing the vaporized metal atoms or ions. The deviated light beam 30 from the vaporization plume is directed to an optical fiber input coupler 31 to couple the light beam 30 to an optical fiber 32. The deviated light beam 30 is transmitted through the optical cable into an optical fiber output coupler 33 to direct the light beam 30 to a detecting means 34. This detecting means is preferably a silicon photodiode and measures the intensity of the light beam 30. The detecting means 34 produces an output voltage proportional to the intensity and transmits this data to the data acquisition system 40. The data acquisition system 40 determines the velocity of the plume by dividing the distance of travel of the plume as determined by dividing the measured distance of the directed light beam 21 above the workpiece 12 by the time interval from the time of initiation of the laser pulse to the time when a change in intensity is detected by the detecting means 34. The depth of the keyhole is determined from the velocity of the vaporization plume using Equation 1. The pulsed laser 10 may be controlled by the data a acquisition system 40 using this information to obtain a precise depth.
FIG. 2 shows the results from one embodiment of the present invention. Nd:YAG spot welds were made on workpiece 12 samples of an iron-nickel alloy. The system used in making the measurements utilized a Nd:YAG laser 10 with an intensity greater than 0.4 MW/cm 2 . The laser was successively operated for discrete time periods of approximately 4 to 20 milliseconds until the desired weld depth was achieved. The light source 20 was a helium-neon laser. The detecting means 34 used was a silicon photodiode. FIG. 2 shows that Equation 1 can be used to linearly relate plume velocity to keyhole weld penetration depth. In FIG. 2, the left side of Equation 1 is plotted as a function of plume velocity. Plume velocities are typically between about 20 to about 40 m/s.
FIG. 3 shows a typical response from the detecting means 34 from prior to initiation of the laser pulse to after detection of the vaporization plume. Based on the penetration depth as determined by the present invention, the data acquisition system can be used to terminate the Nd:YAG laser pulses at the desired weld depth. FIG. 4 shows an example of the determined weld depth as a function of vaporization plume velocity for the test spot welds from the operation of this embodiment.
The foregoing discussion discloses and describes only certain exemplary embodiments of the present invention. One skilled in the art will readily recognize from such discussion, and from the accompanying drawings and claims, that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the following claims. | An apparatus and method for determining the penetration of the weld pool created from pulsed laser welding and more particularly to an apparatus and method of utilizing an optical technique to monitor the weld vaporization plume velocity to determine the depth of penetration. A light source directs a beam through a vaporization plume above a weld pool, wherein the plume changes the intensity of the beam, allowing determination of the velocity of the plume. From the velocity of the plume, the depth of the weld is determined. | 1 |
FIELD OF THE INVENTION
The present invention relates to a botulinus toxin neutralizer which is effective for the prevention and treatment of botulinus intoxication and to a method of preparing such a botulinus toxin neutralizer.
BACKGROUND OF THE INVENTION
Botulinus toxin is a proteinous exotoxin produced by Clostridium botulinum and acts on the peripheral nervous system. When ingested by human, the botulinus toxin gives rise to intoxication called botulism which is accompanied by paralytic symptoms. It is well known that the neurotoxin is absorbed from the alimentary tract and acts peripherally at the neuromuscular junctions controlled by the parasympathetic nerves. The toxin thus interferes with the release of acetylcholine from the chlorinergic motor nerve endings and causes botulism. In respect of the mode of action of the botulinus toxin, it has been widely accepted that a certain acidic glycolipid, viz., the ganglioside GT1b present in the neuromembrane acts as a receptor for the toxin. While other gangliosides such as the gangliosides GQ1b and GD1b also have the ability of combining with botulinus toxin, such an ability of these gangliosides is inferior to that of the ganglioside GT1b and, for this reason, it has been considered that the gangliosides GQ1b and GD1b are less responsible for the action to the botulinus toxin.
The treatment of botulism is extremely difficult and, at the present time, there is practically no other method of treatment than to cease the symptoms. It may be presumed that botulism could be treated with use of the ganglioside GTb1 as an antagonist to the botulinus toxin, in view of the mode of action of the toxin as above discussed. The ganglioside GTb1, which thus acts as an antagonistic receptor for the botulinus toxin, will combine with the toxin and will prevent the onset of the toxicity thereof. A problem is however encountered in that the source presently available of the ganglioside GTb1 is none but the bovine brain, which is so expensive that the method of treating botulism with use of such a ganglioside has seldom been put into practice.
Under these circumstances, it is an object of the present invention to provide an economical botulinus toxin neutralizer which can be used as an antagonistic toxin receptor for the treatment of botulism and which will thus facilitate the prevention and treatment of botulism.
It is another object of the present invention to provide a method of preparing such a botulinus toxin neutralizer.
SUMMARY OF THE INVENTION
In the process of studying milk fat globule membranes (MFGM, herein after referred to simply as fat globule membranes) derived from animal milk, the present inventors found that a substance prepared from such membranes had a potent ability of neutralizing botulinus toxin. The present invention has been completed on the basis of this discovery and, in accordance with a first outstanding aspect of the present invention, there is provided a botulinus toxin neutralizer (hereinafter referred to as a neutralizer according to the first aspect of the present invention) comprising heat-treated fat globule membranes of animal milk. In accordance with another outstanding aspect of the present invention, there is provided a botulinus toxin neutralizer (hereinafter referred to as a neutralizer according to the second aspect of the present invention) comprising gangliosides isolated from fat globule membranes of animal milk.
In accordance with still another outstanding aspect of the present invention, there is provided a method of preparing a botulinus toxin neutralizer from a material containing fat globules of animal milk, comprising the steps of
(a) fractionating the material for separating the membranes of the fat globules from the rest of the material, and
(b) subjecting the separated fat globule membranes to heat treatment.
In accordance with still another outstanding aspect of the present invention, there is provided a method of preparing a botulinus toxin neutralizer from a material containing fat globules, comprising the steps of
(a) fractionating the material for separating the membranes of the fat globules from the rest of the material, and
(b) isolating gangliosides from the globule membranes.
Where animal milk is used as the starting material, the fat globule membranes may be separated from the rest of the animal milk by fractionating the animal milk to separate cream from the rest of the animal milk, washing the cream to remove impurities therefrom, churning the resultant cream to separate the cream into buttermilk and butter granules, and fractionating the buttermilk to separate the globule membranes from the rest of the buttermmilk.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
As will be described in more detail, a botulinus toxin neutralizer according to the first aspect of the present invention is prepared through heat treatment of fat globule membranes of animal milk. When the gangliosides present in such a neutralizer or a semi-processed product of the neutralizer are isolated from the fat globule membranes, there results a botulinus toxin neutralizer according to the second aspect of the present invention.
The fat globule membranes of animal milk are the membranes covering the fat globules of the milk and are formed while the milk fats are being excreted into the mammary gland. The membranes are similar in chemical composition to the membranes of the mammary gland cells and are about 10 nm thick on the fat globules which measure about 1 to 10 microns in diameter in the case of bovine milk. The major constituents of such fat globule membranes include phospholipids, enzymes, proteins, glycoproteins, triglycerides, cholesterols and so forth. Among these constituents of the membranes, proteins and lipids alone account for more than 90% of the total amount with the proteins accounting for 45% and the lipids accounting for 55% of the protein and lipid fraction. Six types of gangliosides have thus far been found present in the lipids and contained in amounts totalling about 6 nano mols (in terms of sialic acid equivalent) per 1 mg of protein. These six types of gangliosides include the ganglioside GD3, GM2 and GM3 of which the ganglioside GD3, in particular, is the most prevalent. It may be noted that the ganglioside GT1b, which is known to be a possible antagonistic botulinus toxin receptor as previously discussed, has not been found to be included among the six gangliosides.
Description will now be made regarding a method of preparing a botulinus toxin neutralizer according to the first aspect of the present invention.
As the starting material for the preparation of such a toxin neutralizer may be used the buttermilk fraction of animal milk which can be readily and economically obtained as a byproduct of a buttermaking process. In an ordinary buttermaking process, cream is prepared by centrifuging animal milk and butter granules are produced when the cream is churned. Fat globule membranes are concentrated in the buttermilk fraction which is left with the butter granules separated from the churned cream. The buttermilk fraction is then processed to separate the fat globule membranes from the rest of the buttermilk. The fat globule membranes thus obtained are heated preferably after they are purified, lyophilized and/or disintegrated into debris in appropriate manners. The substance which results from this heat treatment is a neutralizer according to the first aspect of the present invention.
A method according to the present invention can thus be most advantageously put into practice using the buttermilk fraction of animal milk as the starting material. It should however be borne in mind that the use of such a starting material is not limitative of the present invention. If desired, a method according to the present invention may otherwise be carried out with use of, for example, a suitable equivalent of buttermilk. Such a buttermilk equivalent may be obtainable by adding water to cream of animal milk, centrifuging the resultant mixture for cleaning the cream, and thereafter churning the cream.
Buttermilk or any fraction of animal milk similar in chemical composition to buttermilk is excessively abundant with such milk components as the milk proteins and lactose and is, as it is, not suitable for use as a starting material for the preparation of a toxin neutralizer according to the first aspect of the present invention. It is for this reason preferable that the fat globule membranes separated from the buttermilk or a similar fraction of animal milk be purified by the use of, for example, dialysis, ammonium sulfate fractionation, gel filtration, isoelectric-point precipitation or any other appropriate method. Because, in addition, of the fact that fat globule membranes in general contain various enzymes such as alkali phosphatase, xanthine oxidase and acid phosphatase, it is necessary to have the enzymes inactivated by heating the fat globule membranes after the membranes are thus purified. This heat treatment may be performed by, for example, heating the globule membranes at 62° C. for more than 30 minutes or by using a heating step tantamount to a U.H.T.S.T. (ultra-high-temperature short-time) pasteurization method. As well known in the art, a U.H.T.S.T. pasteurization process uses a heating temperature higher than 100° C. for a short period of time.
The fat globule membranes which have thus been processed may include those having sizes approximately equal to the sizes which the membranes had on the intact fat globules. Such globule membranes tend to precipitate when dispersed in water for the cleaning by centrifuging. It is for this reason preferable that the fat globule membranes which have been purified as discussed above be ultrasonicated into fine debris to form a stable suspension in water before the membranes are subjected to the heat treatment.
The fat globule membranes which have received all the described treatment steps may be lyophilized for later use, or may be otherwise processed by any desired method to produce a pharmaceutical version of a toxin neutralizer according to the first aspect of the present invention. If desired, the fat globule membranes which may be obtained in the form of powder by the disintegration and lyophilization steps may be per se utilized as a toxin neutralizer.
A toxin neutralizer according to the second aspect of the present invention can be prepared by isolating gangliosides from a toxin neutralizer according to the first aspect of the present invention or from a semi-processed product of the neutralizer. Any desired method may be used for the isolation of the gangliosides from the neutralizer or the semi-processed product thereof. One method is to use a mixture of chloroform and methanol as a solvent for extracting lipids from the fat globule membranes and thereafter separate gangliosides from the extracted lipids by a gel filtration method. The ganglioside fraction thus obtained consists of a mixture of six types of gangliosides as stated previously. Regarding these gangliosides, it has not been determined whether all of the six types of gangliosides form the essential components of a toxin neutralizer according to the present invention or only one or more of the gangliosides are effective as such. Where it is desired that the gangliosides thus extracted be further fractionated for refining purposes, it is for this reason important that the fractionation be effected in consideration of the degree of the ability which each of the ganglioside fractions should have for inactivating the botulinus toxin. If the gangliosides are to be refined simply for desalting purposes, either the dialysis or treatment with ion-exchange resin will suit the purposes.
The toxin inactivation ability of a botulinus toxin neutralizer according to the present invention depends on the kind of the animal milk used as the starting material and varies from one animal milk to another. It would for this reason be of no significance to specify a standard unit quantity in which a botulinus toxin neutralizer according to the present invention should be used on a practical basis. Ordinarily, it is advisable for a user of the neutralizer to determine the toxin inactivation ability of a particular neutralizer for a particular case by, for example, a testing method set forth in the Examples to be described and to specify the proper unit quantity in which the neutralizer should be used for the particular case. It may however be mentioned for estimation purposes that, where the neutralizer is to be used for the treatment or prevention of botulism through oral administration, an appropriate dose of the neutralizer will ordinarily range from about 4 mg to about 100 mg for a toxin neutralizer according to the first aspect of the present invention and from about 2 mg to about 500 mg for a toxin neutralizer according to the second aspect of the present invention (per day for an adult).
A botulinus toxin neutralizer provided in accordance with the present invention may be used not only for oral administration but also as an additive to a gastrointestinal washing fluid or to food. Furthermore, a toxin neutralizer according to the second aspect of the present invention, in particular, may also be used in combination with a botulinus toxin antiserum for injection into the blood.
Analysis will now be made into the mode of action of a botulinus toxin neutralizer according to the present invention. When the neutralizer is introduced into the body, all or some of the gangliosides contained in the neutralizer encounter the botulinus toxin and act as antagonistic receptors binding to the toxin. It therefore follows that the toxin is precluded from combining with the cellular tissues at the active site of human body and is thus excreted without acting on the site. When used as an additive to food, the neutralizer binds to the toxin produced by Clostridium botulinum in the food and inactivates the toxin.
A toxin neutralizer according to the present invention is advantageous firstly in that it can be manufactured from the buttermilk which is readily and economically available in the form of a concentrate as a byproduct of buttermaking. Such a starting material merely requires simple fractionation and heat treatment steps or fractionation and isolation steps for being manufactured into a toxin neutralizer. The toxin neutralizer is thus more adapted for production on a large-scale commercial basis and is lower in production cost than existing globule membrane products prepared from bovine brains. Furthermore, a toxin neutralizer according to the present invention is manufactured simply through the fractionation and heat treatment or through the fractionation and isolation of animal milk without involvement of chemical processing of the material and is therefore fully acceptable from the safety point of view.
As will be appreciated from the foregoing description, a botulinus toxin neutralizer according to the present invention will open up the way anew for the treatment of botulism which has long been coped with merely by ceasing the symptoms. A toxin neutralizer according to the present invention will also contribute to the prevention of botulism by, for example, addition of the neutralizer to food or the like.
The present invention will be hereinafter described in more detail in the following Examples of a method according to the present invention.
EXAMPLE 1
One liter of bovine milk containing 3.3% of fat was centrifuged at 3,000 rpm for 15 minutes to obtain cream thereof. The cream was centrifuged to wash the fat globules to remove water-soluble impurities therein with water added to give a total volume of 440 ml, the washing steps being repeated further three times. The cream containing the fat globules cleaned by this centrifuging step was allowed to stand at 4° C. overnight and was churned to separate into buttermilk and butter granules. The buttermilk was made up with ammonium sulfate to 50% saturation and was allowed to stand overnight followed by centrifugation at 3,000 rpm for 30 minutes. Thereafter, the floating fat globule membranes were taken into water to make a suspension, which was then dialyzed against distilled water at 4° C. The resultant preparation was centrifuged at 10,000 rpm for 30 minutes to precipitate fat globule membranes. The fat globule membranes thus precipitated were lyophilized, whereby 650 mg of dried fat globule membranes were finally obtained.
Subsequently, the dried fat globule membranes were suspended in water, followed by ultrasonication of the suspension to disintegrate the membranes into fine debris. The resultant preparation containing the disintegrated fat globule membranes was heated at 100° C. for 30 minutes for inactivating the undesired enzymes which are likely to have strayed into the membranes. A toxin neutralizer was thus obtained as an example of a neutralizer according to the first aspect of the present invention.
Thirty mg of this botulinus toxin neutralizer was dissolved into 1.5 ml of Tris-chloride buffer solution (0.01M, pH 7.2). The resultant solution was allowed to react with 2 μg of purified type A botulinus toxin at 37° C. for 30 minutes to determine the amount of residual toxin by a toxin inactivation ability test. This toxin inactivation ability test was conducted by the known time-to-death method using intravenous injection into mice (Japan J. Bacteriology, Vol. 92, No. 5, 1980). The amount of residual toxin was thus determined to be less than 0.9%, showing that the botulinus toxin used was almost completely neutralized.
EXAMPLE 2
Dried fat globule membranes were obtained folowing the procedure taken in Example 1. Whole lipids were extracted from 1.0 g of fat globule membranes using 20 ml of chloroform/methanol (2:1, v/v) and 10 ml of chloroform/methanol (1:1, v/v). The lipids thus obtained were fractionated into neutral lipid and glycolipid fractions with use of Sephadex A-25 column (of the acetate form). The glycolipids were chemically neutralized with addition of weak alkali, followed by desalting by dialysis and subsequent treatment with an ion-exchange resin. The resultant preparation was lyophilized to obtain 0.8 mg of toxin neutralizer as an example of a neutralizer according to the second aspect of the present invention. This toxin neutralizer (4.7 g) was allowed to react with purified type A botulinus toxin, whereupon a toxin inactivation ability test as used in Example 1 was conducted to determine the amount of residual toxin, which was also found to be less than 0.9%.
For purposes of comparison, a similar toxin inactivation ability test was conducted with 50 μg of a commercially available ganglioside mixture (Sigma Type II, consisting of 20% of GM1, 40% of GD1a, 20% of GD1b and 20% of GT1b). The test proved that there was 9.0% of residual toxin.
EXAMPLE 3
One liter of goat milk containing 4.25% of fat was centrifuged at 3,000 rpm to obtain cream thereof. The cream was centrifuged for washing the fat globules therein with water added to give a total volume of 570 ml, the washing steps being repeated further three times. The cream containing the fat globules thus cleaned was allowed to stand at 4° C. overnight and was subjected to churning to separate into buttermilk and butter granules. The buttermilk was then heated at 100° C. for 10 minutes and was thereafter dialyzed against distilled water at 4° C. The fat globule fraction resulting from the dialysis was lyophilized to obtain 760 mg of dried fat globule membranes as an example of a toxin neutralizer according to the first aspect of the present invention.
The dried fat globule membranes were processed following the steps taken in Example 2, with the result that 302 μg of toxin neutralizer was obtained as an example of a toxin neutralizer according to the second aspect of the present invention. Using a toxin inactivation ability test as used in Example 1, 4.5 μg of this neutralizer was tested to determine the amount of residual toxin, which was found to be 36%.
EXAMPLE 4
Toxin inactivation ability tests for type B and type E botulinus toxins were further conducted using two different types of ganglioside preparation. One type of ganglioside preparation was prepared from bovine milk following the steps of Example 1 as an example of a neutralizer according to the first aspect of the present invention. The other type of ganglioside preparation was prepared from commerically available buttermilk (manufactured by Snow Brand Milk Products Co., Ltd., Tokyo). To prepare the latter type of ganglioside preparation from the commercially available buttermilk, whole lipids were extracted from 1.0 g of the buttermilk using 20 ml of chloroform/methanol (2:1, v/v) and 10 ml of chloroform/methanol (1:1, v/v). The lipids thus extracted were fractionated into neutral lipids and glycolipids with use of Sephadex A-25 column (of the acetate form). The glycolipids were chemically neutralized with weak alkali and the resultant substance was desalted by dialysis and subsequent treatment with an ion-exchange resin and was thereafter lyophilized, with the result that 0.2 mg of gangliosides was obtained as an example of a toxin neutralizer according to the second aspect of the present invention.
Two μg of botulinus toxin of each of the types B and E was mixed with 1 μg and 10 μg of each of the two types of neutralizers thus prepared one from the bovine milk and the other from the commercially available buttermilk. Each of the eight mixtures thus prepared was dissolved in 0.5 ml of 0.01M Tris-HCl buffer (pH 7.2). After reaction at 37° C. for 30 minutes, toxin inactivation ability tests similar to that used in Example 1 were conducted with the eight test samples to determine the amount of residual toxin in each of the samples. The following table shows the results of these tests, wherein "Milk" in the column of "Starting Material" refers to the bovine milk which resulted in a neutralizer according to the first aspect of the present invention and "Buttermilk" in the same column refers to the commercially available buttermilk which resulted in a neutralizer according to the second aspect of the present invention.
______________________________________ Quantity of ResidualType of Starting Neutralizer ToxinToxin Material (μg) (%)______________________________________B Milk 1 57.8 10 2.2B Buttermilk 1 5.7 10 1.5E Milk 1 Less than 2.0 10 Less than 2.0E Buttermilk 1 29.5 10 24.6______________________________________ | A botulinus toxin neutralizer comprising heat-treated fat globule membranes of animal milk or gangliosides isolated from fat globule membranes of animal milk. The neutralizer of the former nature is prepared from a material containing fat globules of animal milk by fractionating the material for separating the membranes of the fat globules from the rest of the material, and subjecting the separated fat globule membranes to heat treatment. The neutralizer of the former nature is prepared from a material containing fat globules by fractionating the material for separating the membranes of the fat globules from the rest of the material, and isolating gangliosides from the globule membranes. | 8 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is related to and claims priority from prior provisional application No. 61/739,729, received by the USPTO on 20 Dec. 2012, entitled “METHODS AND APPARATUS FOR 3D IMAGING AND CUSTOM MANUFACTURING”, the contents of which are incorporated herein by this reference and are not admitted to be prior art with respect to the present invention by the mention in this cross-reference section.
BACKGROUND OF THE INVENTION
[0002] This invention relates to providing methods and apparatus for improved three-dimensional (3D) imaging and custom manufacturing. More particularly this invention relates to providing methods and apparatus making objects requiring very close fits for comfort, retention or performance, wherein some body parts vary so significantly that even a small number of standard sizes cannot address the requirement.
[0003] Before the industrial revolution, all items were hand crafted, though not all were custom fit. During the industrial revolution, standardized objects became cheap to create due to automation. But custom fit solutions remained expensive and made to order. For some objects, a single size and style could meet the requirements of most buyers, and automation was a good solution. But for items like shoes, one size fits all was not a good compromise. Still the cost advantages of automation were so substantial, that manufacturing in a few standard sizes was a good compromise to address both cost and fit. With the advent of standard sizing, commerce changed and you could purchase ready-made goods such as shoes in a variety of sizes.
[0004] However, some objects require very close fits for comfort, retention or performance, and some body parts vary so significantly that even a small number of standard sizes cannot address the customer requirements. One object that falls in this category is a custom fit earpiece such as is typically found on hearing aids. Failure to get a perfect seal causes undesirable acoustical results such as feedback. For this reason, custom fit earpieces remain made-to-order. To date this has been an expensive process largely performed by hand-craftsmanship.
[0005] For this reason low cost custom fit objects, manufactured on demand, and potentially manufactured at the point of sale, has remained largely a dream.
Objects and Features of the Invention
[0006] A primary object of this invention is to provide a means of capturing and storing the three dimensional geometry objects.
[0007] A second object of this invention is to reduce the time, cost and expertise required to capture, transmit and store such 3D geometries.
[0008] A third object of this invention is to use such captured 3D geometries to manufacture and deliver to a consumer a custom object or custom fit objects, on demand, at any desired location, including at the point of sale.
[0009] There has long been a desire to create custom fit objects on demand, at the point of purchase, but such automated manufacturing systems generally do not currently exist. Thus, an additional object of this invention of this invention is fulfilling that desire by combining the necessary technologies for capturing customized or personalized 3D geometries, and for manufacturing items designed to fit those geometries exactly.
[0010] A further primary object and feature of the present invention is to provide such a system that is efficient, inexpensive, and handy. Other objects and features of this invention will become apparent with reference to the following descriptions.
3. SUMMARY OF THE INVENTION
[0011] We here disclose methods and apparatus we have developed for capturing the geometries of, and for manufacturing, three-dimensional objects.
[0012] The geometry of an object fitting within the imaging volume can be captured three dimensionally (referred to herein as “scanning”). A wide variety of 3D objects can be scanned, e.g., a model, figurine, and biometric features. Even biological and biometric features such as fingers, face, nose, or your ear can be imaged and their geometries captured. The 3D objects, once imaged are converted into 3D geometric models. The imaged objects may be replicated, or custom fit. Their replicas may be shaped to conform to the negative space (i.e., negative shape) they create. For instance, captured ear geometries may be used to design and manufacture custom fit earpieces. Once imaged, additional modifications may be done to the geometry model, eliminating the need to physically modify a copied device or custom fit shape.
[0013] Object geometry data can be transferred across the Internet, or stored in the Internet servers (referred to as “in the cloud”), ready to be manufactured at any desired location at any time. Manufacturing may be done using additive manufacturing techniques (referred to as “3D printing”), or negative manufacturing techniques (e.g. “milling machines”) in a variety of different materials.
[0014] By analogy to a fax machine that scans an image at one location and reproduces it at another, the invention allows objects to be 3D scanned at one location and reproduced at a different location. Or by analogy to a copy machine, it may reproduce a copy in the same location. Or by analogy to a network of printers connected to a data storage device, it may reproduce a copy at any later time at any of the 3D printer or milling machine locations.
[0015] Objects may be manufactured at the same location as the scan takes place with available materials and local 3D printer/milling machine station capabilities, enabling convenient replication near to the scanning point. Or they may be manufactured at a remote location where other materials or alternate fabrication methods may be available, and then shipped to the consumer.
[0016] We also disclose a business process that enables a consumer to capture 3D object geometries, to design and manufacture the 3D objects based on those geometries. This can include not only strict replication of the scanned object, but also deriving new objects based on the scanned geometries. A particular embodiment of this process supports making custom fit items based on scans of body parts, such as the manufacture of earpieces custom designed to fit the 3D shape of the purchaser's ears.
[0017] While most any object can be imaged and manufactured, in a preferred embodiment we image ears geometries that are used to manufacture custom-fit earpieces. These earpieces fit the contours of your ears, and may also be customized for hearing protection or for attachment to the specific geometries of a variety of headsets for listening to a media player, phones, tactical communications, hearing aids and other audio devices or sources.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] These and other features and advantages of the invention will be more readily understood from the following detailed description of the invention that is provided in connection with the accompanying drawings, in which:
[0019] FIG. 1 shows a flow chart of the Custom Fit manufacturing Process.
[0020] FIG. 2 shows a system diagram and data flow chart, showing the units that comprise the invention.
[0021] FIG. 3 shows a human ear and the 4 arrows point at 4 areas where shadows are likely if the ear is scanned from only a single vantage point.
[0022] FIG. 4 shows a human ear and the 4 circles are at the 4 points where low wattage lights may be placed next to the skin to diffuse through the skin and illuminate transdermally the structures that lie underneath the ridge of skin.
[0023] FIG. 5 shows four different mechanisms for positioning cameras for imaging a 3D object from multiple locations.
[0024] FIG. 6 shows a sample imaging target ring surrounding an ear.
[0025] FIG. 7 , it shows a sample right panel background.
[0026] FIG. 8 shows a sample left panel background.
[0027] FIG. 9 shows a sample front panel background.
[0028] FIG. 10 shows a sample back panel background.
[0029] FIG. 11 shows a sample floor.
DETAILED DESCRIPTION OF THE INVENTION
[0030] Referring to FIG. 1 , it shows a flow chart of a custom fit manufacturing process as follows.
1. Step 100 : A user desiring to have a custom object manufactured for him or her arrives at the custom fit manufacturing station. 2. Step 110 : The user positions an object, e.g., a body part, to be imaged in the imaging zone (an imaged object). 3. Step 120 : The imaging zone acquires two-dimensional (2D) images of the object and any other necessary information needed to digitally reconstruct the object's 3D geometry. The necessary information acquired depends on imaging method used, but may include absolute or relative positions of the cameras and light sources and their expected imaging pattern when imaging a flat plane. 4. Step 130 : A computational unit converts the 2D images and necessary information into a 3D imaged object model of the imaged object. 5. Step 140 : The computational unit stores the 3D imaged object model in the storage unit. This 3D imaged object model data may be used immediately (via step 170 ) to make one or more of the custom objects, or it can be stored for use at a later time (steps 150 and 160 ). 6. Step 150 : If no more of the custom objects will be manufactured at this time, the process is suspended until the user wishes to manufacture the custom objects based on the stored 3D imaged object model. 7. Step 160 : Once the user's 3D imaged object model is in storage it may be retrieved at any future time, to manufacture a new custom object, e.g., a custom-fit earpiece or a casting mold for the desired object. When the user desires to manufacture the new custom object, the 3D imaged object model data are passed to the next available manufacturing unit at the time of manufacture. 8. Step 170 : Upon request by the user when he or she is ready to manufacture the new custom object, the 3D imaged object model is retrieved into a computation unit where it is transformed into the 3D object or 3D custom-fit object model. The parameters of this custom fit model may be set by the user or by a technician, or determined automatically, depending on application and user preferences. 9. Step 180 : The resulting 3D custom-fit object model, e.g., a custom-fit earpiece data model, is transferred from the computation unit to a 3D Manufacturing station for manufacturing. The 3D custom-fit object model data may be stored as a permanent data storage file if the user is likely to create another just like it later, or it may be transferred as a temporary data store if it is likely to only have a one-time use. 10. Step 190 : The 3D manufacturing station, which may be a 3D additive manufacturing device (e.g., 3D printer), or another computer-aided design (CAD)/manufacturing system such as a Computer Numerical Control (CNC) machine, then manufactures a custom or custom-fit 3D object according to the specification in its 3D object model. When manufacturing is complete, the 3D manufacturing station returns to a suspense state (step 150 ) until the next manufacturing request is made.
[0041] Referring to FIG. 2 , it shows a system diagram and data flow chart, showing the elements that comprise the invention. Note that although only one unit of each type is shown, the invention includes configurations with multiple imaging units, computational units, data storage units and manufacturing units. These units may be physically integrated in a single physical package, or they may be distributed and connected by a communications network, such as WiFi in a store, or via the Internet, enabling the computational unit to use cloud computation by remote servers and the data storage unit to use cloud data storage services.
200 : Imaging Unit. Imaging unit, 200 , is composed of one or more imaging devices, such as the cameras or scanners capable of generating 2D or 3D image files of an object, depending on the 3D technology applied. The cameras and light sources may move in order to sense the geometry of the object from different planes cut through the object, or to capture from different viewpoints, or fixed cameras may be used. Various light sources may be placed at one or more viewpoints or a combination of fixed and moving elements of the imaging unit may be used. The imaging unit may store the generated image files in the data storage unit for later access, or pass them directly to the computational unit. 210 : Image Files. Image file, 210 , generated by the imaging unit is used by the computational unit to create 3D models of the imaged objects that have not already been rendered. 220 : Computational Unit. Computational unit, 220 , may be a personal computer (PC), a server, or specialized hardware for computing and transforming 2D images into a 3D model. The computational unit interacts with the data storage unit, the imaging unit, and the 3D manufacturing unit. 230 : Imaged Object 3D Model. Imaged object 3D model, 230 , generated by the computational unit, holds personalized 3D geometry information defining shape of the imaged object, e.g., jewelry, a figurine, or a human ear. 240 : Data Storage Unit. Data storage unit, 240 , holds 3D models computed from the imaging data. These models may then be transformed into custom fit 3D data models that may or may not be stored long term. The data storage units may also store the imaging data prior to use by a computational unit. 250 : Custom Object 3D Model. Custom object 3D model, 250 , produced by the computational unit is derived from the geometry of the imaged object. The custom object 3D model is transformed as necessary for a desired purpose, e.g., the final custom shape or custom-fit of the imaged object, e.g., jewelry, models or figurines, or a custom-fit earpiece designed for a specific user and headset. Step 260 : 3D Manufacturing Unit. 3D manufacturing unit, 260 , may be the 3D additive manufacturing station (3D printer), the CNC machine or other device that can manufacture the 3D object according to instructions contained in the 3D model.
[0049] Referring to FIG. 3 , showing a human ear (ear) and the 4 arrows pointing at 4 areas where shadows are likely if the ear is scanned from only a single vantage point. The circles show horizontal locations where the best vantage point for positioning imaging and illumination sources to avoid shadows along the line of the attached arrow. A preferred embodiment includes multiple vantage points for imaging and illumination for ensuring sufficient imaging of the imaged object, i.e., the ear, and especially to capture sufficient biometric data of the ear to create a custom fit earpiece.
300 : Location 300 is a good location for a vantage point and illumination to see into inter-tragus notch at base of bowl of the ear. 310 : Location 310 is a good location for a vantage point and illumination to see into helix notch, where it overlaps anti-helix of the ear. 320 : Location 320 is a good location for a vantage point and illumination of a visible part of ear canal. 330 : Location 330 is a good location for a vantage point of ridge of the anti-helix that sometimes extends over concha bowl.
[0054] Referring to FIG. 4 , it shows a human ear and the 4 circles are at the 4 points where low wattage lights may be placed next to the skin to diffuse through the skin and illuminate transdermally the structures that lie underneath the ridge of skin.
400 : Location 400 is a good location for illuminating the inter-tragus notch at the base of the bowl of the ear, and the lower back of the concha under the anti-helix. 410 : Location 410 is a good location for illumination of the helix notch, where it overlaps the anti-helix. 420 : Location 420 is a good location for illumination of the entrance to the ear canal. 430 : Location 430 is a good location for illuminating under the ridge of the anti-helix that sometimes extends over the upper back of the concha bowl.
Continuing to refer to FIG. 4 , it shows locations 400 , 410 , 420 , and 430 where lights may be placed for transdermal illumination of the surrounding areas of the ear.
[0059] Referring to FIG. 5 , it shows 4 types of mechanisms for positioning the cameras for imaging the 3D object from multiple locations.
500 : Robot arm, 500 , enables you to swing around the object being imaged to see it from any vantage point, enabling you to find the best viewpoint to see into concave areas of the 3D object. 510 : A series of cameras, 510 , placed on a hemispherical arm enable imaging the object from fixed elevations. By rotating the arm around the object it can be imaged from any azimuth direction. 520 : By adding a second arm, 520 , that pivots around a 45 degree elevation, a single camera can view the 3D object from any elevation between 0 degrees (equator) and 90 degrees (zenith). If the arm is placed at the equator, any elevation between 90 degrees (zenith) and -90 degrees (nadir) can be imaged. By rotating the arm around the object you can achieve any azimuth as well. Thus through a combination of the hemispherical arm and the second arm enable achieving full or nearly full hemispherical coverage. If the imaged object is on a pedestal or stake, the arms may be pivoted below the equator and thus captured with nearly full spherical coverage, allowing capture of the top and bottom of the object in a single model. Alternatively a object may be imaged in one orientation and then flipped vertically to capture the other side, and the two resulting models can be stitched together by software during the modeling step. 530 : For applications where movement of the 3D object between frames is a concern, the 3D object can be imaged simultaneously from multiple fixed vantage point cameras.
[0064] Referring to FIG. 6 , it shows a sample imaging target ring surrounding an ear. The imaging target ring has a number of marks on it which act as landmarks that allow the photogrammetry software to synchronize the same landmarks as seen from different vantage points. The imaging target ring also has markings of known size that allow the 3D models to be properly scaled.
[0065] Referring to FIG. 7 , it shows a sample right panel background. Backgrounds are landmark target rich for the photogrammetry software to identify many landmark points so that we can triangulate well everywhere. This is especially important when the 3D object itself is smooth and lacks few target points. Because the imaged 3D object is between the camera and the floor or walls, we are better able to determine the precise edges from each vantage point. In our preferred embodiment we image in a hemispherical pattern, focused on the center of the floor of our box. At high elevation angles the camera will see only the floor and 3D object, but at low elevation angles this wall will be seen behind the 3D object. In our preferred embodiment we use high contrast nature photographs rather than synthetic or constructed images, because the photogrammetry landmark recognition models have been optimized for naturally occurring organic shapes. Each wall is a completely different image from each other wall to avoid any landmark confusion during modeling that could occur if there was repetition or symmetry.
[0066] Referring to FIG. 8 , it shows a sample left panel background. As with the right panel, front panel and back panel, this panel will be imaged from some camera positions when the camera is at a low elevation angle. This image shares characteristics of the other wall and floor designs. It is high contrast, irregular (random), non-repeating, and nonself-similar at different scales. Images that repeat or are self-similar at different scales can make it easy for the photogrammetry software to confuse two distinct different points as the same landmark, which will result in a distorted model of the 3D object. Selection of images such as these avoid these problems.
[0067] Referring to FIG. 9 , it shows a sample front panel background. As with the right panel, left panel and back panel, this panel will be imaged from some camera positions when the camera is at a low elevation angle. This image shares characteristics of the other wall and floor designs, but is of a different object to ensure its landmarks won't erroneously be mapped to the same point on other walls. Differences in size or shape of the wall images are determined by the precise dimensions of the scanner, which may vary based on the 3D object being imaged.
[0068] Referring to FIG. 10 , it shows a sample back panel background. As with the right panel, left panel and front panel, this panel will be imaged from some camera positions when the camera is at a low elevation angle. This image shares characteristics of the other wall and floor designs, but is of a different 3D object to ensure its landmarks won't erroneously be mapped to the same point on other walls. Differences in size or shape of the wall images are determined by the precise dimensions of the scanner, which may vary based on object being imaged.
[0069] Referring to FIG. 11 , it shows a sample floor background. As with the wall panel backgrounds, the floor background provides a target rich environment for finding landmarks that can be matched from image to image. Because the 3D object is placed on the floor parts of the floor are always visible unless the camera elevation is on the equator. The thin lines on the floor (circle and star pattern) are used in testing to verify cameras are operating from desired positions, and to initially set the dimensional scale and axes of the scanner using an image object of known dimensions and position. By specifying the exact dimensions and positions of known landmark points on the floor, we are able reverse the triangulation process to determine the precise camera positions where images were taken with respect to the same reference axes and scale. We store these positions in a “template” that we can use to provide automated scaling and cropping during normal processing. Our mechanicals and electronics ensure we use the same camera positions each time, thus we now know the precise camera positions used each time. Given the known distances between cameras, and the angles to common reference points in different images we are now able to accurately determine the scale of the unknown 3D object. Also since we know the actual distance of the floor and walls from the cameras, we can automatically crop the floor and walls from the model leaving only the intended 3D object modeled.
[0070] In a preferred embodiment, we can image either physical impressions of the ear (a convex object), or the ear itself (a concave object).
[0071] Creating a good 3D model of the ear is especially difficult for several reasons. Human skin is translucent and intense incident light, such as from a laser tends to both diffuse and reflect. This poses a problem for scanners relying on laser or structured light technologies that use incident light.
[0072] For this reason, in a preferred embodiment the inventors prefer using photogrammetry for capturing ear geometries, which has not been used for this purpose before.
[0073] However, a problem for photogrammetry is that for good results, you need to identify point landmarks from multiple vantage points that you can use in triangulation. Except for exceptionally freckled humans, most ears are largely featureless, which would make it difficult for photogrammetry to yield accurate results, which is one reason photogrammetry has not been used before for capturing ear geometries. Moreover, physical impressions taken from the ears are generally monochromatic, smooth with continuously varying curves, making it hard to find landmarks on the imaged target object. However, the inventors were able to work around this limitation by surrounding the ear with a printed ring or bowl marked with landmark points that enable photogrammetry to accurately identify these points, and when imaging impressions we captured images within an enclosed space with special backgrounds that provide many of the landmarks used for triangulation even though the target object lacks them. By imaging the ear and the surrounding landmarks we are able to capture the visible shapes with landmark points.
[0074] Additionally photogrammetry has not been used for capturing ears because photogrammetry requires the image to contain an object of known scale to get the size right. Since ears don't naturally have any features of precisely known size, this is a problem for photogrammetry. However, because we created the landmark points on a surrounding ring or bowl having a known size, we solved the scaling problem. This use of the landmark points enables photogrammetry as an acceptable solution for capturing ear geometries.
[0075] Additionally, because the photogrammetry apparatus consistently takes images from the same positions, we capture a test object of a known fixed size. And, because we already know the scale of the 3D object, rather than using triangulation to find its size and distance, we reverse the triangulation to find the distance of each camera from some of the registration points. This allows us to calculate the camera locations with precision. Since the device does not change its operating locations, we are able to detect the camera positions relative to each other.
[0076] As mentioned before, a disadvantage of laser line and structured light scanning methods for ear scanning is the translucency of skin which diffuses the incident light so it is no longer a well-defined point. An advantage of this embodiment using photogrammetry is that translucency of skin can actually be employed to better capture parts of the ear that are hard to directly illuminate.
[0077] We have identified four major ear features that must be well captured to achieve a good fit for custom fit earpieces. They are: (1) the outer part of the ear canal from the concha to the second bend, (2) the helix lock where the helix goes over the anti-helix, (3) the intertragal notch between the tragus and anti-tragus, and (4) the concha under the anti-helix ridge.
[0078] Again, referring to FIG. 3 , which identifies camera and illumination positions for best imaging these areas, the size of the lighting elements and the cameras may make it difficult to simultaneously illuminate and image from these positions. And in some cases the ridges so completely curl over the concha or entrance to the ear canal that illumination of the area is nearly impossible. This is most significantly a problem around the ear canal.
[0079] An advantage of this preferred embodiment for an ear scanner is that by using photogrammetry we can turn the translucency of the skin from a disadvantage into an advantage. We can place light sources, such as low wattage LEDs proximate to the skin in these areas. The light will diffuse through the obscuring ridge of skin and illuminate the interior transdermally. For instance a light source proximate to the tragal fold will diffuse through that skin and illuminate the outer part of the ear canal. Proper placement of light sources can assist with transdermally illuminating the intertragal notch (with sources over the tragal fold and intertragus), the concha (on the antitragus and antihelix, and of the helix lock with illumination placed on top of the helix). Because these sources are outside of the concha area, they do not obscure imaging the interior of the concha from any viewpoint. They can in fact be hidden by the aforementioned ring or bowl that provides scale and landmark synchronization information for photogrammetry.
[0080] A preferred embodiment relies on multiple imaging vantage points. There are multiple ways to image from these vantage points, and different choices may be preferred based on whether the application is imaging an ear (subject to motion) or an ear impression.
[0081] Use of multiple cameras simultaneously capturing the target, can be advantageous for capturing ears, since it minimizes the time that user must interact with the scanner, and also minimizes the possibility of the ear moving between images which would confound the photogrammetric modeling.
[0082] For an object such as an ear impression, or piece of jewelry that is stationary, motion between image captures is not an issue, and cost may be reduced by reducing the number of the cameras and moving them between multiple viewpoints. At the limit a single camera may be employed, although depending on time vs. cost vs. redundancy tradeoffs other numbers of the cameras may be used in combination with motion.
[0083] There are many ways the cameras may be driven to their desired locations. These include a robot arm that can trace any path, rotational arms that drive the cameras around the object in an azimuth direction, elevational arms that can move the cameras up and down in elevation, combinations of azimuthal and elevational arms, or even hemispherical or helical screw tracks.
[0084] A preferred embodiment puts together the components necessary to make low cost custom fit manufacturing, including manufacturing at point of sale, a reality.
[0085] We image an object fitting inside the scanning zone. These may be simple objects like models, figurines or jewelry or complex objects like biometric features such as ears. Captures of 3D ear geometries, either directly from ears, or indirectly from negative space impression molds taken from ears, are used to design and manufacture custom fit earpieces using Computer Aided Design (CAD) and Computer Aided Manufacturing (CAM) software, and manufacturing technologies such as Additive Manufacturing (3D Printers) or computer numerically controlled machines that use negative manufacturing techniques.
[0086] Our invention can apply these methods to creation of many custom fit objects, but the manufacturing time can vary with the complexity, volume and number of materials comprising the final object. An object as small and simple as an earpiece or piece of jewelry could be manufactured in under an hour with existing manufacturing technologies, while an object as large or as complex as high performance shoe would likely take much longer with existing manufacturing techniques. For this reason, this preferred embodiment of the invention initially creates small, simple, single material goods such as jewelry, models, figurines, and custom fit earpieces. As manufacturing technology improves, we expect to produce more complex multiple material goods that have other components embedded in the product to enhance its usefulness or value, but still manufactured in a timely manner.
[0087] A preferred embodiment of this invention begins by addressing the question “Why is it so hard to get custom fit earpieces?”. Over the last eighty years the hearing aid industry evolved from a standard “one size fits all” earpiece, to custom fit earpieces. One of the primary factors that led to the move to custom fit earpieces was the miniaturization of the hearing aid devices, which increasingly put the microphones closer and closer to the speakers.
[0088] This is a concern for the designer of hearing aids, because hearing aids must amplify the signal a great deal. But if the amplified sound reaches the microphone, “feedback” occurs and a painful screeching sound results. If a secure seal of the ear canal can be achieved, the amplified sound directed to the ear drum can be acoustically isolated from the microphone on the other side and the possibility of feedback is reduced. For this reason, the needs of the hearing aid industry has been driving the development of methods and apparatus for the capture of ear geometries and for manufacturing custom fit earpieces.
[0089] But once the technology existed for capturing ear geometries and produce custom fit objects, applications to other areas such as industrial hearing protection, music and communications also became possible.
[0090] Because of this connection to the growing hearing aid industry, the traditional way to produce such custom ear plugs, earpieces, adapters and components for hearing aids or communications devices has required consumers wanting such devices to visit a trained audiologist, who would inject a fast hardening putty into each of the consumer's ears. After the putty hardens (typically in 15-30 minutes), the audiologist would ship the ear impressions to a custom manufacturer. The manufacturer would then use the consumer's ear molds to construct an inverse mold, and then use the inverse mold to make a new object that was identical in shape to the molds that came from the consumer's ears. In the case of a hearing aid, music listening device or communications device, additional manufacturing steps might be required to construct a hole that could direct sound from the device's speaker through the custom earpiece to a part of the ear canal proximate to the ear drum.
[0091] The newly manufactured earpiece would be sent back to the original audiologist who would ask the patient to schedule another appointment where the audiologist would validate that the earpieces were sufficiently snug to prevent the feedback problem, yet not so tight that they were painful to wear. The high demands of these conflicting requirements, and the multi week process between each mold taking and fitting appointment made obtaining a very good impression the first time very important. This took some skill, especially to navigate the syringe around two separate “bends” in each ear canal, and without damaging the delicate eardrum. Capturing the deep geometry of the ear canal, allowing the hearing aid designer to place the end of the device as close to the ear drum as possible, and as far away from the microphone as possible was critical to success of hearing aid fittings.
[0092] One disadvantage of this method is that the original putty molds shrink over time, thus if the consumer needs a replacement earpiece or is fit for a different device at a future time, the consumer must replicate their visit to the audiologist and a new mold will have to be made.
[0093] With the advent of laser 3D geometry scanners, some manufacturers decided that rather than make the 2nd inverse mold they would use a laser scanner and create a digital 3D geometry data model of each original ear impression mold. Since the geometry model does not change over time the way the original molds do, this can be used to generate additional copies on demand without new molds. However, as the ear is a part of the human body which continues to grow over a lifetime, frequent re-captures are typically necessary in the Hearing Aid business where a tight fit to avoid feedback is most critical. A preferred embodiment of this invention facilitates capture of the geometries of such physical molds so they do not need to be shipped.
[0094] In addition, this growth rate is slow enough that in less demanding applications such as music listening or communications where feedback is not an issue, earpieces made based on geometries digitally captured at a single fitting could be adequate for many years or even decades.
[0095] Even with growing applications in noise protection and communications that were less demanding in their demands for capturing deep ear geometries, because of the potential damage to the ear drum if mold impression taking technique is poor, getting the initial ear molds continued to done primarily by trained medical professionals causing the initial mold taking process to be an expensive, inconvenient and time consuming process.
[0096] A preferred embodiment comprises a new way to capture this information that does not involve using putty, but would instead use optical means to capture ear geometries. This was further developed and perfected into the invention, which is disclosed below.
[0097] Methods for capturing 3D geometry information and building 3D CAD models are not new. Among the common methods for capturing 3D geometries are moving laser line scanners, structured light scanners, and photogrammetry to name a few. All of these methods for capturing 3D point cloud information can be used with preferred embodiments of this invention.
[0098] However, a problem for any imaging system is the problem of shadows. If the surface cannot be seen from the vantage point of the imaging device, or is not illuminated by an illumination device, the 3D model will have a defect. This is why 3D scanning is typically only used for capturing convex shapes which can be viewed from a single vantage point, or where the object can be placed on a carousel that rotates in a predictable way in front of a fixed camera and light source.
[0099] In terms of manufacturing an object that should fill the negative space of a concavity (i.e., negative shape), the defects (areas not imaged or not imaged well) in the negative shape will result in voids between the manufactured object and the imaged object.
[0100] To ensure that we do not suffer from significant optical shadowing, we capture images from multiple vantage points to maximize accurate 3D rendering.
[0101] Photogrammetry is the science of determining 3D geometric properties from 2D photographic images. Photogrammetry does an excellent job of recreating 3D objects. In its simplest embodiment, stereo cameras image an object from two locations. Geometrical positions illuminated and visible to both the cameras can be determined by running rays from each camera to the common point. By adding more vantage points and circumnavigating the object we can determine the geometry of the entire object. In fact, entire cityscapes can be captured with images taken while circling or in multiple flyovers.
[0102] The same technology, photogrammetry, is used to create 3D films for the movie industry. Photogrammetry techniques are very good for capturing shapes; however, unless distances between vantage points are known precisely, they depend on knowing the size of features in the images to scale properly. One embodiment of the invention that uses photogrammetry takes advantage of the apparatus to ensure that we know the scale of the imaged objects by first deriving and then reusing known camera positions to yield both scale and better precision in the shape capture.
[0103] Laser scanning technology has been around for decades and is another excellence source capable of 3D rendering. It depends on having a laser and camera at a known distance apart. A point on the surface of the object illuminated by the laser reflects to the camera. We know by the laws of optics that the angle of incidence equals the angle of reflectance. Therefore if we know the angle of the laser relative to the base line connecting the laser and camera, we know two angles and one side of the triangle they form. By triangulation, we can calculate the distances and thereby derive the geometry. By creating a laser line, we can capture many points with a single image and thus speed up the process.
[0104] A newer image technique called Structured-Lighting extends this principle even further, painting many lines across the surface in patterns that allow the system to resolve which visible line corresponds to which transmitted light and angle, thus allowing multiple “lines” to be captured in a single image.
[0105] A disadvantage of the laser and structured light methods is that they rely on painting the surface of the object with bright light. If the illuminated surface reflects or diffuses light, a single incident light ray may wind up illuminating multiple reflected points, or the area of diffusion, making it hard to determine the precise location of the illuminated point with accuracy. This is particularly a concern for imaging human skin, such as the surface of the ear, since it is subject to both diffusion of bright light and irregular reflections.
[0106] These and many more methods exist for acquiring 3D geometries.
[0107] While the combination of the 3D scanner and 3D printer or CNC machine is useful for duplicating a shape or its inverse, the 3D printer can print any 3D model, including ones that are designed from scratch without an initial scan. By placing a 3D printer or CNC machine at a point of sale location, on demand manufacturing with mass customization reaches a new level of convenience, and eliminates shipping costs and delays.
[0108] A preferred embodiment of this invention consists of an imaging unit, a computation unit, a data storage unit and a 3D manufacturing unit. The imaging system, computation unit, and printer may all be tightly integrated in a single device, or they may be fielded as multiple devices that intercommunicate. For instance, some computations may be done by servers on the Internet, and data may also be stored on remote servers, and 3D scanners may be at one location but 3D printers used in manufacturing may be in yet another location.
[0109] A user of the invention places an object to be imaged at the focal zone of the imaging unit. For instance, in one embodiment jewelry, models, household décor, figurines or physical ear impressions are placed in the image zone and a 3D model of the imaged object is created in order to create an exact replica. In a preferred embodiment, an ear is imaged in order to create an object that is not a replica of the ear, but rather to a custom fit earpiece that fills the negative space of the concha (bowl) of the ear.
[0110] The output of this imaging unit is a set of 2D images. The image data may be stored in a data storage unit before being passed on to the computation unit.
[0111] The 2D images are converted into 3D imaged object models using common algorithmic image analysis tools that calculate 3D geometries using photogrammetry, laser line triangulation, structured light or other 3D imaging methods. This 3D data transformation is done by a computation unit. The resulting 3D imaged object model is stored in the data storage unit.
[0112] The 3D imaged object model (in a preferred embodiment: a 3D ear model) is then translated by the computation unit, using 3D CAD software, to smooth edges, fill areas not well captured, remove excess material, to extrude extra material to provide a place for anchoring any attachments, or perform other customization desired. This translation creates the desired 3D Custom object model that will be used in manufacturing. In a preferred embodiment where we create custom fit earpieces, these transformations are typically to create an anchor hole to hold the post of a headset, and to route a sound tunnel from the end of the headset through the earpiece into the ear canal. The output of this transformation step is a 3D Custom object model.
[0113] In the final step of the fabrication process of a preferred embodiment of this invention, we convert the 3D custom object model into a finished manufactured object using automated 3D manufacturing methods. These fabrication processes take place in the 3D manufacturing unit. In a preferred embodiment, we create finished products such as: jewelry, models, household décor, figurines, or earpiece are made using 3D additive manufacturing and printing of the desired object. However, in other embodiments of the invention can use subtractive methods such as CNC machines and other manufacturing technologies to develop products to meet customer needs.
Operation
[0114] The User positions the object to be fitted (e.g. jewelry, models, house hold décor, figurines, physical ear impression or an ear), into the imaging zone of the apparatus. The imaging apparatus captures images of the object.
[0115] In the next step, the captured 2D images are output from the imaging unit into the computational unit. This process converts the captured 2D images into a 3D geometry model of the imaged object to be fit or replicated. We use a pattern background that avoids replication or self-similar elements to provide a target rich environment for triangulating even if the object being imaged lacks its own landmarks. We also can add additional landmarks to the target object by sprinkling powder, painting a surface pattern using pigment or light, or using a different material containing contrast markers embedded within the mold making material to ensure that the molds so produced have lots of optical landmarks.
[0116] In the following step, the 3D imaged object model is stored in the data storage device for retrieval when the user wishes to manufacture a custom-fit device. In most cases this data is immediately used as input to the object transformation process, although once stored the process may be repeated at this step to create additional custom or custom-fit objects as replacements for use with new accessories (e.g. different headset models) without the need for re-imaging.
[0117] In the succeeding step, the 3D model of the imaged object is transformed into a 3D model of the desired custom object to be manufactured. This may be an entirely automated computation process, or may involve additional input from a technician depending on the complexity of the transformation desired.
[0118] Once the desired 3D custom or custom-fit object model has been produced, it is passed to the 3D manufacturing apparatus that then physically replicates the custom fit object based on its 3D model. This final manufacturing step may be a simple single step: a direct to 3D print operation; or it may involve multiple steps including making of casting molds and subsequent casting of parts, or various finishing operations.
Alternatives
[0119] There are many kinds of cavities and surfaces that can be 3D scanned using preferred embodiments of this invention, and many custom fit objects can be manufactured from the resulting 3D geometry files, as we disclose here.
[0120] In a preferred embodiment of the invention the application of these methods and apparatus are used to scan the 3D geometries of human ears, and to create custom fit ear pieces that may be used for noise reduction and hearing protection; or as part of a personal or portable sound delivery system such as a music player in-ear headset; or as part of an ear piece for a communications system, such as a bluetooth cellular phone, call center telephone or tactical radio walkie-talkie.
[0121] While there are several advantages to applying the invention to this specific application, there is nothing about the invention which would limit its application to 3D imaging of other objects, nor to manufacturing physical replicas or custom-fit or custom designed objects of other types.
[0122] For instance, a preferred embodiment of this invention can be applied to several other medical applications, including capture of the 3D geometry of other body parts, such as feet, vaginal, nasal, oral or anal cavities, or combined with laparoscopy, of internal body cavities or blood vessels. From these 3D scans, custom fit orthotics, vaginal, oral or anal inserts, stents and other custom fit 3D objects can be produced.
[0123] Beyond medical applications, these same techniques can be used to produce custom fit personalized jewelry, garments, or sculptures and other adornments, plus home décor, figurines or sculptures.
[0124] Furthermore, preferred embodiments of this invention are not limited to the scanning of biological surfaces or production of custom fit objects only for use in biological contexts. Preferred embodiments of this invention can also be applied to creating a custom fit patch to a hole or crack in a ceiling, floor, wall or other surface, or to join two or more objects securely.
[0125] While our preferred implementation of this invention uses optical imaging methods, it should be understood that our invention can work using non-visible electromagnetic radiation as well, including infrared, ultraviolet, microwave and radio waves and x-rays. It may also be extended to other forms of energy waves such as ultra-sound or computed tomography where 2D images are transformed into 3D images. | The invention provides improved machines and systems for generating faithful 3D geometric models that correspond to the shape of an imaged 3D physical object, for storing, transmitting, and transforming those 3D models, and for manufacturing 3D objects based upon those models. The invention also provides improved processes for such capture, transmission, storage, and transformation of the 3D models and manufacturing of objects from those models. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 14/180,121, filed on Feb. 13, 2014, which is a broadening reissue of U.S. application Ser. No. 12/796,560, filed on Jun. 8, 2010, issued as U.S. Pat. No. 8,113,303 on Feb. 14, 2012, which is a continuation of U.S. application Ser. No. 11/855,770, filed Sep. 14, 2007 issued as U.S. Pat. No. 7,757,785 on Jul. 20, 2010, which is a continuation of U.S. patent application Ser. No. 11/117,647, filed Apr. 28, 2005, now abandoned, which claims priority, pursuant to 35 U.S.C. §119(e), to U.S. Provisional Patent Application No. 60/648,863, filed Feb. 1, 2005, U.S. Provisional Patent Application No. 60/584,307 filed Jun. 30, 2004, and U.S. Provisional Patent Application No. 60/566,751 filed Apr. 30, 2004. These applications are incorporated herein by reference in their entireties.
BACKGROUND
[0002] 1. Technical Field
[0003] The disclosure relates generally to modified cutters.
[0004] 2. Background Art
[0005] Rotary drill bits with no moving elements on them are typically referred to as “drag” bits. Drag bits are often used to drill a variety of rock formations. Drag bits include those having cutters (sometimes referred to as cutter elements, cutting elements or inserts) attached to the bit body. For example, the cutters may be formed having a substrate or support stud made of cemented carbide, for example tungsten carbide, and an ultra hard cutting surface layer or “table” made of a polycrystalline diamond material or a polycrystalline boron nitride material deposited onto or otherwise bonded to the substrate at an interface surface.
[0006] An example of a prior art drag bit having a plurality of cutters with ultra hard working surfaces is shown in FIG. 1 . The drill bit 10 includes a bit body 12 and a plurality of blades 14 that are formed on the bit body 12 . The blades 14 are separated by channels or gaps 16 that enable drilling fluid to flow between and both clean and cool the blades 14 and cutters 18 . Cutters 18 are held in the blades 14 at predetermined angular orientations and radial locations to present working surfaces 20 with a desired back rake angle against a formation to be drilled. Typically, the working surfaces 20 are generally perpendicular to the axis 19 and side surface 21 of a cylindrical cutter 18 . Thus, the working surface 20 and the side surface 21 meet or intersect to form a circumferential cutting edge 22 .
[0007] Nozzles 23 are typically formed in the drill bit body 12 and positioned in the gaps 16 so that fluid can be pumped to discharge drilling fluid in selected directions and at selected rates of flow between the cutting blades 14 for lubricating and cooling the drill bit 10 , the blades 14 and the cutters 18 . The drilling fluid also cleans and removes the cuttings as the drill bit rotates and penetrates the geological formation. The gaps 16 , which may be referred to as “fluid courses,” are positioned to provide additional flow channels for drilling fluid and to provide a passage for formation cuttings to travel past the drill bit 10 toward the surface of a wellbore (not shown).
[0008] The drill bit 10 includes a shank 24 and a crown 26 . Shank 24 is typically formed of steel or a matrix material and includes a threaded pin 28 for attachment to a drill string. Crown 26 has a cutting face 30 and outer side surface 32 . The particular materials used to form drill bit bodies are selected to provide adequate toughness, while providing good resistance to abrasive and erosive wear. For example, in the case where an ultra hard cutter is to be used, the bit body 12 may be made from powdered tungsten carbide (WC) infiltrated with a binder alloy within a suitable mold form. In one manufacturing process the crown 26 includes a plurality of holes or pockets 34 that are sized and shaped to receive a corresponding plurality of cutters 18 .
[0009] The combined plurality of surfaces 20 of the cutters 18 effectively forms the cutting face of the drill bit 10 . Once the crown 26 is formed, the cutters 18 are positioned in the pockets 34 and affixed by any suitable method, such as brazing, adhesive, mechanical means such as interference fit, or the like. The design depicted provides the pockets 34 inclined with respect to the surface of the crown 26 . The pockets 34 are inclined such that cutters 18 are oriented with the working face 20 at a desired rake angle in the direction of rotation of the bit 10 , so as to enhance cutting. It will be understood that in an alternative construction (not shown), the cutters can each be substantially perpendicular to the surface of the crown, while an ultra hard surface is affixed to a substrate at an angle on a cutter body or a stud so that a desired rake angle is achieved at the working surface.
[0010] A typical cutter 18 is shown in FIG. 2 . The typical cutter 18 has a cylindrical cemented carbide substrate body 38 having an end face or upper surface 54 referred to herein as the “interface surface” 54 . An ultra hard material layer (cutting layer) 44 , such as polycrystalline diamond or polycrystalline cubic boron nitride layer, forms the working surface 20 and the cutting edge 22 . A bottom surface 52 of the cutting layer 44 is bonded on to the upper surface 54 of the substrate 38 . The joining surfaces 52 and 54 are herein referred to as the interface 46 . The top exposed surface or working surface 20 of the cutting layer 44 is opposite the bottom surface 52 . The cutting layer 44 typically has a flat or planar working surface 20 , but may also have a curved exposed surface, that meets the side surface 21 at a cutting edge 22 .
[0011] Cutters may be made, for example, according to the teachings of U.S. Pat. No. 3,745,623, whereby a relatively small volume of ultra hard particles such as diamond or cubic boron nitride is sintered as a thin layer onto a cemented tungsten carbide substrate. Flat top surface cutters as shown in FIG. 2 are generally the most common and convenient to manufacture with an ultra hard layer according to known techniques. It has been found that cutter chipping, spalling and delamination are common failure modes for ultra hard flat top surface cutters.
[0012] Generally speaking, the process for making a cutter 18 employs a body of cemented tungsten carbide as the substrate 38 , wherein the tungsten carbide particles are cemented together with cobalt. The carbide body is placed adjacent to a layer of ultra hard material particles such as diamond or cubic boron nitride particles and the combination is subjected to high temperature at a pressure where the ultra hard material particles are thermodynamically stable. This results in recrystallization and formation of a polycrystalline ultra hard material layer, such as a polycrystalline diamond or polycrystalline cubic boron nitride layer, directly onto the upper surface 54 of the cemented tungsten carbide substrate 38 .
[0013] It has been found by applicants that many cutters develop cracking, spalling, chipping and partial fracturing of the ultra hard material cutting layer at a region of cutting layer subjected to the highest loading during drilling. This region is referred to herein as the “critical region” 56 . The critical region 56 encompasses the portion of the cutting layer 44 that makes contact with the earth formations during drilling. The critical region 56 is subjected to the generation of high magnitude stresses from dynamic normal loading, and shear loadings imposed on the ultra hard material layer 44 during drilling. Because the cutters are typically inserted into a drag bit at a rake angle, the critical region includes a portion of the ultra hard material layer near and including a portion of the layer's circumferential edge 22 that makes contact with the earth formations during drilling.
[0014] The high magnitude stresses at the critical region 56 alone or in combination with other factors, such as residual thermal stresses, can result in the initiation and growth of cracks 58 across the ultra hard layer 44 of the cutter 18 . Cracks of sufficient length may cause the separation of a sufficiently large piece of ultra hard material, rendering the cutter 18 ineffective or resulting in the failure of the cutter 18 . When this happens, drilling operations may have to be ceased to allow for recovery of the drag bit and replacement of the ineffective or failed cutter. The high stresses, particularly shear stresses, can also result in delamination of the ultra hard layer 44 at the interface 46 .
[0015] One type of ultra hard working surface 20 for fixed cutter drill bits is formed as described above with polycrystalline diamond on the substrate of tungsten carbide, typically known as a polycrystalline diamond compact (PDC), PDC cutters, PDC cutting elements, or PDC inserts. Drill bits made using such PDC cutters 18 are known generally as PDC bits. While the cutter or cutter insert 18 is typically formed using a cylindrical tungsten carbide “blank” or substrate 38 which is sufficiently long to act as a mounting stud 40 , the substrate 38 may also be an intermediate layer bonded at another interface to another metallic mounting stud 40 .
[0016] The ultra hard working surface 20 is formed of the polycrystalline diamond material, in the form of a cutting layer 44 (sometimes referred to as a “table”) bonded to the substrate 38 at an interface 46 . The top of the ultra hard layer 44 provides a working surface 20 and the bottom of the ultra hard layer cutting layer 44 is affixed to the tungsten carbide substrate 38 at the interface 46 . The substrate 38 or stud 40 is brazed or otherwise bonded in a selected position on the crown of the drill bit body 12 ( FIG. 1 ). As discussed above with reference to FIG. 1 , the PDC cutters 18 are typically held and brazed into pockets 34 formed in the drill bit body at predetermined positions for the purpose of receiving the cutters 18 and presenting them to the geological formation at a rake angle.
[0017] In order for the body of a drill bit to be resistant to wear, hard and wear-resistant materials such as tungsten carbide are typically used to form the drill bit body for holding the PDC cutters. Such a drill bit body is very hard and difficult to machine. Therefore, the selected positions at which the PDC cutters 18 are to be affixed to the bit body 12 are typically formed during the bit body molding process to closely approximate the desired final shape. A common practice in molding the drill bit body is to include in the mold, at each of the to-be-formed PDC cutter mounting positions, a shaping element called a “displacement.”
[0018] A displacement is generally a small cylinder, made from graphite or other heat resistant materials, which is affixed to the inside of the mold at each of the places where a PDC cutter is to be located on the finished drill bit. The displacement forms the shape of the cutter mounting positions during the bit body molding process. See, for example, U.S. Pat. No. 5,662,183 issued to Fang for a description of the infiltration molding process using displacements.
[0019] It has been found by applicants that cutters with sharp cutting edges or small back rake angles provide a good drilling ROP, but are often subject to instability and are susceptible to chipping, cracking or partial fracturing when subjected to high forces normal to the working surface. For example, large forces can be generated when the cutter “digs” or “gouges” deep into the geological formation or when sudden changes in formation hardness produce sudden impact loads. Small back rake angles also have less delamination resistance when subjected to shear load. Cutters with large back rake angles are often subjected to heavy wear, abrasion and shear forces resulting in chipping, spalling, and delamination due to excessive downward force or weight on bit (WOB) required to obtain reasonable ROP. Thick ultra hard layers that might be good for abrasion wear are often susceptible to cracking, spalling, and delamination as a result of residual thermal stresses associated with forming thick ultra hard layers on the substrate. The susceptibility to such deterioration and failure mechanisms is accelerated when combined with excessive load stresses.
[0020] FIG. 3 shows a prior art PDC cutter held at an angle in a drill bit 10 for cutting into a formation 45 . The cutter 18 includes a diamond material table 44 affixed to a tungsten carbide substrate 38 that is bonded into the pocket 34 formed in a drill bit blade 14 . The drill bit 10 (see FIG. 1 ) will be rotated for cutting the inside surface of a cylindrical well bore. Generally speaking, the back rake angle “A” is used to describe the working angle of the working surface 20 , and it also corresponds generally to the magnitude of the attack angle “B” made between the working surface 20 and an imaginary tangent line at the point of contact with the well bore. It will be understood that the “point” of contact is actually an edge or region of contact that corresponds to critical region 56 (see FIG. 2 ) of maximum stress on the cutter 18 . Typically, the geometry of the cutter 18 relative to the well bore is described in terms of the back rake angle “A.”
[0021] Different types of bits are generally selected based on the nature of the geological formation to be drilled. Drag bits are typically selected for relatively soft formations such as sands, clays and some soft rock formations that are not excessively hard or excessively abrasive. However, selecting the best bit is not always straightforward because many formations have mixed characteristics (i.e., the geological formation may include both hard and soft zones), depending on the location and depth of the well bore. Changes in the geological formation can affect the desired type of a bit, the desired ROP of a bit, the desired rotation speed, and the desired downward force or WOB. Where a drill bit is operated outside the desired ranges of operation, the bit can be damaged or the life of the bit can be severely reduced.
[0022] For example, a drill bit normally operated in one general type of formation may penetrate into a different formation too rapidly or too slowly subjecting it to too little load or too much load. For another example, a drill bit rotating and penetrating at a desired speed may encounter an unexpectedly hard formation material, possibly subjecting the bit to a “surprise” or sudden impact force. A formation material that is softer than expected may result in a high rate of rotation, a high ROP, or both, that can cause the cutters to shear too deeply or to gouge into the geological formation.
[0023] This can place greater loading, excessive shear forces and added heat on the working surface of the cutters. Rotation speeds that are too high without sufficient WOB, for a particular drill bit design in a given formation, can also result in detrimental instability (bit whirling) and chattering because the drill bit cuts too deeply or intermittently bites into the geological formation. Cutter chipping, spalling, and delamination, in these and other situations, are common failure modes for ultra hard flat top surface cutters.
[0024] Dome cutters have provided certain benefits against gouging and the resultant excessive impact loading and instability. This approach for reducing adverse effects of flat surface cutters is described in U.S. Pat. No. 5,332,051. An example of such a dome cutter in operation is depicted in FIG. 4 . The prior art cutter 60 has a dome shaped top or working surface 62 that is formed with an ultra hard layer 64 bonded to a substrate 66 . The substrate 66 is bonded to a metallic stud 68 . The cutter 60 is held in a blade 70 of a drill bit 72 (shown in partial section) and engaged with a geological formation 74 (also shown in partial section) in a cutting operation. The dome shaped working surface 62 effectively modifies the rake angle A that would be produced by the orientation of the cutter 60 .
[0025] Scoop cutters, as shown at 80 in FIG. 5 (U.S. Pat. No. 6,550,556), have also provided some benefits against the adverse effects of impact loading. This type of prior art cutter 80 is made with a “scoop” or depression 90 formed in the top working surface 82 of an ultra hard layer 84 . The ultra hard layer 84 is bonded to a substrate 86 at an interface 88 . The depression 90 is formed in the critical region 56 . The upper surface 92 of the substrate 86 has a depression 94 corresponding to the depression 90 , such that the depression 90 does not make the ultra hard layer 84 too thin. The interface 88 may be referred to as a non-planar interface (NPI).
[0026] What is still needed, however, are improved cutters for use in a variety of applications.
SUMMARY
[0027] In one aspect, the present disclosure relates to a modified cutting element that includes a base portion, an ultrahard layer disposed on said base portion, and at least one modified region disposed adjacent to a cutting face of the cutter.
[0028] In one aspect, the present disclosure relates to a drill bit that includes a bit body; and at least one cutter, the at least one cutter comprising a base portion, an ultrahard layer disposed on said base portion, and at least one modified region disposed adjacent to a cutting face of the cutter.
[0029] Other aspects and advantages of the disclosure will be apparent from the following description and the appended claims.
BRIEF DESCRIPTION OF DRAWINGS
[0030] FIG. 1 is a perspective view of a prior art fixed cutter drill bit sometimes referred to as a “drag bit”;
[0031] FIG. 2 is a perspective view of a prior art cutter or cutter insert with an ultra hard layer bonded to a substrate or stud;
[0032] FIG. 3 is a partial section view of a prior art flat top cutter held in a blade of a drill bit engaged with a geological formation (shown in partial section) in a cutting operation;
[0033] FIG. 4 is a schematic view of a prior art dome top cutter with an ultra hard layer bonded to a substrate that is bonded to a stud, where the cutter is held in a blade of a drill bit (shown in partial section) and engaged with a geological formation (also shown in partial section) in a cutting operation;
[0034] FIG. 5 is a perspective view of a prior art scoop top cutter with an ultra hard layer bonded to a substrate at a non-planar interface (NPI);
[0035] FIGS. 6A , 6 B, and 6 C show a side, front, and perspective view of a cutter in accordance with an embodiment of the present invention;
[0036] FIG. 7 shows a cutter in accordance with another embodiment of the present invention; and
[0037] FIG. 8 shows a blade including cutters in accordance with an embodiment of the present invention.
[0038] FIG. 9 shows a PDC bit including cutters formed in accordance with an embodiment of the present invention.
[0039] FIGS. 10A , 10 B, and 10 C are perspective and cross-sectional views of an ultra hard top layer having a varied geometry chamfer circumferentially around the cutting edge of the working surface of the ultra hard layer wherein the size of the chamfer is varied circumferentially around the cutting edge according to one embodiment;
[0040] FIG. 11 is a graph showing the average chamfer size as varied with different cutting depths for a cutter having varied chamfer as compared to a cutter having fixed geometry chamfer.
[0041] FIG. 12 shows an ultra hard layer according to one or more embodiments.
[0042] FIG. 13 shows a cutter according to one or more embodiments.
DETAILED DESCRIPTION
[0043] The present disclosure relates to shaped cutters that provide advantages when compared to prior art cutters. In particular, embodiments of the present disclosure relate to cutters that have structural modifications to the cutting surface in order to improve cutter performance. As a result of the modifications, embodiments of the present disclosure may provide improved cooling, higher cutting efficiency, and longer lasting cutters when compared with prior art cutters.
[0044] Embodiments of the present disclosure relate to cutters having a substrate or support stud, which in some embodiments may be made of cemented carbide, for example tungsten carbide, and an ultra hard cutting surface layer or “table” made of a polycrystalline diamond material or a polycrystalline boron nitride material deposited onto or otherwise bonded to the substrate at an interface surface. Also, in selected embodiments, the ultra-hard layer may comprise a “thermally stable” layer. One type of thermally stable layer that may be used in embodiments of the present disclosure is leached polycrystalline diamond.
[0045] A typical polycrystalline diamond layer includes individual diamond “crystals” that are interconnected. The individual diamond crystals thus form a lattice structure. A metal catalyst, such as cobalt may be used to promote recrystallization of the diamond particles and formation of the lattice structure. Thus, cobalt particles are typically found within the interstitial spaces in the diamond lattice structure. Cobalt has a significantly different coefficient of thermal expansion as compared to diamond. Therefore, upon heating of a diamond table, the cobalt and the diamond lattice will expand at different rates, causing cracks to form in the lattice structure and resulting in deterioration of the diamond table.
[0046] In order to obviate this problem, strong acids may be used to “leach” the cobalt from the diamond lattice structure. Examples of “leaching” processes can be found, for example in U.S. Pat. Nos. 4,288,248 and 4,104,344. Briefly, a hot strong acid, e.g., nitric acid, hydrofluoric acid, hydrochloric acid, or perchloric acid, or combinations of several strong acids may be used to treat the diamond table, removing at least a portion of the catalyst from the PDC layer.
[0047] Removing the cobalt causes the diamond table to become more heat resistant, but also causes the diamond table to be more brittle. Accordingly, in certain cases, only a select portion (measured either in depth or width) of a diamond table is leached, in order to gain thermal stability without losing impact resistance. As used herein, thermally stable polycrystalline diamond compacts include both of the above (i.e., partially and completely leached) compounds. In one embodiment, only a portion of the polycrystalline diamond compact layer is leached. For example, a polycrystalline diamond compact layer having a thickness of 0.010 inches may be leached to a depth of 0.006 inches. In other embodiments, the entire polycrystalline diamond compact layer may be leached. A number of leaching depths may be used, depending on the particular application, for example, in one embodiment the leaching depth may be 0.05 mm.
[0048] FIGS. 6A-6C show multiple views of a cutter formed in accordance with an embodiment of the present invention. In FIG. 6A , a cutter comprises a substrate or “base portion,” 600 , on which an ultrahard layer 602 is disposed. In this embodiment, the ultrahard layer 602 comprises a polycrystalline diamond layer. As explained above, when a polycrystalline diamond layer is used, the layer may further be partially or completely leached. A beveled edge 606 may be provided on at least one side of the ultrahard layer 602 , but more commonly, may be placed on at least two sides, so that the cutter may be removed and reoriented for use a second time. Further, at least one modified region 604 is formed on the ultrahard layer 602 . FIGS. 6B and 6C show that, in this embodiment, two modified regions 604 have been formed on the ultrahard layer 602 . In particular, in FIG. 6C the modified regions 604 comprise tapered portions that have been machined from the ultrahard layer 602 .
[0049] The original height of the diamond table layer is shown as unmodified portion 608 , as the modified regions 604 are designed such that the unmodified portion 608 has a discrete width in this embodiment. In some instances the modified region or regions 604 may be formed when the cutter is actually being bonded together (i.e., a modified region is originally built into the ultrahard layer), but in other instances, the modified region may be formed after the formation of the ultrahard layer, by using electrical discharge machining, for example. In addition, in select embodiments, only portions of the modified surface may be leached. Those having ordinary skill in the art will recognize that masking agents may be used to prevent leaching in certain areas, to provide regions that are leached and legions that are unleached.
[0050] Wire electrical discharge machining (EDM) is an electrical discharge machining process with a continuously moving conductive wire as tool electrode. The mechanism of metal removal in wire EDM involves the complex erosion effect of electric sparks generated by a pulsating direct current power supply between two closely spaced electrodes in dielectric liquid. The high energy density erodes material from both the wire and workpiece by local melting and vaporizing. Because the new wire keeps feeding to the machining area, the material is removed from the workpiece with the moving of wire electrode. Eventually, a cutting shape is formed on the workpiece by the programmed moving trajectory of wire electrode.
[0051] As the term is used herein, a modified region constitutes at least one area, adjacent to the cutting face, that has a lower overall height than the cutting face itself. Cutters containing the modified region 604 have a number of advantages when compared to prior art planar cutters. For example, because the modified region is a depressed area adjacent to the cutting face, improved cooling (due to better fluid flow and/or air flow) around the cutting edge may be seen, which may help prevent failure due to thermal degradation.
[0052] In the embodiment shown in FIG. 6 c , the beveled edge 606 is formed such that when placed into a pocket, the beveled edge 606 will form the cutting face of the cutter. Those having ordinary skill in the art will appreciate that the size of the beveled edge may be modified depending on the application. For example, in selected applications, the size may range from five thousandths of an inch (0.005 inches) to about fifty thousandths of an inch (0.050 inches). In addition, the bevel may be located at other portions, or additional beveled regions may be provided. In selected embodiments, the modified region 604 is provided such that a self-sharpening effect occurs at the cutting face. That is, as portions of the cutter chip away, a fresh portion is exposed. Having this self-sharpening beveled edge 606 may provide higher cutting efficiency as compared to prior art cutters, as the beveled edge may initially fracture rock more efficiently than a typical planar contact. This feature may be particularly useful in higher hardness formations. Embodiments may also include cutters having shaped working surfaces with a varied geometry chamfer. Referring now to FIG. 10A , FIG. 10A shows an ultra hard top layer 800 for a cutter that has a shaped working surface 102 including a varied geometry chamfer 104 circumferentially around the cutting edge 106 . The bevel 104 is varied in size circumferentially around the cutting edge 106 according to one embodiment. The change in the size or the width of the bevel is demonstrated in the elevation section views of FIGS. 10B and 10C taken along section lines B-B and C-C of FIG. 1 OA, respectively. In this embodiment, the width 108 in FIG. 10B is smaller than the width 110 in FIG. 10C . The angle 112 of the bevel at section B-B, FIG. 10B , is the same as angle 114 at section line C-C, FIG. 10C ; however, in other embodiments, the angle of the bevel is varied circumferentially around the cutting edge. It will be understood that a varied geometry of a bevel could also be provided as a combination of varied size and varied angle. Additionally, in one or more embodiments, the bevel is formed so that its size increases away from the area of the cutter surface engaged with the geological formation. For example, referring to FIG. 11 , the amount of the variable size bevel in contact with the formation increases with the depth of cut. Thus, when the cutter digs into the formation, a greater portion of the cutting edge has a larger bevel to give more protection against chipping and spalling.
[0053] In FIG. 7 , another embodiment of the present invention is shown. In FIG. 7 , a cutter 700 , is shown having a base portion 702 and a ultrahard layer 704 disposed thereon. Further, a beveled edge 706 is provided at a cutting face of the insert. In this embodiment, a modified region 708 extends over substantially all of the cutter 700 . In this embodiment, the modified region 708 comprises a substantially continuous “saddle shaped” region. In this embodiment, if the modified region is formed after the deposition of an ultrahard layer, the modified region may be formed in a single manufacturing pass, whereas with the multiple modified regions in FIGS. 6A , 6 B, and 6 C, multiple manufacturing passes may be required. As can be seen from FIG. 7 , the ultrahard material layer has an exposed upper surface 710 and a peripheral surface 712 , such that the upper surface intersects the peripheral surface along a peripheral edge 714 . As can be seen, the peripheral edge 714 continuously decreases in height and increases in height as measured from a first plane 716 perpendicular to a longitudinal axis 718 . The peripheral edge decreases from a maximum height 719 as measured from a plane 716 to a minimum height of 720 as measured from the same plane 716 . As second plane 722 along the longitudinal axis 718 intersects the peripheral edge at a first point 724 and a second point 726 . A third plane 728 along the longitudinal axis 718 insects the peripheral edge at a third point 730 and a fourth point 732 . As can be seen from FIG. 7 , the peripheral edge has a first convex portion 740 extending from the first point 724 in a direction towards the third point 730 . In addition, a first concave portion 742 extends from the first convex portion 740 to the third point 730 . Similarly, a second concave portion extends from the third point in a direction towards the second point 726 and a second convex portion extends from the second concave portion to the second point 726 . Moreover, a third convex portion extends from the second point 726 in a direction towards the fourth point 732 and a third concave portion extends from the third convex portion to the fourth point 732 . In addition, a fourth concave point extends from the fourth point 732 in a direction towards the first point 724 and a fourth convex portion extends from the fourth concave portion to the first point 724 .
[0054] After formation of the saddle-shaped cutter, mill tests were performed to determine the performance of the cutters. Test results showed that approximately a 20% increase in performance when compared to prior art cutters was seen when a polycrystalline diamond surface was used. In addition, when thermally stable polycrystalline diamond was used as the ultrahard layer, a performance jump of nearly 70% was seen as compared to unmodified thermally stable polycrystalline diamond cutters. As stated above, without being limited to any particular theory, that the improved performance may be due to a number of factors such as, improved cooling around the cutting face, higher cutting efficiency (due to the non-planar interaction at the cutting face), and the fact that a non-planar interface leads to less flaking of the thermally stable polycrystalline diamond.
[0055] Cutters formed in accordance with embodiments of the present invention may be used either alone or in conjunction with standard cutters depending on the desired application. In addition, while reference has been made to specific manufacturing techniques, those of ordinary skill will recognize that any number of techniques may be used.
[0056] FIG. 8 shows a view of cutters formed in accordance with embodiments of the present invention disposed on a blade of a PDC bit. In FIG. 8 , modified cutters 804 are intermixed on a blade 800 with standard cutters 802 . Similarly, FIG. 9 shows a PDC bit having modified cutters 904 disposed thereon. Referring to FIG. 9 , the fixed-cutter bits (also called drag bits) 900 comprise a bit body 902 having a threaded connection at one end 903 and a cutting head 906 formed at the other end. The head 906 of the fixed-cutter bit 900 comprises a plurality of blades 908 arranged about the rotational axis of the bit and extending radially outward from the bit body 902 . Modified cutting elements 904 are embedded in the blades 908 to cut through earth formation as the bit is rotated on the earth formation. As discussed above, the modified cutting elements may be mixed with standard cutting elements 905 .
[0057] FIG. 12 shows another embodiment of an ultra hard top layer 140 for a cutter with a shaped working surface 142 and having a varied geometry chamfer 144 circumferentially around a cutting edge 146 at the intersection of the shaped working surface 142 and a side surface 148 . The shaped working surface 142 includes one or more depressions 150 a , 150 b , and 150 c extending radially outwardly to the cutting edge 146 . While three depressions 150 a - c are depicted uniformly spaced around the shaped working surface 142 , fewer or a greater number with uniform or non-uniform spacing may be formed without departing from certain aspects of the disclosure. For example, one or more depressions 150 a - c can be formed as one or more planar surfaces or facets in a face 154 .
[0058] Depending upon the embodiment, the face 154 may be a planar shaped surface, a dome shaped surface or a surface having another shape. The depressions 150 a - c in this embodiment comprise planar surfaces or facets each at an obtuse angle relative to a central axis 152 of the cylindrical ultra hard top layer. The obtuse angle is different from the angle of other portions of the working surface, such that a relative depressed area defining the depressions 150 a - c is formed the face 154 . Where the surrounding portions of the face 154 are planar and at a 90-degree angle with respect to the axis of the cutter, the obtuse angle is generally greater than 90 degrees with respect to the axis 152 of the cutter. However, according to alternative embodiments of the invention, the obtuse angle may be less than 90 degrees. It will also be understood that in other alternative embodiments, each of the depressions 150 a - c can be multi-faceted or comprised of multiple planar surfaces. Alternatively, the depressions 150 a - c can also be formed with simple curved surfaces that may be concave or convex or can be formed with a plurality of curved surfaces or with a smooth complex curve.
[0059] The depressions 150 a - c may be formed and shaped during the initial compaction of the ultra hard layer 140 or can be shaped after the ultra hard layer is formed, for example by Electro Discharge Machining (EDM) or by Electro Discharge Grinding (EDG). The ultra hard layer 140 may, for example, be formed as a polycrystalline diamond compact or a polycrystalline cubic boron nitride compact. Also, in selected embodiments, the ultra-hard layer may comprise a “thermally stable” layer. One type of thermally stable layer that may be used in embodiments may be a TSP element or partially or fully leached polycrystalline diamond. The depressions 150 a - c extend generally at an angle relative to the face 154 outward to the edge of the cutter. It has been found that a varied chamfer 144 can be conveniently made with a fixed angle and fixed depth EDM or EDG device. For example, an EDM device will typically cut deepest into the edge 146 where the raise areas of face 154 extend to the edge 146 and will cut less deep where the depressions 150 a - c extend to the edge 146 . The chamfer 144 is cut the least at the lowest edge point in each depression 150 a - c and progressively deeper on either side of the lowest edge point. A varied width or size chamfer is conveniently formed circumferentially around the edge 146 of the ultra hard cutter layer 140 . Alternatively, variable or programmable angle and depth EDM or EGM can be used to form the variable geometry chamfer. FIG. 13 shows a three-dimensional model of a cutter 160 having an ultra hard layer 162 with a shaped working surface 164 . The ultra hard layer 162 is bonded to a substrate 166 at a non-planar interface 168 according to one embodiment of the invention.
[0060] While the invention has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope of the invention as disclosed herein. Accordingly, the scope of the invention should be limited only by the attached claims. | A cutter for a drag bit may include a substrate and an ultrahard layer on an end surface of the substrate. The ultrahard layer may include an exposed surface having at least three depressions extending from an interior of the exposed surface radially outward to a peripheral edge formed between the working surface and a side surface of the ultrahard layer, the at least three depressions separated from each other by at least three raised regions forming an apex of the exposed surface, the at least three raised regions connected to each other proximate the central axis and extending from proximate the central axis to the peripheral edge. Other working surfaces are also included. | 4 |
This application is a continuation of application Ser. No. 111,450 filed Oct. 22, 1987, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for reducing sheeting during polymerization of alpha-olefins and more particularly to a process for reducing sheeting during polymerization of ethylene.
2. Summary of the Prior Art
As is well known to those skilled in the art, low pressure, high or low density polyethylenes can now be conventionally provided by a fluidized bed process utilizing several families of catalysts to produce a full range of low density and high density products. The appropriate selection of catalysts to be utilized depends in part upon the type of end product desired, i.e., high density, low density, extrusion grade, film grade resins and other criteria and are generally described e.g., in U.S. Pat. No. 4,532,311 issued on July 30, 1985.
In general, the above catalysts are introduced together with the polymerizable materials, into a reactor having an expanded section above a straight-sided section. Cycle gas enters the bottom of the reactor and passes upward through a gas distributor plate into a fluidized bed located in the straight-sided section of the vessel. The gas distributor plate serves to ensure proper gas distribution and to support the resin bed when gas flow is stopped.
Gas leaving the fluidized bed entrains resin particles. Most of these particles are disengaged as the gas passes through the expanded section where its velocity is reduced.
Unfortunately the utilization of certain type catalysts, referred to in said U.S. Patent as Type IV catalysts, as well as vanadium based catalysts are prone to cause sheeting (sheets) during production of polyolefins by polymerization of alpha olefins in the fluidized bed process.
In order to satisfy certain end use applications for ethylene resins, such as for film, injection molding and roto molding applications, these type catalysts, i.e., Type IV have been used. However, attempts to produce certain ethylene resins utilizing the Type IV catalysts or vanadium based catalysts supported on a porous silica substrate in certain fluid bed reactors, have not been entirely satisfactory from a practical commercial standpoint. This is primarily due to the formation of "sheets" in the reactor after a brief period of operation. The "sheets" can be characterized as constituting a fused polymeric material.
The sheets vary widely in size, but are similar in most respects. They are usually about 1/4 to 1/2 inch thick and are from about one to five feet long, with a few specimens even longer. They have a width of about 3 inches to more than 18 inches. The sheets have a core composed of fused polymer which is oriented in the long direction of the sheets and their surfaces are covered with granular resin which has fused to the core. The edges of the sheets can have a hairy appearance from strands of fused polymer.
After a relatively short period of time during polymerization, sheets begin to appear in the reactor, and these sheets plug product discharge systems forcing shutdown of the reactor.
Accordingly, it will be seen that there presently exists a need to improve the polymerization techniques necessary for the production of polyolefin products utilizing titanium based catalysts in fluidized bed reactors.
It is therefore an object of the present invention to provide a process to substantially reduce or eliminate the amount of sheeting which occurs during the low pressure fluidized bed polymerization of alpha olefins utilizing titanium based compounds as catalyst.
These and other objects will become readily apparent from the following description taken in conjunction with the accompanying drawing which generally indicates a typical gas phase fluidized bed polymerization process for producing high density and low density polyolefins modified slightly however to illustrate the present process for reducing or eliminating sheeting.
SUMMARY OF THE INVENTION
Broadly contemplated the present invention provides an improvement in the method for polymerization of alpha-olefins in a reaction zone of a fluid bed reactor utilizing titanium based catalysts or other catalysts prone to cause sheeting during said polymerization and wherein a gaseous feed stream comprising monomer, comonomer, an inert gas and hydrogen are continuously passed through said fluidized bed under reactive and sheet forming conditions, withdrawing from said reaction zone polymer product and a recycle stream comprising unreacted gases and solid particles, cooling said recycle stream and recycling said cooled recycle stream to said reaction zone, the improvement comprising, reducing or substantially eliminating sheeting in said reactor by introducing said gaseous feed stream comprising monomer, comonomer, an inert gas and hydrogen into said recycle stream comprising unreacted gases and solid particles at a point prior to cooling of said stream, and thereafter cooling and directing said recycle stream and said gaseous feed stream into said reaction zone.
It has been found that the amount of static voltage generated by impurity addition to fluidized bed polymerization reactors is highly dependent upon the point of addition of the impurity to the cycle. The point of impurity addition that causes the greatest static response is directly into the fluid bed at the fluid stagnant zone. When impurities were injected into the cycle at a point far removed from the fluid bed, (such as upstream of the cycle gas cooler) the resulting static charging effect is greatly attenuated. Thus according to the present invention, by locating monomer, comonomer, nitrogen and hydrogen feedstreams to the process (these streams will contain static causing impurities on occasion) upstream of the cycle gas cooler, static charging is reduced. The reduction of static charging in the fluid bed results in better reactor performance by reducing the risk of sheet and chunk formation which are often the direct result of static electricity. According to this invention sheeting is minimized, and therefore resultant downtime to remove these sheets is also eliminated.
DETAILED DESCRIPTION OF THE INVENTION
Referring particularly to the sole FIGURE of the drawing, a conventional fluidized bed reaction system for polymerizing alpha olefins includes a reactor 10 which consists of a reaction zone 12 and a velocity reduction zone 14.
The reaction zone 12 includes a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of polymerizable and modifying gaseous components in the form of make-up feed and recycle gas through the reaction zone. To maintain a viable fluidized bed, the mass gas flow rate through the bed is normally maintained above the minimum flow required for fluidization, and preferably from about 1.5 to about 10 tim G mf and more preferably from about 3 to about 6 times G mf . G mf is used in the accepted form as the abbreviation for the minimum gas flow required to achieve fluidization, C. Y. Wen and Y. H. Yu, "Mechanics of Fluidization", Chemical Engineering Progress Symposium Series, Vol 62, p. 100-111 (1966).
It is highly desirable that the bed always contains particles to prevent the formation of localized "hot spots" and to entrap and distribute the particulate catalyst throughout the reaction zone. On start up, the reactor is usually charged with a base of particulate polymer particles before gas flow is initiated. Such particles may be identical in nature to the polymer to be formed or different therefrom. When different, they are withdrawn with the desired formed polymer articles as the first product. Eventually, a fluidized bed of the desired polymer particles supplants the start up bed.
The appropriate catalyst used in the fluidized bed is preferably stored for service in a reservoir 16 under a blanket of a gas which is inert to the stored material, such as nitrogen or argon.
Fluidization is achieved by a high rate of gas recycle to and through the bed, typically in the order of about 50 times the rate of feed of make up gas. The fluidized bed has the general appearance of a dense mass of viable particles in possible free-vortex flow as created by the percolation of gas through the bed. The pressure drop through the bed is equal to or slightly greater than the mass of the bed divided by the cross-sectional area. It is thus dependent on the geometry of the reactor.
Make-up gas is fed to the bed at a rate equal to the rate at which particulate polymer product is withdrawn. The composition of the make-up gas is determined by a gas analyzer 18 positioned above the bed. The gas analyzer determines the composition of the gas being recycled and the composition of the make-up gas is adjusted accordingly to maintain an essentially steady state gaseous composition within the reaction zone.
To insure complete fluidization, the recycle gas and, where desired, part or all of the make-up gas are returned to the reactor at base 20 below the bed. Gas distribution plate 22 positioned above the point of return ensures proper gas distribution and also supports the resin bed when gas flow is stopped.
The portion of the gas stream which does not react in the bed constitutes the recycle gas which is removed from the polymerization zone, preferably by passing it into velocity reduction zone 14 above the bed where entrained particles are given an opportunity to drop back in to the bed.
The recycle gas is then compressed in a compressor 24 and thereafter passed through a heat exchanger 26 wherein it is stripped of heat of reaction before it is returned to the bed. By constantly removing heat of reaction, no noticeable temperature gradient appears to exist within the upper portion of the bed. A temperature gradient will exist in the bottom of the bed in a layer of about 6 to 12 inches, between the temperature of the inlet gas and the temperature of the remainder of the bed. Thus, it has been observed that the bed acts to almost immediately adjust the temperature of the recycle gas above this bottom layer of the bed zone to make it conform to the temperature of the remainder of the bed thereby maintaining itself at an essentially conStant temperature under steady conditions. The recycle is then returned to the reactor at its base 20 and to the fluidized bed through distribution plate 22. The compressor 24 can also be placed downstream of heat exchanger 26.
Hydrogen may be used as a chain transfer agent for conventional polymerization reactions of the types contemplated herein. In the case where ethylene is used as a monomer the ratio of hydrogen/ethylene employed will vary between about 0 to about 2.0 moles of hydrogen per mole of the monomer in the gas stream.
According to the present invention the hydrogen, nitrogen monomer and comonomer feedstream (gas feed) are introduced into the gas recycle stream prior to the point where the recycle gas stream enter heat exchanger 26 such as through line 42.
Any gas inert to the catalyst and reactants can also be present in the gas stream. The cocatalyst is added to the gas recycle stream upstream of its connection with the reactor as from dispenser 28 through line 30.
As is well known, it is essential to operate the fluid bed reactor at a temperature below the sintering temperature of the polymer particles. Thus to insure that sintering will not occur, operating temperatures below sintering temperatures are desired. For the production of ethylene polymers an operating temperature of from about 90° C. to 100° C. is preferably used to prepare products having a density of about 0.94 to 0.97 while a temperature of about 75° C. to 95° C. is preferred for products having a density of about 0.91 to 0.94.
Normally the fluid bed reactor is operated at pressures of up to about 1000 psi, and is preferably operated at a pressure of from about 150 to 350 psi, with operation at the higher pressures in such ranges favoring heat transfer since an increase in pressure increases the unit volume heat capacity of the gas.
The catalyst is injected into the bed at a rate equal to its consumption at a point 32 which is above the distribution plate 22. A gas which is inert to the catalyst such as nitrogen or argon is used to carry the catalyst into the bed. Injecting the catalyst at a point above distribution plate 22 is an important feature. Since the catalysts normally used are highly active, injection into the area below the distribution plate may cause polymerization to begin there and eventually cause plugging of the distribution plate. Injection into the viable bed, instead, aids in distributing the catalyst throughout the bed and tends to preclude the formation of localized spots of high catalyst concentration which may result in the formation of "hot spots".
Under a given set of operating conditions, the fluidized bed is maintained at essentially a constant height by withdrawing a portion of the bed as product at a rate equal to the rate of formation of the particulate polymer product. Since the rate of heat generation is directly related to product formation, a measurement of the temperature rise of the gas across the reactor (the difference between inlet gas temperature and exit gas temperature) is determinative of the rate of the particulate polymer formation at a constant gas velocity.
The particulate polymer product is preferably withdrawn at a point 34 at or close to distribution plate 22. The particulate polymer product is conveniently and preferably withdrawn through the sequential operation of a pair of timed valves 36 and 38 defining a segregation zone 40. While valve 38 is closed, valve 36 is opened to emit a plug of gas and product to the zone 40 between it and valve 36 which is then closed. Valve 38 is then opened to deliver the product to an external recovery zone and after delivery, valve 38 is then closed to await the next product recovery operation.
Finally, the fluidized bed reactor is equipped with an adequate venting system to allow venting the bed during the start up and shut down. The reactor does not require the use of stirring means and/or wall scraping means.
The reactor vessel is normally constructed of carbon steel and is designed for the operating conditions stated above.
The polymers to which the present invention is primarily directed and which cause the sheeting problems above referred to in the presence of titanium or vanadium catalysts are linear homopolymers of ethylene or linear copolymers of a major mol percent (≧90%) of ethylene, and a minor mol percent (≦10%) of one or more C 3 to C 8 alpha olefins. The C 3 to C 8 alpha-olefins should not contain any branching on any of their carbon atoms which is closer than the fourth carbon atom. The preferred C 3 to C 8 alpha-olefins are propylene, butene-1, hexene-1, and octene-1. This description is not intended to exclude the use of this invention with alpha-olefin homopolymer and copolymer resins in which ethylene is not a monomer.
The homopolymers and copolymers have a density ranging from about 0.97 to 0.91. The density of the copolymer, at a given melt index level is primarily regulated by the amount of the C 3 to C 8 comonomer which is copolymerized with the ethylene. Thus, the addition of progressively larger amounts of the comonomers to the copolymers results in a progressive lowering of the density of the copolymer. The amount of each of the various C 3 to C 8 comonomers needed to achieve the same result will vary from monomer to monomer, under the same reaction conditions. In the absence of the comonomer, the ethylene would homopolymerize.
The melt index of a homopolymer or copolymer is a reflection of its molecular weight. Polymers having a relatively high molecular weight, have relatively high viscosities and low melt index.
Having set forth the general nature of the invention, the following examples illustrate some specific embodiments of the invention. It is to be understood, however, that this invention is not limited to the examples, since the invention may be practiced by the use of various modifications.
Examples 1 and 2 are examples of conventional operations and were conducted in a fluidized bed reactor as described in the sole FIGURE of the drawing except that the gas feed was conventional i.e., the gas feed was introduced into the system in the line after the heat exchanger the line feeding into the bottom of the reactor.
EXAMPLE 1
A fluidized bed reactor was started up at operating conditions designed to produce a film grade low density ethylene copolymer product having a density of 0.918 g/cc, a melt index of 1.0 dg/mm, and a sticking temperature of 140° C. The reaction was started by feeding catalyst to a reactor precharged with a bed of granular resin similar to the product to be made. The catalyst was a mixture of 5.5 parts titanium tetrachloride, 8,5 parts magnesium chloride and 14 parts tetrahydrofuran deposited on 100 parts Davison grade 952 silica which had been dehydrated at 800° C. and treated with four parts triethylaluminum prior to deposition and was activated with thirty five parts tri-n-hexyl aluminum subsequent to deposition. Prior to starting catalyst feed, the reactor and resin bed were brought up to the operating temperature of 85° C., were purged of impurities by circulating nitrogen through the resin bed. Ethylene, butene and hydrogen concentrations were established at 53, 24, and 11% respectively. cocatalyst was fed at a rate of 0.3 parts triethylaluminum per part of catalyst.
Reactor start-up was normal. After producing product for 29 hours and equivalent to 6 1/2 times the weight of the fluidized bed, temperature excursions of 1° to 2° C. above bed temperature were observed using thermocouples located just inside the reactor wall at an elevation of 1/2 reactor diameter above the gas distributor plate. Prior experience had shown that such temperature excursions are a positive indication that sheets of resin are being formed in the fluidized bed. Concurrently, bed voltage (measured using an electrostatic voltmeter connected to a 1/2 inch diameter spherical electrode located one inch from the reactor wall at an elevation of 1/2 reactor diameter above the gas distributor plate) increased from reading of approximately +1500 to +2000 volts to a reading of over +5000 volts and then dropped back to +2000 volts over a three minute period. Temperature and voltage excursions continued for approximately 12 hours and increased in frequency and magnitude. During this period, sheets of fused polyethylene resin began to show up in the resin product. Evidence of sheeting became more severe, i.e., temperature excursions increased to as high as 20° C. above bed temperature and stayed high for extended periods of time and voltage excursions also became more frequent. The reactor was shut down because of the extent of sheeting.
EXAMPLE 2
The fluidized bed reactor used in Example 1 was started up and operated to produce a linear low density ethylene copolymer suitable for extrusion or rotational molding and having a density of 0.934, a melt index of 5 and a sticking temperature of 118° C. The reaction was started by feeding catalyst similar to the catalyst in Example 1 except activated with 28 parts tri-n-hexylaluminum, to the reactor precharged with a bed of granular resin similar to the product to be made. Prior to starting catalyst feed the reactor and resin bed were brought up to the operating temperature of 85° C., and were purged of impurities with nitrogen. The concentrations of ethylene (52%, butene (14%), hydrogen (21%) were introduced into the reactor. Cocatalyst triethylaluminum was fed at 0.3 parts per part of catalyst. The reactor was operated continuously for 48 hours and during that period produced resin equivalent to 9 times the amount of resin contained in the bed. After this 48 hour period of smooth operation, sheets of fused resin began to come out of the reactor with the normal, granular product. At this time voltages measured 1/2 reactor diameter above the distributor plate averaged +2000 volts and ranged from 0 to +10,000 volts, while skin thermocouples at the same elevation indicated excursions of ≧15° C. above the bed temperature. Two hours after the first sheets were noted in the product from the reactor, it was necessary to stop feeding catalyst and cocatalyst to the reactor to reduce the resin production rate because sheets were plugging the resin discharge system. One hour later, catalyst and cocatalyst feeds were restarted. The production of sheets continued and after two hours catalyst and cocatalyst feed were again stopped and the reaction was terminated by injecting carbon monoxide. The voltage at this time, was ≧12,000 volts and the thermocouple excursions continued until the poison was injected. In total, the reactor was operated for 53 hours and produced 101/2 bed volumes of resin before the reaction was stopped due to sheeting.
EXAMPLE 3
Continuous polymerization of ethylene was sustained in a fluidized bed reactor. A film-grade low-density copolymer having a density of 0.918 g/cm 3 and a melt index of 2.0 gd/min was produced by feeding catalyst and cocatalyst to the reactor. Catalyst consisted of a mixture of 5 parts TiCl 3 .1/3AlCl 3 , 7 parts MgCl 2 , and 17 parts tetrahydrofuran deposited on 100 parts of Davison grade 955 silica which had been dehydrated at 600° C. and treated with 5.5 parts triethylaluminum prior to deposition and activated with 33 parts tri-n-hexylaluminum and 11 parts diethylaluminum chloride subsequent to deposition. The cocatalyst, triethylaluminum, was fed at a sufficient rate to maintain a molar ratio of Al to Ti of 40 to 1. The fluidized bed was maintained at a temperature of 85° C. Concentrations of ethylene, butene, and hydrogen in the reactor were 34, 11, and 8 mol percent, respectively. Copolymer resin was periodically withdrawn from the reactor in order to maintain a constant fluidized bed height within the reactor. Catalyst was fed directly into the fluidized bed; all other feeds were introduced into the gas recycle line upstream of both the heat exchanger and compressor.
Various quantities of either water vapor or oxygen in nitrogen were then continuously fed to the gas recycle line for periods of several hours at a time. The feed location was downstream of the compressor, upstream of the heat exchanger. The rates of introduction of water or oxygen are reported on a ppmw basis with respect to rate of removal of copolymer from the reactor. During their introduction, both inlet temperature of the cycle gas, measured below the fluidized bed, and static voltage in the bed were monitored. An increase of 1° C. in inlet temperature represented a loss in production rate of about 20%. Static voltage was measured by monitoring the voltage on a hemispherical steel probe located in the fluidized bed, one inch in from the inside wall, three bed diameters above the distributor plate. Measurements of catalyst activity and static are shown below:
______________________________________ Con- Catalyst Activity Change in Magnitude centration Change in Inlet of Static LevelImpurity ppmw Temp. °C. Volts______________________________________H.sub.2 O 2.4 No Change No ChangeH.sub.2 O 4.8 +0.7° 50H.sub.2 O 4.1 +0.4° 50O.sub.2 3.0 No Change No ChangeO.sub.2 7.8 +1.0° No Change______________________________________ *Triethylaluminum was fed to recycle line downstream of heat exchanger.
Reactor operation remained smooth throughout these tests. This example shows that introduction of impurity levels up to 7.8 ppmw caused little or no static when the impurities were introduced into the recycle line upstream of the heat exchanger.
EXAMPLE 4
Continuous polymerization of ethylene was again sustained in a fluidized bed reactor. A high density copolymer having a resin density of 0.946 g/cm 3 and a flow index (190° C., 21.6 kg) of 9 dg/min was produced by feeding catalyst, cocatalyst, and promoter to the reactor. The catalyst was a mixture of 55 parts VCl 3 , 1.5 parts diethylaluminum chloride, and 13 parts tetrahydrofuran deposited on 100 parts of Davison grade 953 silica which had been dehydrated at 600° C. Triethylaluminum was fed at a rate to maintain the molar ratio of Al to V at 40 to 1. Trichlorofluoromethane was fed between the compressor and heat exchanger at a molar ratio with respect to triethylaluminum of 0.75 to 1. The temperature of the fluidized bed was maintained at 100° C. Concentrations of ethylene, hexene, and hydrogen in the reactor were 73, 1, and 1.6 mol percent, respectively. Operation of the fluidized bed was otherwise similar to that in the previous Example.
One concentration of water vapor and two concentrations of oxygen were then introduced into the reactor, each for a several -hour period. These impurities were mixed with nitrogen and continuously introduced into the recycle gas at a point just downstream of the compressor, upstream of the heat exchanger. While each of these impurities was being fed to the recycle line, both catalyst activity and static were monitored as explained in the previous Example. Results were:
______________________________________ Con- Catalyst Activity Change in Magnitude centration Change in Inlet of Static LevelImpurity ppmw Temp. °C. Volts______________________________________H.sub.2 O 4.0 No Change No ChangeO.sub.2 5.0 No Change 10O.sub.2 9.0 No Change 50______________________________________
Reactor operation remained good while these impurities were being fed. The results show that with a different catalyst system and different resin properties than in the previous Example, impurities introduced upstream of the heat exchanger at levels up to 9 ppmw again had little or no effect on static.
EXAMPLE 5
Continuous polymerization of ethylene was sustained in a fluidized bed reactor. A film grade low density copolymer having a density of 0.918 g/cm 3 and a melt index of 2.0 dg/min was produced by feeding catalyst and cocatalyst to the reactor. Catalyst consisted of a mixture of 5 parts TiCl 3 . 1/3 AlCl 3 , 7 parts MgCl 2 , and 17 parts tetrahydrofuran deposited on 100 parts of Davison grade 955 silica which had been dehydrated at 600° C. and treated with 5.5 parts triethylaluminum prior to deposition and activated with 33 parts tri-n-hexylaluminum and 11 parts diethylaluminum chloride subsequent to deposition. The cocatalyst, triethylaluminum, was fed at a sufficient rate to maintain a molar ratio of Al to Ti of 30:1. The fluidized bed was maintained at 88° C. Concentrations of ethylene, butene and hydrogen in the reactor were 37, 12, and 9 mol %, respectively. Copolymer resin was periodically withdrawn from the reactor in order to maintain a constant fluidized bed height within the reactor. Catalyst was fed directly into the fluidized bed; all other feeds were introduced into the gas recycle line upstream of both heat exchanger and compressor.
A stream of nitrogen saturated with water vapor water was then fed to the reactor downstream of the compressor, upstream of the heat exchanger. The rate of water addition was in the amount of 20 ppm of water per part ethylene addition to the recycle stream. This water feed was added continuously for 2 and 1/2 hours and during this time there was no change in the static voltage potential in the fluidized bed. Static voltage remained at zero volts for the duration of the water addition. Static voltage was measured by monitoring the voltage on a hemispherical steel probe located in the fluidized bed, one inch in from the inside wall, three bed diameters above the distribution plate. The feed location of the saturated water stream was then transferred to just downstream of the heat exchanger. Water addition to this latter location was in the amount of 8 ppm water per part ethylene addition to the gas recycle. Upon introducing water to this new location downstream of the heat exchanger, negative static of -250 volts was generated immediately. Within ten minutes after water addition downstream of the heat exchanger, the temperature indicated by a wall thermocouple in the side of the polymerization reactor in the fluidized bed zone rose to 92° C., or 4° C. above bed temperature. This reading is indicative of sheet formation at this location at the wall in the fluidized bed.
EXAMPLE 6
Co-polymerization of ethylene and butene was sustained in a fluidized bed reactor. The product copolymer was a film grade resin of 0.918 grams/cm 3 and a melt index of 1 dg/min. The catalyst consisted of a mixture of 5 parts TiCl 3 1/3 AlCl 3 , 7 parts MgCl 2 , and 17 parts tetrahydrofuran deposited on 100 parts of Davison grade 955 silica. The silica had been dehydrated at 600° C. and treated with 5.7 parts triethylaluminum prior to disposition and activated with 32 parts tri-n-hexyl aluminum and 11 parts diethylaluminum chloride subsequent to disposition. The catalyst triethylaluminum, was fed at a sufficient rate to maintain molar ratio of Al to Ti of 30 to 1. The fluidized bed was maintained at a temperature of 88° C. Concentrations of ethylene, butene, and hydrogen in the reactor were 46, 16, and 14 mole percent, respectively. Resin was periodically withdrawn from the reactor in order to maintain a constant fluidized bed height within the reactor. Catalyst was fed directly into the fluidized bed and all other feeds were introduced into the cycle gas stream downstream of both the compressor and heat exchanger.
Static voltage was measured in the fluidized bed by monitoring the voltage on a hemispherical steel probe located one inch from the inside wall, and one bed diameter above the distributor plate.
Water was then added to ethylene feed in the amount of 0.6 ppm on an ethylene feed basis. This water addition caused an immediate static voltage response in the fluidized bed from zero to -1600 volts.
The water addition point was then switched from downstream to upstream of the heat exchanger, and the negative static dissipated to zero volts almost immediately.
The water addition point was then toggled 3 more times between the heat exchanger inlet and discharge. On each occasion negative voltage appeared whenever water was fed to the heat exchanger outlet and the voltage dissipated immediately when the water was fed to the heat exchanger inlet. Water feed to the heat exchanger inlet in the amount of 0.8 ppm water per part ethylene feed to the recycle stream continuously for three hours caused no static voltage in the reactor.
EXAMPLE 7
The same reactor producing resin under the same conditions as in Example 6 was again used to test the effect of water feed location upon static on a separate occasion.
In this instance, water fed to the heat exchanger outlet in the amount of 0.3 ppm per part ethylene feed to the recycle caused -500 volts of static in the fluidized bed. When the feed location was switched to the heat exchanger inlet, water feed rates of up to 1.4 ppm per part ethylene feed caused no static in the fluidized bed. A continuous water feedrate of 1.2 ppm per part ethylene feed for four hours caused no static in the fluidized bed.
EXAMPLE 8
The same reactor producing copolymer resin under the same conditions as in Examples 6 and 7 was used to examine the effect of methanol feed location upon static voltage and sheeting in the fluidized bed.
In this case, nitrogen saturated with methanol at 20° C. was first fed to the heat exchanger outlet at a rate of 1.3 ppm methanol per part ethylene feed to the reactor recycle and the static voltage in the reactor immediately rose to +4000 volts. Simultaneously, a thermocouple measuring temperature at the inner wall of the reactor at a height of one plate diameter above the distributor plate rose from 86° C. to 94° C. indicating that a sheet was formed at this time. Since the reactor temperature was 88° C. at the time, any wall thermocouple reading in excess of 88° C. was indicative of sheet formation.
When the methanol feed was switched to upstream of the heat exchanger, static voltage dissipated to zero volts almost instantaneously. In addition no wall thermocouple excursions to above the temperature in the fluidized bed occurred when the methanol was fed upstream of the heat exchanger.
The methanol feed was toggled a total of 3 times between the heat exchanger outlet and inlet. In each case, positive static ranging from +700 to +4000 volts occurred immediately when methanol was fed downstream of the heat exchanger and static dissipated to zero, volts when methanol was fed upstream of the heat exchanger. | A process for reducing sheeting during gas phase polymerization of alpha-olefins utilizing catalysts prone to cause sheeting wherein the gaseous feed stream containing monomer comonomer hydrogen and inert gas is introduced into the reactor through the recycle stream to the reactor at a point prior to cooling the recycle stream. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to petroleum field exploration and production. The invention notably is a method for accounting for the evolution of petrophysical properties during diagenesis, for study of fluid flows within a heterogeneous formation. The method allows determination of the potential location of an underground reservoir within a sedimentary basin, or to enhance the recovery of hydrocarbons in a reservoir, or an underground reservoir.
[0003] 2. Description of the Prior Art
[0004] Diagenesis designates all the physico-chemical mechanisms responsible for the conversion of sediments into sedimentary rocks. During diagenesis, part of the sediments is dissolved, and then transported. During transport, the change in the thermodynamic conditions causes ion precipitation leading to sediment cementation and to rock formation (lithification). These thermodynamic changes are either due to physical property variations (pressure, temperature), or to chemical composition changes (mixing with other dissolved minerals). The minerals can then be redissolved, then crystallized again. The alternation of these dissolution and precipitation cycles leads to the progressive evolution of the medium.
[0005] Diagenesis thus is a process converting a homogenous granular porous medium to a heterogeneous consolidated medium. The petrophysical properties of the resulting sedimentary rocks closely depend on the diagenetic cycle that modifies the initial porosities and permeabilities. The unequal development of diagenesis in time and in space is responsible for the heterogeneities observed at local scale as well as at the scale of the sedimentary basin.
[0006] Better comprehension of these phenomena allows extrapolation of more reliably the characteristics of the rocks from the samples that may have been taken and analyzed.
[0007] Applied to the petroleum field, this information leads to better field development while improving reservoir characterization. On the one hand, the reserves can be assessed more precisely if it is possible to estimate the porosity evolution due to diagenesis, which has a direct impact on the amount of potentially accumulated hydrocarbons. On the other hand, the production plan can be adjusted to the estimated permeabilities by best optimizing the extraction facilities. Thus, reconstruction of the diagenetic cycle is a means for better characterizing heterogeneities and it therefore constitutes an appreciable help when working out a production scenario.
[0008] The petroleum industry thus needs tools allowing petrophysical diagenesis modelling. It determines the evolution over time of the petrophysical properties of the rocks, in particular permeability and porosity, as a result of the dissolution-precipitation cycles of the diagenesis.
[0009] There is currently no method providing the evolution of permeabilities and porosities during diagenesis. However, for a facies, that is a rock type associated with a particular diagenetic history, geologists summarize their observations in empirical correlations. Such an approach is illustrated in the study by Lucia, F. Jerry, “Carbonate Reservoir Characterization”, Springer, (2007), EAN13: 9783540727408.
[0010] Petrophysicists have established models for relating permeability to porosity. One of the most famous ones is the Kozeny-Carman law (Carman P. C., Fluid flow through granular bed, Trans. Inst. Chem. Eng. Lond., 1937, 15, p. 150-166). However, these correlations are valid only at a given time, always for a given structure type (facies). Now, during diagenesis, the structure is modified and the porous medium can follow a different permeability-porosity relation. To date, it is not known how to quantify their respective modification.
[0011] Thus, the invention relates to a method of monitoring the evolution of the petrophysical properties of a porous medium during diagenesis. It is based on a pore-scale study, by modelling the pore network of the porous medium (rock) whose geometry varies during diagenesis.
SUMMARY OF THE INVENTION
[0012] The invention relates to a method for quantitative determination of a permeability and porosity evolution of a porous medium during a diagenesis, the porous medium comprising a pore network. The method comprises:
[0000] defining a diagenesis cycle comprising cycles of precipitation and dissolution in the porous medium, as well as an initial pore network structure, by physical measurements and observations of the medium,
constructing a representation of the pore network by a Pore Network Model (PNM) comprising a set of nodes of known geometry connected by channels of known geometry; then, for each cycle of the diagenesis cycle, carrying out steps a) to d) below:
a). determining an ion concentration on the walls of each node and channel;
b). deducing therefrom a geometry variation for the nodes and channels of the PNMI;
c). determining a permeability and a porosity of the modified PNM model;
d). repeating a) to c) until completion occurs according to the diagenesis cycle; and
determining a relationship between permeability of the porous medium and the porosity of the porous medium during the diagenesis.
[0013] According to the invention, the representation of the pore network can be constructed by mercury invasion experiments on cores extracted from the porous medium. Other petrophysical properties, such as relative permeability and capillary pressure, can also be determined at the end of each cycle of the diagenesis cycle.
[0014] According to the invention, the porosity can be determined by volume calculations, knowing the geometry of the PNM, and the permeability can be determined using Darcy's law.
[0015] The invention also relates to a method of determining the potential location of an underground reservoir within a sedimentary basin making up a porous medium. According to method, a relationship is determined between the permeability of the porous medium and the porosity of the porous medium during diagenesis cycle undergone by the basin, by the method according to the invention. Fluid flows within the basin are then studied by means of a basin simulator informed by this relationship.
[0016] The invention furthermore relates to a method for enhancing hydrocarbon recovery in an underground reservoir making up a porous medium, wherein heterogeneities of the reservoir are determined by determining a relationship between the permeability and the porosity of the reservoir during diagenesis cycle undergone by the reservoir, by the method according to the invention, and fluid flows within the reservoir are studied by a reservoir simulator determined by the relationship.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] Other features and advantages of the method according to the invention will be clear from reading the description hereafter of embodiments given by way of non limitative example, with reference to the accompanying figures wherein:
[0018] FIG. 1 shows stages of the method according to the invention for studying the diagenesis from a petrophysical point of view at pore scale;
[0019] FIG. 2 diagrammatically shows a unit cell of a “pore network” model with a cubic node (pore body) and six channels of triangular section (pore throats or thresholds);
[0020] FIG. 3 shows a diagenetic cycle in a homogeneous medium for which the intrinsic dissolution rate is equal to the precipitation rate;
[0021] FIG. 4 illustrates a diagenetic cycle in a homogeneous medium for which the intrinsic dissolution rate is 100 times lower than the precipitation rate;
[0022] FIG. 5 shows a diagenetic cycle in a heterogeneous medium for which the intrinsic dissolution rate is 100 times lower than the precipitation rate. The presence of heterogeneity inverts the overall permeability evolution direction;
[0023] FIG. 6 shows the solute concentration field observed in the network for the diagenetic cycle of FIG. 5 during precipitation. The high concentrations (in black) are generally present in the larger pores, which explains the more marked porosity drop in FIG. 5 in relation to FIG. 4 ; and
[0024] FIG. 7 illustrates, for the diagenetic cycle of FIG. 5 , the translation of the pore size distribution during dissolution. It is a simple translation due to the slowness of the reaction in relation to the diffusive transport, which allows the solute concentration to be homogenized.
DETAILED DESCRIPTION OF THE INVENTION
[0025] The invention relates to a method of determining the evolution of the petrophysical properties of rocks during diagenesis. This information can be used by a basin simulator and/or a reservoir simulator within the field of petroleum exploration and production.
[0026] FIG. 1 illustrates the various stages of this method that comprises:
[0000] A. Determining a diagenesis cycle (SD)
B. Determining the evolution of the petrophysical properties during diagenesis
[0027] 1. Constructing a Porous Network Model (PNM)
[0028] 2. Determining the porosity and permeability evolution
2a. Determining the initial porosity (Φ) and permeability (K): ECO 2b. Determining the overall ( c ) and local (c) concentrations: TR 2c. Determining structure modifications of the porous network: MS 2d. Determining the porosity and the permeability after the reaction: ECO.
[0033] By following the diagenesis cycle defined in A, 2a to 2d are successively carried out for a precipitation reaction (Pr), then for a dissolution reaction (Dis), as illustrated in FIG. 1 .
[0034] A. Determining a Diagenesis Scenario
[0035] The date of formation of a sedimentary basin is determined from field studies (geological, geophysical, petrophysical studies): 10 million years ago for example. By analogy with the present, the basis of the geological science that supposes that the same causes lead to the same effects, it is possible to define the structure of this porous medium. One then speaks of an initial structure (SI). This medium thereafter undergoes the effects of the diagenesis and is converted to a rock. To evaluate these effects, a diagenesis cycle has to be defined. It defines the chronology of the alternations of precipitation and dissolution cycles. For example, it is considered that the rock has undergone, for the first 200,000 years that followed its setting, precipitations, then dissolutions for a million years, then again precipitations for two million years, then . . .
[0036] At this stage, this diagenetic cycle allows prediction of the evolution of the petrophysical properties during diagenesis only qualitatively, that is permeability or porosity rise or drop. Quantification of these evolutions is the subject of point B.
[0037] B. Determining the Evolution of the Petrophysical Properties During Diagenesis
[0038] 1. Constructing a Pore Network Model
[0039] According to the invention, the diagenesis cycle, that is ion transport, dissolution and precipitation phenomena, are modelled at pore scale. A simplified spatial representation of the pore network formed by the pores of the rock is therefore used.
[0040] A well-known representation type, referred to as “Pore Network Modelling” (PNM), is therefore used. A detailed description of this PNM technique in terms of approach, model characteristics and construction is presented in the following document:
Laroche, C. and Vizika, O., “Two-Phase Flow Properties Prediction from Small-Scale Data using Pore-Network Modeling”, Transport in Porous Media, (2005), 61, 1, 77-91.
[0042] This PNM is a conceptual representation of a porous medium whose goal is to account for the flow and transport phenomena physics, without taking the real structure of the network formed by the pores of the porous medium (rock) into consideration. The structure is modelled by a three-dimensional pore network making up the nodes, interconnected by channels, representing the links between the pores. Although it does not describe the exact morphology of the porous medium, such a model can take into account the essential topology and morphology characteristics of the porous space. A real porous medium comprises angulosities and recesses that favour the flow of the wetting fluid, even when the center of the channel or of the pore is filled by a non-wetting fluid. To account for this fact, which influences the recovery, angular sections are preferably considered for the pores and the channels. The pore network is therefore represented by a three-dimensional cubic matrix of pores interconnected by channels and having generally a coordination number of six (but it can be variable), which means that 6 channels are connected to each pore. As illustrated in FIG. 2 , a node (N) and its channels (C) are referred to as unit cell, or cell, of the network model.
[0043] To construct such a model, it is necessary to carry out mercury invasion experiments (mercury porosimetry) in the laboratory. This known technique, allows determination of the size distributions of the thresholds represented by the channels in the network model (PNM).
[0044] The size distribution of the pores is determined from this distribution. A correlation is therefore considered between the pores and their adjacent channels. An aspect ratio (AR) relating the pore diameter d p to the channel diameter d c is then established. During construction of the network, the channel diameters are randomly assigned in accordance with the experimental distribution obtained by mercury porosimetry. It can be noted that, in the case of a triangular section, the diameter corresponds to that of the circle inscribed in the triangle being considered.
[0045] 2. Determining the Porosity and Permeability Evolution
[0046] The PNM then allows describing the effects of a reactive flow on the transport properties and on the structure evolution.
[0047] A numerical approach is used to simulate the evolution of the petrophysical properties caused by the alternation of dissolutions and precipitations. From a petrophysical point of view, study of the diagenesis is structured around two tasks: solution of the reactive transport, which determines the concentration field in the pore network, and calculation of the structure changes potentially caused by the reactions.
[0048] These two aspects of the diagenesis are solved separately: the method according to the invention is a method referred to as “step by step”: the transport part (including flow) is solved on a constant geometry basis and the pore structure modifications are determined with constant concentrations.
[0049] 2a. Determining the Initial Porosity and Permeability
[0050] The porosity of the pore network, corresponding to the core-scale porosity, can then be determined. In fact, the porosity is defined as the ratio of the void volume to the total volume. The total volume of the pore network is known (Lx*Ly*Lz, product of the lengths of the pore network in each direction), and the void volume corresponds to the volumes of the pores and to the volumes of the channels. These volumes are obtained by simple geometrical calculations (volume of a cylinder, of a sphere, . . . ).
[0051] Flow determination is a preliminary condition for any transport study in the presence of convection. It consists, for a given initial rock structure, determines the pressure field. For each channel of a unit cell of the PNM, the conductances are calculated from the known Poiseuille solution for a laminar flow. These conductances linearly connect the flow rate and the pressure difference between two adjacent nodes.
[0000] Q ij =g ij ( P i −P j )
[0000] where:
[0052] Q ij is the flow rate between pores i and j.
[0053] g ij is the hydraulic conductance of the channel between nodes i and j.
[0054] P i and P j are respectively the pressures of node i and of node j.
[0055] The conservation of the flow rates at the nodes is then written. Thus n equations are obtained with seven unknowns each, if a network of n pores is assumed having a coordination number equal to 6.
[0000]
∑
j
=
1
6
Q
ij
=
∑
j
=
1
6
g
ij
(
P
i
-
P
j
)
=
0
[0056] This linear system can be synthesized in the following matricial form:
[0000] Ax=b
[0000] where:
[0057] A is the matrix containing the conductances
[0058] x is the unknown vector of the n pressures
[0059] b is the second member vector containing the boundary conditions.
[0060] The n unknown pressures are then determined by a conventional solution methods such as, for example, the biconjugate gradient method.
[0061] Knowing the pressures, it is possible to calculate, by means of the conductances, the flow rates, then the velocities in each channel.
[0062] At network scale, the permeability relating the total flow rate to the pressure gradient is deduced from Darcy's equation.
[0063] A detailed description of these permeability and porosity determination techniques is given in the following document: Laroche, C. and Vizika, O., “Two-Phase Flow Properties Prediction from Small-Scale Data Using Pore-network Modeling”, Transport in Porous Media, (2005), 61, 1, 77-91.
[0064] 2b. Determining the Ion Concentrations
[0065] Solution of the reactive transport solves, over the entire PNM, the macroscopic convection-dispersion equation for a reactive solute in the presence of a reaction (precipitation, dissolution). Assuming a linear kinetic law (but the methodology can be applied to more complex reactions), this equation is written as follows:
[0000]
∂
c
_
∂
t
+
∇
·
(
v
_
*
c
_
-
D
_
*
∇
c
_
)
+
γ
_
*
(
c
_
-
c
*
)
=
0
[0000] where:
[0066] c is the mean concentration of a unit cell of the network
[0067] c* is the equilibrium concentration
[0068] y * is the apparent reactive coefficient derived from volume and/or surface reactions
[0069] v * is the mean velocity of the solute, different from the mean velocity of the fluid
[0070] D * is the dispersion coefficient, or dispersion tensor of the solute (not reduced to the Taylor-Aris dispersion).
[0071] Coefficients y *, v * and D * are referred to as macroscopic coefficients. These coefficients are analytically calculated for each unit cell of the network, by solving the microscopic equations and by performing a scale change. It is then possible to determine the deposition maps, and to deduce therefrom their impact on the petrophysical properties.
[0072] Concentration field c is the unknown vector of the system to be solved by integrating the conservation equation at the node (mass balance). These balances involve the matter fluxes (ions) between the pores, which can be expressed as a function of the mean concentrations at the nodes and of the macroscopic transport coefficients.
[0073] The first stage calculates the previous macroscopic coefficients for each unit cell of the network. It is thus possible to use the analytical method of moments and to solve the associated eigenvalue problem. This technique is described for example in the following document:
Shapiro M., Brenner H., Dispersion of a Chemically Reactive Solute in a Spatially Model of a Porous Medium, Chemical Engineering Science, 1988, 43, p. 551-571.
[0075] This theory is based on the integration, on a medium assumed to be infinite or periodic, of the previous macroscopic equation weighted by the positions. In other words, the spatial moments are calculated. These moments are compared with those calculated from the system of local equations, presented hereafter, allowing calculation of the local concentration c, that is the concentration within a pore or a channel as a function of its distance to the centre. This system of equations has an analytical solution for elementary geometries, such as those used in the construction of the PNM model. The technique described in the following document can for example be used for analytically solving this system:
Bekri S., Thovert J.-F., Adler P. M., “Dissolution of Porous Media”, Chem. Eng. Sci., (1995) 50, 17, p. 2765-2791.
[0077] By identification, it is then possible to express the macroscopic coefficients by the local parameters (kinetic constant on the wall, local velocities of the fluid, molecular diffusion, . . . ).
[0000]
{
∂
c
∂
t
+
∇
·
(
vc
-
D
∇
c
)
=
0
(
vc
-
D
∇
c
)
·
n
=
κ
c
sur
S
p
[0000] where:
[0078] D is the molecular diffusion coefficient,
[0079] n is the normal to the wall pointing towards the solid,
[0080] K is the reaction velocity constant, and
[0081] S p is the surface of the wall.
[0082] During the second stage, knowing these coefficients explicitly, the partial derivative equation of the macroscopic transport, which amounts to an ordinary differential equation in asymptotic regime, is solved analytically in a channel. After determining the mean concentrations along the axis of the channel, the matter fluxes entering each pore are deduced. This calculation allows estimation of the fluxes with a precision unparalleled by ordinary numerical approximations, of air upstream scheme type for convection and of linear approximation type for diffusion.
[0083] Finally, during the third stage, the system of equations is written in matricial form. The matrix equation is then solved by inversion so as to obtain the concentration field. The network-scale (core) concentration field is thus obtained from a calculation of the ion fluxes at pore scale.
[0084] 2c. Determining Structure Modifications of the Pore Network
[0085] The structural modifications of the pore network correspond to a change in the diameter of the pores and/or channels as a result of the precipitation and dissolution reactions.
[0086] The mean ion concentrations and the wall concentration (c at S p ) are determined in stage 2b. After experimentally measuring the intrinsic kinetics κ of the reaction studied, calcite dissolution for example, the reactive flux density φ i of ions emitted or consumed is calculated from this concentration at the interface.
[0000] φ i =κ( c−c* )
[0087] Knowing the reaction stoichiometry, the molar mass and the density of the mineral formed, these fluxes are connected to an infinitesimal layer of mineral created or removed, therefore to a relative growth rate of the pore. Of course, this layer is not necessarily uniform. Its distribution in the network depends on the reaction and flow regimes.
[0000]
ϕ
m
=
αϕ
t
∂
d
∂
t
=
M
ρ
ϕ
m
}
⇒
d
(
t
+
δ
t
)
=
d
(
t
)
+
δ
t
·
α
M
ρ
κ
(
c
-
c
*
)
[0000] where:
[0088] α is the stoichiometric coefficient
[0089] φ m is the mineral flux density in mol·m −2 ·s −1
[0090] M and ρ are the molar mass and the density of the mineral respectively
[0091] d represents the diameter of a pore or of a channel. Thus, d(t) is the diameter of a pore or of a channel at the time t, and d(t+δt) corresponds to the diameter of this pore or of this channel at the time t+δt.
[0092] The deformation time δt to be applied is optimized according to the desired precision as regards the intensity of the permeability and porosity variations.
[0093] 2d. Determining the Porosity and the Permeability after the Reaction
[0094] After each deformation stage (stage 2c), the petrophysical properties are recalculated as in stage 2a.
[0095] By following the diagenesis cycle (SD) defined in stage A, stages 2a to 2d are successively carried out for a precipitation reaction, then for a dissolution reaction, as illustrated in FIGS. 1 and 3 .
[0096] In addition to the interest of observing the diagenesis at pore scale by drawing up deposition maps of the network, the method makes it possible to store, after each structural modification, the new porosities and permeabilities in order to obtain different correlations. The permeability and porosity evolution can be used by a basin simulator and/or a reservoir simulator within the context of petroleum exploration and production. These correlations are integrated in the reservoir or basin simulators as input data upon reconstruction of the geological history of the field.
[0097] In the petroleum field, knowing the diagenetic cycle can lead to a better field development as a result of a better characterization, past and present, of the reservoir. On the one hand, the reserves can be assessed more precisely by estimating the porosity evolution due to diagenesis, which has a direct impact on the amount of potentially accumulated hydrocarbons. On the other hand, the reservoir production plan can be adjusted to the estimated permeabilities by best optimizing the extraction facilities. Thus, reconstruction of the diagenetic cycle is a way of better characterizing heterogeneities and it therefore constitutes an appreciable help when working out the production scenario.
[0098] The method thus allows determination of the potential location of underground reservoirs within a sedimentary basin (using a basin simulator) or to enhance the recovery of hydrocarbons in a reservoir or an underground reservoir (using a reservoir simulator).
[0099] Applications
[0100] The method according to the invention is applied hereafter to three different examples, extremely simplified. These examples allow illustration of the ability of the method to describe and interpret the consequences of diagenesis on petrophysical properties.
[0101] In the examples hereafter, the permeabilities and the porosities are normalized by their initial value, that is their value prior to diagenesis. The normalized permeabilities are denoted by K n and the normalized porosities are denoted by φ n . Furthermore, in each example, one a diagenesis cycle is selected comprising, twice, a precipitation stage followed by a dissolution stage, whose lengths are arbitrarily set. In reality, the length has to coincide with the diagenetic cycle established by the geologist. It is considered that there is no exterior matter supply and that, at the end of the dissolution period, all of the previously precipitated solute has been dissolved. Consequently, at the end of the cycle, the porosity is equal to the initial porosity (assuming that the crystals formed or removed have the same specific volume). However, this does not mean that the initial pore size distribution is obtained again, hence the probable permeability change. In fact, the permeability is linked with the diameter of the restrictions (channels) between the pores. Now, depending on the regime, dissolved matter may precipitate again, preferably either in the thresholds (channels) or in the pores, which leads to a permeability drop or rise respectively.
[0102] The diagenetic cycles observed are different according to the hydrodynamic and reaction regimes. Therefore, in order to be able to compare the experiments, the dimensionless numbers that govern the known reactive transport are succinctly introduced, that is:
[0103] the Péclet number, denoted by Pe, which compares the convective fluxes with the diffusive fluxes; and
[0104] the Péclet-Damköhler number, denoted by PeDa, which compares the reaction velocity with the velocity of transport of the solute to the wall.
[0105] For each example, the method is applied in order to determine the evolution of the porosity (φ n ) and of the permeability (K n ) during the diagenesis.
Example 1
Homogeneous Initial Geometry (all the Pores have the Same Diameter)
[0106] According to this example, a three-dimensional homogeneous network of 250 pores (10*5*5) is considered. The precipitation and dissolution reaction regimes are the same: Pe=10, PeDa=0.1 for the precipitations and the dissolutions.
[0107] In this instance, there is no permeability evolution. The initial and final porosity and permeability conditions are the same. The dissolution (Dis) and the precipitation (Pr) must have a different reaction regime to be able to eventually observe a permeability evolution. Otherwise, the effects of the other are cancelled, as illustrated in FIG. 3 . FIG. 3 shows permeability (K n ) versus porosity (φ n ) for a simulated diagenetic cycle in a three-dimensional homogeneous network of 250 pores (10*5*5), with Pe=10, PeDa=0.1 for the precipitations and the dissolutions.
Example 2
Homogeneous Initial Geometry (all the Pores have the Same Diameter)
[0108] According to this example, a three-dimensional homogeneous network of 250 pores (10*5*5) is considered. This time, however, the precipitation and dissolution reaction regimes are different: PeDa=0.01 for dissolutions and PeDa=1 for precipitations. This corresponds to a dissolution that is one hundred times slower than the precipitation.
[0109] The method gives the evolution of the network-scale calculated permeability and porosity. FIG. 4 shows permeability (K n ) versus porosity (φ n ) for the diagenetic cycle in the three-dimensional homogeneous network of 250 pores (10*5*5). A marked permeability drop is observed during the diagenesis. This is explained by the enlargement of the pores and the reduction of the channels.
[0110] Since precipitation and dissolution do not cause the same deformation, because of different reactive regimes, the diagenetic cycle leads to an accentuation of the heterogeneity between pores and channels.
Example 3
Heterogeneous Initial Geometry (all the Pores do not have the Same Geometry)
[0111] One advantage of the method according to the invention is readily taking into consideration the effect of the pore network structure. To illustrate this capacity, diagenesis is simulated in a more realistic pore network with a pore size distribution.
[0112] According to this example, mean reactive regimes identical to the previous cases are selected: Pe=10, PeDa=1 for precipitation and PeDa=0.01 for dissolution. The heterogeneous character of the diameters generates a heterogeneity within the reaction regime.
[0113] By applying the method according to the invention, it is established that there are nearly two orders of magnitude between the apparent reactive coefficient of the larger pores and that of the smaller ones. This decrease in the apparent reactive coefficient of the larger pores is translated into an accumulation of the solute in these volumes, which can be readily checked on a concentration map ( FIG. 6 , where the high concentrations are shown in black, the circles represent the pores and the lines connecting the pores represent channels). Consequently, the precipitation, which is proportional to the chemical unbalance, will be stronger in these pores and, to a lesser extent, along the paths connecting them. This is translated into a more marked porosity drop at the end of the first precipitation periods (compare FIGS. 4 and 5 ). The dissolution remains substantially uniform. It is possible to readily check this assertion from the method by plotting the pore size distribution. In this case, it is practically translated towards the larger pores, as illustrated in FIG. 7 , where the curve with the diamonds represents the number of pores (NbP) versus diameter d ip of the pores before the reaction, and the curve with the squares represents the number of pores (NbP) versus diameter d p of the pores after the reaction.
[0114] On the other hand, the modification of the precipitation part entirely disrupts the course of the diagenetic cycle ( FIG. 5 ). In fact, the matter dissolved in the restrictions settles in the pores, which leads to a very significant permeability increase. It is thus possible to explain, with the method according to the invention, how a totally different diagenetic cycle can be observed despite identical mean dimensionless numbers.
[0115] In summary, these experiments show that, for the reactive regime that is selected, in the case where the initial structure is homogeneous, a permeability decrease occurs, whereas for a certain heterogeneous distribution, the same regime leads to a permeability increase. In other words, small initial perturbations within the medium are likely to cause marked heterogeneities during diagenesis. On the other hand, if the reaction is very slow, precipitation and dissolution become reversible and the curves merge as in FIG. 3 .
[0116] The method according to the invention thus is an efficient and simple tool for:
[0117] physically modelling transport, dissolution and precipitation phenomena at pore scale;
[0118] interpreting the mechanisms by means of hydrodynamic and reaction regimes, as well as the structural properties of the medium;
[0119] providing relationships allowing a scale change between the pore and the core then, using the correlations obtained in existing reservoir simulators, between the core and the reservoir.
[0120] The method furthermore allows carrying out a sensitivity study on some key parameters such as the pore size distribution or the aspect ratio, thus allowing study of various diagenesis cycles.
[0121] Finally, the method has been described within the context of permeability and porosity determination of a porous medium. However, by updating the structure of the pore network model, the invention applies to any petrophysical properties such as capillary pressure and relative permeabilities. | A method for quantitative determination of the permeability and porosity evolution of a porous medium during diagenesis having application to oil reservoir development is disclosed. A diagenesis scenario and an initial structure of the pore network of the porous medium are defined.
A representation of the pore network is constructed by a PNM model. The steps of the diagenesis scenario are determining the ion concentration on the pore and channel walls of the PNM model, for a precipitation or dissolution reaction according to the scenario, and deducing therefrom a geometry variation of the PNM model, the porosity is calculated geometrically and the permeability is calculated from Darcy's law for the modified PNM model; the foregoing steps are repeated according to the diagenesis scenario and a relationship is deduced between the permeability of the porous medium and the porosity of the porous medium during diagenesis. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a rotation detector and rotation controller using this detector. In particular, the present invention is preferably applicable to a rotary encoder, which detects the rotation position of the disk, the amount and direction of the displacement of the rotation position, the rotation speed and acceleration and the like, by illuminating a radial diffraction grating and a code pattern on a disk attached to a relative rotation object with a light beam, and by detecting a modulated signal light obtained therefrom. The rotation detector and controller are applicable to a device, such as a motor with an encoder, which makes the object rotationally move by controlling the current and direction of the driving unit such as an AC motor and the like.
2. Related Background Art
Incremental rotary encoders have been used for high precision measurement of information on the rotation of the object, such as displacement, speed, acceleration and the like. Further, absolute rotary encoders, which detect the absolute rotation position of the rotor in the motor, have been used for brushless motors, such as AC motors. Therefore, combination rotary encoders which can obtain both signals are employed for controlling the rotation position of the object using AC motors and the like.
Conventional high precision incremental encoders detecting the displacement, as shown in Japanese Patent Publication Nos. 58-26002 and 58-45687 on the object, output incremental encoder signals by illuminating a monochrome light beam in which fine grating elements are recorded on the scale, by making periodic changes of the amount of the light with grating movement by means of the interference between at least two kinds of diffracted light among a plurality of diffracted light obtained therefrom, and by detecting a photoelectric element.
Further, conventional absolute rotary encoders, as disclosed in U.S. Pat. No. 3,591,841, have a structure which outputs the absolute rotation position of the disk, by forming a plurality of transmittable/non-transmittable or reflective/nonreflective patterns, such as grey code patterns, on the circuits, having different radii, on the rotation disk, so that only one combination of the codes exists in one rotation, and by detecting transmitted or reflected light at the specified position on each circuit. A typical absolute encoder for the motor outputs the position between the rotor and stator in the motor, by forming a plurality of transmittable/non-transmittable or reflective/nonreflective patterns, such as grey code patterns, on the circuits, having different radii, on the rotation disk, so that only M combinations of the codes exists corresponding to the structure of the motor, the number of the pole M, and by detecting the transmitted or reflected light at the specified position on each circuit.
In recent years, although a more compact encoder, for example, a disk having a diameter of 10 millimeters, has been required, it is difficult to miniaturize the combination encoder based on the different principles as described above. The miniaturization, in which two optical systems based on the different detection principles are placed together and each system is intended to miniaturize, has a limitation and some problems as follows: A plurality of light sources are separately required for the absolute encoder portion and the incremental encoder portion so that heat generation increases with the increased current consumption, and the structure becomes more complicated due to the increased number of parts required. In particular, since a device having an incremental encoder portion using a grating interference system requires a certain size so that the accuracy of the interference can be maintained, it is even more difficult to miniaturize this when another rotation detector is provided together.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a rotation detector sufficiently enabling miniaturization and a rotation control device, even if another rotation information detector is provided at the same time in the device for detecting rotation information using the grating interference system.
According to one embodiment of the present invention, an apparatus for detecting information on relative rotation of an object having a first diffraction grating and a predetermined data recording section includes a first detecting device for detecting by interfering diffracted light from the first diffraction grating to detect relative rotation information of said object, a second detecting device for detecting light from the predetermined data recording section from the object to detect rotation information regarding the object, and a light beam illuminating device for illuminating the first diffraction grating and the predetermined data recording section together.
According to another embodiment, the apparatus for detecting information on relative rotation of an object having a first diffraction grating and predetermined data recording section includes first and second photoelectric converting devices and an illuminating device. The first photoelectric converting device interfered and diffracted light from the first diffraction grating to obtain incremental rotation information regarding the object from an output from the first photoelectric converting device. The second photoelectric converting device detects information on transmittance/non-transmittance of the light by the predetermined data recording section to obtain incremental rotation information regarding the object other than the incremental rotation information from the output from said first photoelectric converting device. The illuminating means illuminates the diffraction grating and the predetermined data recording section together.
According to a still further embodiment of the present invention, the apparatus for detecting information described above, including first and second photoelectric converting devices and an illuminating device, is an apparatus in which the second photoelectric converting device detects information on reflection/non-reflection of the light by the predetermined data recording section.
According to a still further embodiment, the present invention is directed to an apparatus for controlling relative rotation of two objects. The apparatus includes a scale section, a detecting unit, and a control system. The scale section is provided on a first side of the two objects, and has a diffraction grating and a predetermined data recording section. The detecting unit is provided on a second side of the two objects. The detecting unit includes first and second photoelectric converting sections and an illuminating system as described above. The second photoelectric converting section may detect the transmittance/non-transmittance or the reflection/non-reflection of the light from the predetermined data recording section. The control system controls relative rotation of the two objects based on the outputs from the first and second photoelectric converting sections.
In still another embodiment, the present invention is directed to an apparatus for detecting information on relative rotation of an object having a diffraction grating and a predetermined data recording section. The apparatus includes first and second detecting devices, and a light guiding device. The first detecting device detects by making the diffracted light from the diffraction grating interfere to detect incremental rotation information regarding the object. The second detecting device detects light from the predetermined data recording section of the object to detect rotation information regarding the object. The light guiding device introduces light emitted from the diffraction grating and the predetermined data recording section together to the first and second detecting devices.
In still another embodiment, the present invention is directed to an apparatus for detecting information on relative rotation of an object having a diffraction grating and predetermined data recording section. The apparatus includes first and second photoelectric converting sections, and a common optical member. The first photoelectric converting section receives the interfered and diffracted light from the diffraction grating to obtain incremental rotation information regarding the object by an output from the first photoelectric converting section. The second photoelectric converting section detects transmittance/non-transmittance information by the predetermined data recording section to obtain rotation information regarding the object by an output from the second photoelectric converting section, other than the incremental rotation information. The common optical member introduces light emitted from the diffraction grating and the predetermined data recording section together to the first and second photoelectric converting sections.
Further objects, features and advantages of the present invention will become apparent from the following description of the preferred embodiments with reference to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram illustrating an optical arrangement of a rotary encoder in a first embodiment of the present invention;
FIG. 2 is an enlarged diagram of the optical arrangement of the rotary encoder in the first embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating light paths in the rotary encoder in the first embodiment of the present invention;
FIG. 4 is a diagram showing patterns of the diffraction gratings formed in the rotary encoder in the first embodiment of the present invention;
FIG. 5 is a schematic diagram illustrating an optical arrangement of a rotary encoder in a second embodiment of the present invention;
FIG. 6 is a schematic diagram illustrating an optical arrangement of a rotary encoder in a third embodiment of the present invention;
FIG. 7 is an enlarged diagram of the optical arrangement of the rotary encoder in the third embodiment of the present invention;
FIG. 8 is a schematic diagram illustrating light paths in the rotary encoder in the third embodiment of the present invention;
FIG. 9 is a diagram showing patterns of the diffraction gratings formed in the rotary encoder in the third embodiment of the present invention;
FIG. 10 is a schematic diagram illustrating an optical arrangement of a rotary encoder in a fourth embodiment of the present invention;
FIG. 11 is a schematic diagram illustrating light paths in the rotary encoder in the fifth embodiment of the present invention;
FIG. 12 is a schematic diagram illustrating light paths in the rotary encoder in a sixth embodiment of the present invention;
FIG. 13 is a schematic diagram illustrating light paths in the rotary encoder in a seventh embodiment of the present invention;
FIG. 14 is a schematic diagram illustrating light paths in the rotary encoder in a eighth embodiment of the present invention; and
FIG. 15 is a outlined block diagram illustrating a motor driver system in a ninth embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 is a schematic diagram illustrating an optical arrangement of a rotary encoder in the first embodiment of the present invention, FIG. 2 is an enlarged diagram of the optical arrangement, FIG. 3 is a schematic diagram illustrating light paths, and FIG. 4 is a diagram showing patterns of the diffraction gratings formed. In these figures, a disk D is provided on an object of which the relative rotation is detected, and other members, other than the disk D and each member on the disk D, are arranged by fixing each other and are isolated from the disk D.
A divergent light beam, emitted from a light source LGT such as LED, is converted to a parallel beam by a collimator lens LNS1, and the converted parallel beam illuminates the surface of the relatively rotating light transmittable disk D.
On the surface of the disk D, light transmittable, radial diffraction grating GT, formed over the entire circuit on the disk D, having a pattern as shown in FIG. 4, a home position code pattern Z formed by a light transmittable pattern at the home position, and light transmittable, absolute code patterns U, V, and W, provided so as to indicate angle information of each position over the entire circuit, as shown in FIGS. 1 and 2, are recorded along different circuits (tracks) respectively. The parallel light beam has a spread which can illuminate each partial region of the radial grating GT tracks, the home position code pattern Z track, and the absolute code pattern U, V, and W tracks together, as shown in FIG. 2, in which only the light beam incident on each sensor described below is depicted. A photoelectric element array SARY consists of incremental detecting portions SA, SA, SB, and SB, home position code detecting portions SZ1 and SZ2, and absolute code detecting portions SU, SV, and SW. The number of radial grating elements GT is taken as N on one circuit.
As described with reference to FIG. 3, two ± first order light beams, R+ and R-, are generated from the radial grating GT, illuminated with the above parallel light beam, wherein the grating pitch P=2π/N radian. These first order light beams R+ and R- are diffracted with the first diffraction grating GBS1 (grating pitch P=π/N radian), having a pattern as shown in FIG. 4, to convert to light beams R+- and R-+ by bending their light paths and to intersect at the points P and Q, respectively, in the space. The second diffraction grating GBS2, having a pattern as shown in FIG. 4, is placed at the intersection, and the light beams R+- and R-+ are diffracted by the second diffraction grating GBS2 (grating pitch P=2π/N radian) and are converted to the light beams R+-+ and R-+-, respectively, which emerge as light-or-dark signal light as the result of the mutual interference (Refer to FIG. 3).
The diffraction grating GBS2 is divided into four regions GBS2-A, GBS2-B, GBS2-A, and GBS2-B at the point P0 as the boundary as shown in FIG. 4, in which the phases of the grating arrays are shifted one-eighth pitch from each other. Each of the first and second diffraction gratings GBS1 and GBS2, and the radial grating GT have preferably a fine structure of lamellar grating which does not generate zero order diffraction light.
Since the light beam R illuminated on the disk D has a spread, the beam R reaches to the diffraction grating GBS1 in an almost superimposed state even after diffraction by the radial grating GT. For example, when the diameter of the light beam is 500 μm, the number of the radial grating elements is 2,500, the recording radius r on the disk D is 5,000 μm, and the wavelength λ of the LED is 0.86, the first diffraction angle θ becomes as follows:
θ=arcsin {λ·N/(2πr)}=3.92°
When the gap h between the radial grating GT and diffraction grating GBS1 is 500 μm, the distance between centers of diffraction beams on diffraction grating GBS1 becomes 68.5 μm.
The light beams R+-+ and R-+-, diffracted by the diffraction grating GBS2, emerge from the grating so that their light paths are superimposed on each other and their optical axes are parallel. Thus, the symmetry of all the light paths from the light source is preserved and the beams interfere each other. When the radial grating shifts one pitch by the rotation of the disk D, the phase of the wavefront of the diffraction light R+-+ shifts by +2π, and the phase of the wavefront of the diffraction light R-+- shifts by -2π. Thus, lightness-and-darkness of the interfered light changes twice in a sinusoidal manner per one pitch shift of the radial grating with the rotation of the disk. Moreover, since the diffraction grating GBS2 is divided into four regions at the point P0 as the boundary as described above, and the phases of the grating arrays are shifted by one-eighth pitch from each other, the interfered phase in each region, or the phase of lightness-and-darkness, changes twice in a sinusoidal manner due to the shift by one-fourth period.
The light, interfered in each region, enters the respective photoelectric element SA, SB, SA, or SB, and a sinusoidal analog signal current, having a period of 2N per rotation, is generated four times with the shift of each one-fourth period from each photoelectric element by turns. By using these four sinusoidal analog signals having phase shifts, the relative, incremental amount and direction of the rotation of the disk D are calculated in a signal processing circuit, not shown in the figures. Since the calculation itself is well-known, the explanation will be omitted.
On the other hand, in the track in which the home position code pattern Z is formed on the disk D, the portion not forming the pattern is non-transmittable so that incident parallel light beam cannot transmit this portion. When the parallel light beam illuminates the home position including the position of the home position code pattern Z during the rotation of the disk D, the parallel light beam enters the photoelectric elements SZ1 and SZ2 through the home position code pattern Z.
The home position code pattern consists of two light transmittable pattern portions, which are shifted in the rotational direction from each other, as shown in FIG. 2. The position in the radial direction of each pattern corresponds to the position of the photoelectric element SZ1 or SZ2, respectively. When the home position code pattern Z is illuminated with the parallel light beam, transmitted light enters the photoelectric elements SZ1 and SZ2 by the amount corresponding to the position of the pattern in the radial direction. When the home position code patterns Z1 and Z2 move in the illuminating region by the rotation of the disk D, the cross-section of the transmitted light, projected to the photoelectric elements SZ1 and SZ2, varies. Thus, the total amount of the light beam illuminating the photoelectric elements SZ1 and SZ2 varies, where the amount of the light received by each of the photoelectric elements SZ1 and SZ2 independently varies at the different timing due to the mutual positional difference of the patterns Z1 and Z2 in the rotational direction. Therefore, two bell-shaped analog signals, each having a peak at different times from each other, are generated from the photoelectric elements SZ1 and SZ2 by the rotation of the disk D. The home position signal may be generated, for example, as a pulse signal when both outputs from the photoelectric elements SZ1 and SZ2 are the same. Such a pulse signal may be generated from a signal processing circuit, not shown in the figures, which receives each output from the photoelectric elements SZ1 and SZ2. In such a way, the passage of the home position of the disk D is detected.
On the other hand, among of the above parallel light beam, illuminated on the track, in which the absolute code patterns U, V, and W exist, the transmitted light beam is continually projected on photoelectric elements SU, SV, and SW during the rotation of the disk D, at the time that the parallel light beam illuminates the absolute code patterns U, V, and W. Since a absolute code signal group is output from the photoelectric elements SU, SV, and SW in response to the current position in the rotation direction of the disk D, the absolute position can be identified by a signal processing circuit, not shown in the figures, from the combination of these binary signals. Since the methods for identifying the absolute position are well-known, a further explanation will be omitted.
As described above, the light beams which transmitted and were modulated by the disk illuminating region enter on the photoelectric element array SARY.
Both the diffraction grating GT for detecting the amounts of the incremental rotation by the grating interference/diffraction method, and the pattern for detecting other information on the rotation; i.e., the absolute position of the rotation and the home position, by detecting light transmittance/non-transmittance, not such a grating interference/diffraction method, are illuminated by the same optical illuminating system together, so a compact simplified structure can be achieved, and thus a more compact apparatus will be achieved. In particular, by the structure in which a parallel light beam illuminates both the diffraction grating for the grating interference method and the pattern for detecting the transmittance/non-transmittance of the light at the same time, the measurement or detection by the different method can be achieved using the same optical system.
FIG. 5 is a schematic diagram illustrating an optical arrangement of a rotary encoder in the second embodiment of the present invention. A similar expression to FIG. 1 is used, and the explanation on the same members as the first embodiment will be omitted. In the following embodiments, the same notation is assigned to the same portion or member as the first embodiment.
In the second embodiment, an interference light beam for incremental measurement, and light beams from the absolute code pattern and home position code pattern are projected to the photoelectric element array SARY by using an image projecting lens LNS2. Therefore, the photoelectric element SARY is arranged in the opposite direction to the first embodiment. By such a structure in which the interference light for incremental measurement, the absolute code pattern and the home position code pattern are projected onto the photoelectric element SARY through the image projecting lens LNS2, the detection accuracy is further improved due to the improvement in the resolution at the edge of the absolute pattern and home position pattern. Moreover, since such a image projecting lens LNS2 is commonly used for all the projections of the interference light for the incremental measurement, the absolute code pattern and the home position code pattern, the structure can be miniaturized and simplified so as to enable compact apparatuses to be built.
FIG. 6 is a schematic diagram illustrating an optical arrangement of a rotary encoder in the third embodiment of the present invention, FIG. 7 is an enlarged diagram of this optical arrangement, FIG. 8 is a schematic diagram illustrating light paths in the rotary encoder, and FIG. 9 is a diagram showing patterns of the diffraction gratings formed in this rotary encoder. The explanation will be omitted for the same members as in the first embodiment. The third embodiment differs from the first embodiment in that the reflected diffraction light due to the radial diffraction grating GT on the disk D is used in the third embodiment.
The light beams emitted from the light source LGT, such as an LED, are converted to the parallel light beams through the collimator lens LNS1, and are transmitted to a beam splitter BS. Part of the light beams are converted to two diffraction lights R+ and R- through a first diffraction grating GBS3 having a pattern (grating pitch P=4π/N radian) as shown in FIG. 9, and illuminate the relatively rotating disk D. The remaining light beams, not transmitted to the region of the diffraction grid GBS3, illuminate the relatively rotating disk D without modification.
On the disk D, a reflecting type of radial diffraction grating GT, a reflecting type of home position code pattern Z, and reflecting type of absolute code patterns U, V and W are recorded on different circuits or tracks. The parallel light beam has a spread sufficient to illuminate all the partial regions of the radial grating GT track, the home position code pattern Z track, and the absolute code pattern U, V and W tracks together, as shown in FIG. 7. Only part of the light beam incident on each sensor is drawn in FIG. 7.
Two ± first order reflected diffraction light beams R+- and R-+ formed by the radial grating (the grating pitch P=2π/N radian) are again diffracted by the first diffraction grating GBS3 (the grating pitch P=4π/N radian) to form light beams R+-+ and R-+-, which interfere each other due to the overlap of their optical paths and emit light and dark signal lights (refer to FIG. 8).
The first diffraction grating GBS3 and radial grating GT desirably have a fine structure of lamella grating not forming zero order diffraction light. Further, the diffraction grating GBS3 is divided into four regions, i.e. GBS-A, GBS-B, GBS-A, and GBS-B at the boundary of the point P0, and the phase of each grating is shifted by one-eighth pitch from each other.
Since the light beam R illuminated on the disk D has a spread, it is reflected almost in the overlapped state on the radial grating GT after the reflection by the reflection grating GBS3, and is again introduced to the diffraction grating. For example, when the radius of the illuminating light beam is 500 μm, the number of the radial gratings N is 2,500, the radius r of the recording on the disk D is 5,000 μm, and the wavelength λ of LED is 0.86 μm, the incident angle of the disk illuminating light θ becomes as follows:
θ=arcsin{λ·N/(4πr)}=1.96°
Letting the gap h, between the radial grating GT and diffraction grating GBS3, =500 μm, the distance between centers of diffraction beams on diffraction grating GBS3 is 34.2 μm.
The light beams R+-+ and R-+-, re-diffracted by the diffraction grating GBS3, are emitted so that light paths of the optical axes overlap with each other and become parallel to each other. Since all paths from the light source can be kept symmetrical, the light beams interfere with each other. On the interference, when the radial grating moves by one pitch with the disk rotation, the phases of the wavefronts of the diffraction light beams R-+- shift by +2π and -2π, respectively. Thus, the lightness-and-darkness of the interfered light sinusoidally changes twice by the one-pitch shift of the radial grating due to disk rotation.
Moreover, since the diffraction grating GBS3 is divided into four regions at the boundary of the point P0 as described above, and each grating is arranged so that each phase is shifted by one-eighth, the interfered phase in each region shifts by one-fourth, and lightness-and-darkness sinusoidally change twice.
Since the interfered light beams from these regions are reflected with the beam splitter BS and are illuminating respective photoelectric elements SA, SB, SA and SB, four sinusoidal analog signals, each having a period of 2N per rotation, are generated from the photoelectric elements SA, SB, SA and SB, with shifting by one-fourth period from each other. By using such four phase-shifted sinusoidal analog signals, the amount and direction of the relative incremental rotation are calculated in a signal processing circuit not shown in the figures. Since the calculation is well-known, the explanation will be omitted here.
On the other hand, since the track, in which the home position code pattern Z is formed on the disk D, is provided so as not to form the reflected light at the portion not having the home position code pattern Z, the reflected light does not form even if the aforementioned parallel light beam enters. When the disk D reaches near the home position during each rotation and the parallel light beam enters the portion of the home position code pattern Z, the light beam enters the photoelectric elements SZ1 and SZ2 after reflection by this pattern.
The home position code patterns Z1 and Z2 consist of two light reflecting patterns, as shown in FIG. 7, which are shifted in the rotational direction from each other, both are provided to correspond with the positions of the photoelectric elements SZ1 and SZ2 in the radial direction. When the home position code pattern Z is illuminated with the aforementioned parallel beam, the reflected light enters the photoelectric elements SZ1 and SZ2 through the beam splitter BS in response to the rotational positions of patterns Z1 and Z2. When the home position code pattern moves in the illuminating region by the rotation of the disk D, the cross-section of the light reflected at the home position code patterns Z1 and Z2 and projected to the photoelectric elements SZ1 and SZ2. Thus the total amount of the light incident upon photoelectric elements SZ1 and SZ2 varies. The amount of received light of each of the photoelectric elements SZ1 and SZ2 independently varies at a different timing due to the mutual positional difference in the rotation direction. Thus, two bell-shaped analog signal currents, each having a different peak, is generated from the photoelectric elements by the rotation of the disk D. The home position signal may be, for example, a pulse signal generated when the outputs of the photoelectric elements SZ1 and SZ2 are the same. The passage of the home position of the disk D can be detected in such a way.
On the other hand, the aforementioned parallel light beam illuminating the track in which the absolute code patterns U, V and W exist, is continually projected on either of the photoelectric elements SU, SV and SW through the beam splitter BS as the reflected light, only when the light beam illuminates either transmittable portion among the absolute code patterns U, V and W. An absolute code signal group is output from the photoelectric elements SU, SV and SW in response to the rotational position of the disk D, and the absolute position is identified by a signal processing circuit not shown in the figures. As the method for identifying the absolute position is well-known, the explanation will be omitted here.
As described above, even when using the optical reflection type of diffraction grating and code patterns, the diffraction grating GT for detecting the incremental amount of rotation by the grating diffraction method and the patterns for detecting other information, such as absolute rotational position and home position, on the rotation by light-and-blackness of the light are illuminated together using the single illuminating optical system. Thus, the apparatus can be further miniaturized by the compact, simple structure.
FIG. 10 is a schematic diagram illustrating an optical arrangement of a rotary encoder in the fourth embodiment of the present invention, in a way similar to FIG. 6. On the same portion as the third embodiment, the explanation will be omitted. In this embodiment, the optical system of the third embodiment is partially modified so that the interfered light for incremental measurement, absolute code pattern and home position code pattern are projected on the photoelectric element array SARY by the image projecting lens LNS2 through the beam splitter BS. Thus, the arrangement of the photoreceptor array SARY is the reverse of that of the third embodiment. By such a structure, the edge resolution of the absolute pattern and home position pattern is improved, resulting in further detecting accuracy.
FIGS. 11 through 13 are schematic diagrams illustrating light paths in the rotary encoders in the fifth through seventh embodiments of the present invention depicted in a way similar to FIG. 3. The explanation of the same portion as the first and second embodiments will be omitted here.
Each embodiment represents modification of the first or second embodiment. Among them, in the fifth embodiment shown in FIG. 11, the positions of the disk D having the radial grating GT and the second diffraction grating GBS2 are reversed. Two ± first order diffraction light beams R+ and R- are formed from each region in the second diffraction gratings GBS2 divided into four sections, GBS2-A, GBS2-B, GBS2-A and GBS2-B, the light beams R+- and R-+ are formed by the reflection of the ± first order diffraction light beams R+ and R- with the first diffraction grating GBS1, and finally the light beams R+-+ and R-+- are formed by reflecting with the radial grating at the crossing point.
Next, in the sixth embodiment shown in FIG. 12, the second diffraction grating GBS2 is not divided differing from the fifth embodiment, but the radial grating GT is divided into two regions, GT-A and GT-B, in the radial direction, of which the phase is shifted by one-fourth period from each other. In this case, the detector consists of only the photoelectric elements SA and SB in response to these two regions.
Moreover, in the seventh embodiment in shown FIG. 13, the arrangements of the disk D having a radial grating GT and the second diffraction grating GBS2 are reversed similar to the first and second embodiments.
In either case among these embodiments, the diffraction grating GT and the first and second diffraction grating GBS1 and GBS2, for detecting the amount of the incremental rotation by the grating interference/diffraction method, and the patterns for detecting other rotational information, such as absolute rotating position and home position, by the detection of the transmittance/non-transmittance of the light differing from the grating interference method, are illuminated with the single illuminating optical system together. Thus, a compact, simple structure can be achieved, resulting in a further miniaturized apparatus.
FIG. 14 is a schematic diagram illustrating light paths in the rotary encoder in the eighth embodiment of the present invention, depicted in a way similar to FIG. 8. The explanation on the same structure as the third and fourth embodiments will be omitted. This embodiment is a modification of the third or fourth embodiment. In this embodiment, the diffraction grating GBS3 is not divided, thereby differing from the third or fourth embodiment, but in contrast, the radial grating GT is divided into two regions, GT-A and GT-B, provided in the radial direction so that the phases of two regions are relatively shifted to one-fourth period. In this case, the photoelectric element array consists of only photoelectric elements SA and SB.
FIG. 15 is a outlined block diagram illustrating a motor driver system in the ninth embodiment of the present invention, wherein DH represents a detecting head including all parts of the optical system from the light source LGT to the photoelectric element array SARY in any of the first through eighth embodiments, but does not include disk D which is shown separately, PU represents a signal processing circuit which measures the amount and direction of the incremental rotation, and the position of the discrete rotation, detects the home position, and generates control signals by processing the signal from each photoreceptor in the photoelectric element array SARY, IM represents an input section to input the command of the rotation to the signal processing circuit PU, MD represents a motor driver for controlling the drive of the motor in response to the control signals from the signal processing circuit PU, MT represents a motor, and SF represents a shaft driven by the motor and transmits the driving power to each driven portion not shown in FIG. 15.
The signal processing circuit PU generates control signals based on the output from each photoelectric element in the photoelectric element array SARY and input command information from the input section. The drive of the shaft SF is controlled by the motor MT receiving the control signals. By such a structure, the detecting head HD is miniaturized and a more compact motor driver system can be achieved.
Further, the optical system can be developed by the following alterations:
(1) In the optical path for division, deflection and synthesis of the light beam by three diffraction gratings, numbers N1, N2 and N3 per circuit of the first, second and third radial diffraction gratings may be modified within the range satisfying the following relation:
n1·N1+n2·N2+n3·N3=0
wherein n1, n2 and n3 represent the diffraction orders by the first, second and third diffraction gratings, respectively. Therefore, the number, N, of radial diffraction gratings, not provided on the disk D and thus not requiring the recording on the entire circuit, is not always an integer, but may be a real number. In the first embodiment, n1=+1, n2=-1, n3=+1, N1=2,500, N2=5,000, and N3=2,500.
(2) The absolute code pattern U, V and W may be modified for a common pure binary code, grey code or the like, not for the motor control.
(3) The division number and phase difference amount of the phase difference signal generating diffraction grating (GBS2 in FIG. 1) for the measurement of the incremental amount of the rotation may be changed. For example, by setting the dividing number to two, the phases of interfered signals generated are shifted by 90 degree each other, or by setting the dividing number to six, the phases are shifted by 60 degree each other.
(4) The home position detecting method may be changed to a method for detecting the peak of the correlation function by overlapping two random pitch patterns, not the aforementioned method in which the detecting pattern is obtained from the differential signal of two signals shifted in the rotation direction.
While the present invention has been described with reference to what are presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. To the contrary, the invention is intended to cover various modifications and equivalent arrangements, included within the spirit and scope of the appended claims. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions. | In an apparatus for detecting information on the rotation of an object using a grating interference system, the present invention provides a rotation detecting apparatus, which can be sufficiently miniaturized even when using another rotation information detecting section at the same time, and an apparatus for controlling the rotation using the same. The apparatus has a first detecting device for detecting by making the diffracted light from the diffraction grating interfere to detect rotation information of the object, a second detecting device for detecting the light from the predetermined data recording section to detect rotation information of the object, and a light beam illuminating device common to the first and second detecting means for illuminating the diffraction grating and the predetermined data recording section together. | 6 |
BACKGROUND
1. Technical Field
Embodiments of the present invention relate to Direct Memory Access (DMA) system used for communications. More particularly, the present invention relates to a system for providing DMA communication for intellectual property (IP) cores of a programmable logic device (PLD) such as a Field Programmable Gate Array (FPGA).
2. Related Art
A common theme in FPGA-based architectural design is the interface between an embedded processor and one or more IP blocks. Communications across such interfaces typically include both data and control information. In particular, communications with IP cores generally involves movement of data and control tokens between hardware and software based Finite State Machine (FSM) elements. This communication may be achieved via typically three general approaches, (1) First In First Out (FIFO) streaming interface, (2) BUS transaction interface, and (3) DMA. Each case has advantages and disadvantages.
The first communication approach, FIFO, (First-In-First-Out), is conceptually simple. The FIFO depends on a simple streaming interface, with its associated bi-directional flow control, i.e., overflow/underflow. The FIFO is amenable to rate matching, and affords a simple hardware implementation model. This interface model is appropriate to broad dataflow processing classes of significant interest. One downside of FIFO is the parsing of control and data tokens. If simple flow control signals, (e.g., overflow, underflow), are not sufficient for the task at hand, control must be applied via a separate FIFO channel, with appropriate control/data synchronization. Further, FIFO does not permit random-access. Thus, whenever random-access is required, data must be buffered in some auxiliary RAM resource. In summary, FIFO-based streaming is most appropriate where simple serial data streaming is sufficient to the IP core processing model, and is accompanied by minimal-complexity FSM control.
FIG. 1 is a block diagram illustrating a standard bidirectional FIFO-based processor/IP core communication interface used in an FPGA. The processor shown is a Reduced Instruction Set Computer (RISC) 4 , connecting to a single IP core 6 . The FIFO buffers 12 1-3 and 13 1-3 provide a particularly simple symmetrical interface between the processor and IP core. A dual port Block RAM (BRAM) 2 a of the FPGA forms the RISC processor 4 Instruction/Data memory resource. Data may then be propagated between the I/D BRAM 2 a and the IP core 6 using the RISC processor 4 . The control signals used between the RISC processor 4 and BRAM 2 a include Chip Select (CS), and Write ENable (WEN), along with the ADdRess (ADR) and DATA transferred between the RISC 4 and BRAM 2 a . The processor 4 and IP core 6 employ signals for management of the data interface, according to some streaming protocol typically implemented using the FSM 10 associated with the IP core 6 . Instructions for data flow control between the RISC 4 and IP core can include: Data ReaDY (DRDY), OVerFlow (OVF), and UnDerFlow (UDF) that are transferred along with DATA information. The IP core 6 can include an FPGA BRAM memory 2 b for auxiliary data or control signal storage. The FIFOs 12 1-3 and 13 1-3 provide a buffering function, affording some degree of asynchronous rate matching across the interface, depending upon FIFO depth, relative clock rates, and other factors. The FIFO communication technique has also been applied to streaming processor/co-processor communication models separate from an FPGA. When the processing model requires a more complex data organization, such as block-transfer, random access, or multiple buffer partitioning, using FIFOs is less efficient relative to a DMA or a BUS system.
A second communication method, using a BUS, represents an abstraction of the communications channel in form of a set of defined operations at the interface. Typical operations include READ/WRITE DATA (from/to a specified address), READ (IP Core/Channel) STATUS, WRITE (IP Core) CONTROL, READ INTERRUPT, and other operations. These operations are abstracted in the form of an Applications Programming Interface (API) that includes a set of function calls within a software programming environment. The API then implements IP Core/processor communications in form of a highly simplified procedural semantic. However, this convenience and flexibility comes at a cost. The BUS is by nature a shared resource. Thus, communications with multiple peripherals engenders arbitration, and is accompanied by a total bandwidth constraint. At high rates, arbitration typically engenders a significant overhead. To some extent generic master/slave DMA transaction and block-oriented (pipelined) data transfer may relieve bandwidth restrictions, but at a cost of significantly increased complexity and arbitration loss. Further, IP cores as BUS peripherals may require an internal rate matching buffer as means to structure data path-BUS communications. Thus, an essential doubling of required BUFFER/MEMORY resources may result, since data may be buffered on both sides of the BUS. This is in addition to hardware resources needed for BUS/BUS-Arbiter infrastructure. In sum, with multiple IP cores or peripherals, BUS transaction may engender high overhead in terms of hardware resources, control complexity, and aggregate bandwidth limitations.
FIG. 2 shows a block diagram illustrating communications between a processor 4 and IP core 6 using a standard BUS system 14 . The RISC processor transfers data between the BRAM 2 a and IP core 6 , as in FIG. 1 . Advantages of the BUS include simplification and unification of processor 4 —IP core 6 communication in terms of a master/slave or peer-to-peer control model. To the extent bus arbitration overhead does not emerge as a limiting factor, another advantage the BUS offers is straightforward extensibility to multiple/diverse peripherals or IP cores 6 . Disadvantages accrue primarily with regard to; (a) arbitration overhead, (b) hardware-level complexity, (c) and where burst-mode transactions are not supported, (i.e., no pipelining), there may exist significant transaction overhead. Further, data generated or consumed at the processor 4 or IP core 6 may still require rate-match buffering at the bus interface. Under such circumstances, data must again be stored in two separate locations.
A third type of communication, DMA provides high efficiency, speed, and flexibility in comparison to alternative approaches based upon FIFO streaming or BUS arbitration. The advantages of a DMA system can be extended to FPGA designs where the associated DMA controller and system components required do not significantly impact configuration resources of the FPGA. The DMA option hinges upon high-speed transfers between IP core data buffers and memory without processor intervention. Disadvantages accrue with regard to complexity, (typically a distinct control envelope for each IP core), and scalability, (too many DMA clients degrade overall memory performance). It is desirable to provide a DMA solution that addresses these disadvantages.
SUMMARY
According to embodiments of the present invention, communications between IP cores and a processor is serviced by a DMA system. Processor—IP core communications is supported with datapath and control information shared in a common memory-mapped resource, such as a dual-port BRAM. DMA control signal detection is provided through a side-channel decoder block, to allow high-speed pipelined buffer transfers. This provides significant performance advantages relative to FIFO, BUS, and traditional DMA systems.
Dual-port BRAM between a processor and an IP core buffers data and control signals transferred between a buffer memory jointly controlled by the processor and dual port BRAM memory. Control events are propagated via a signal path separate from datapath in form of a side-channel controller. The separate controller occurs in form of a decoder.
In operation, the decoder determines if a reserved BRAM memory location has been accessed. This is accomplished by detection of one or more of Chip Select (CS), Write Enable (WEN), and address (ADR) value combinations. For example, if a signal is identified as a control signal, the decoder generates an event vector that is transmitted to the receiving device (either an IP core or processor).
BRIEF DESCRIPTION OF THE DRAWINGS
Further details of the present invention are explained with the help of the attached drawings in which:
FIG. 1 is a block diagram illustrating a standard bidirectional FIFO-based processor/IP core communication interface used in an FPGA;
FIG. 2 shows a block diagram illustrating processor/IP core communications in an FPGA using a standard BUS system;
FIG. 3 shows a block diagram illustrating processor/IP core communications using a DMA interface servicing the multiple IP cores;
FIG. 4 shows a block diagram illustrating processor/IP core communications with a DMA interface in a FPGA formed using dual-port BRAM of the FPGA plus DMA side-channel control implemented over a bus subsystem;
FIG. 5 illustrates one embodiment of the present invention that replaces the bus-based DMA control channel of FIG. 4 with a BRAM address/control decoder block;
FIGS. 6-7 illustrate reconfiguration of the decoder block of FIG. 5 to provide SLAVE/MASTER or PEER-to-PEER communications;
FIG. 8 illustrates scaling of the components of FIG. 5 to provide MASTER/SLAVE communication between a processor and multiple IP cores; and
FIG. 9 is a flow chart showing one non-limiting example of steps for designing and instantiating a DMA-based system for communication between a processor and IP cores.
DETAILED DESCRIPTION
FIG. 3 shows a block diagram illustrating communication between a processor 4 and multiple IP cores 24 using a DMA interface. The DMA interface includes a DMA controller 20 as arbiter for all memory accesses and mediates IP core specific control signals necessary to IP core DMA operations. The DMA interface further includes a DDR/QDR memory 22 partitioned according to address block size and an offset that is accessed by the DMA controller 20 . The DMA system incorporates mapping of specific memory partitions to peripheral/IP core device drivers and I/D cache 21 existing in the RISC address space. DMA also implements memory-to-memory transfers based upon the assumed memory-map without processor intervention. Data, address and control signals are employed as a basis for DMA Controller 20 regulation of data flow between the RISC processor 4 , IP Core bank 24 , and DDR/QDR RAM 22 . Note that other types of processors may also be used. One example of a device that may include the DMA system of FIG. 3 is a video frame buffer, where video data acquired by a frame grabber peripheral interface is DMA transferred to a DDR/QDR memory and operated upon by image processing algorithms executing in the IP cores 24 as accessed by the RISC processor 4 . This type of arrangement is available in principle to FPGA designers, but in spite of the performance advantages is not often used because of the highly distinct nature of DMA in this configuration, attendant complexity, and bandwidth sharing at the common memory resource 22 .
In FIG. 4 , one possible implementation of a memory mapped DMA existing independent of the I/D cache memory resource 21 is shown. In the configuration of FIG. 4 , a bilateral DMA buffer in the form of a dual-port BRAM memory 2 b of the FPGA is mapped into the address space of a RISC processor 4 . This DMA is then leveraged for IP Core 6 datapath communications. The RISC processor 4 and IP core 6 process READ/WRITE access at the DMA buffer 2 b on separate BRAM ports and in a common address space. The processor also accesses the I/D BRAM 2 a and DMA buffer 2 b memory elements in a unified address space. Address and control signals between the RISC processor 4 , DMA controller 30 and BRAM storage 2 a include two sets of CS, WEN, DATA and ADR, one for each I/D component. Control signals between the memory DMA controller 30 and BRAM 2 b and IP core 6 include DATA, ADR, CS and WEN. Appropriate control agent synchronization is imposed such that data is not corrupted during concurrent processor/IP core addresses, namely RISC processor 4 DMA API calls in conjunction with IP core FSM DMA operations. A separate side-channel control is constructed in the form of a bidirectional GPIO bus peripheral 32 , whereby a specific DMA transfer FSM protocol is implemented. In particular, the IP core FSM 10 and processor-based application are informed of processor-to-IP core/IP core-to-processor DMA transfer status via the BUS 14 .
In summary, the configuration of FIG. 4 realizes many DMA performance advantages. Particularly noteworthy is: (a) data is buffered only once using BRAM 2 b and (b) data transfer is rate-matched across the dual-port memory interface. However, there also exist disadvantages to this arrangement: (a) the added complexity of a bus sub-system 14 for a DMA control side-channel, (b) additional API calls at the processor associated with control word transactions at the bus interface 14 , and (c) potential DMA/DMA control latency/skew issues caused by bandwidth sharing on the arbitrated bus 14 .
FIG. 5 illustrates one embodiment of the present invention that addresses disadvantages of FIG. 4 . In FIG. 5 , the bus is replaced by a BRAM address/control decoder block 36 . The control input to decoder 36 from DMA controller 30 includes the processor BRAM address bus (ADR), plus associated Chip Select (CS) and Write ENable (WEN) signals. Control output occurs in the form of an encoded (event) vector indicating the processor 4 has applied a READ or WRITE operation for a control operation including control code, status code, or an interrupt code to some reserved buffer region in BRAM 2 b . Processor DMA control event vectors are then applied to a reserved IP core FSM control agent register file.
A MASTER/SLAVE communication discipline is implied between the processor and IP core displayed in FIG. 5 . However, SLAVE/MASTER or PEER-to-PEER may be optionally implemented with decoding of the IP core BRAM address plus associated control signals, as indicated in FIGS. 6-7 . In FIG. 6 , a SLAVE/MASTER configuration is achieved with the DMA control decoder 36 input derived from the IP core and the output event vector applied to RISC processor 4 registration file 40 . In FIG. 7 , a PEER/PEER configuration is achieved by instancing of two separate decoders 36 a and 36 b to provide bilateral control between the IP core 6 and RISC processor 4 , in both directions.
In the configuration of FIGS. 5-7 , an address space subset 38 of the BRAM 2 b is reserved for DMA CONTROL, STATUS, and INTERRUPT or other control data fields (commonly referred to herein as control fields). Any READ or WRITE operation on a reserved BRAM 2 b memory location generates a DMA transfer event vector. An event vector thus generated serves as FSM input at the receiving device, triggering a READ operation at associated control data fields. Control processing sequences are then executed by the receiving device based upon decoding of control data field contents. At termination of processing, the DMA control sequence is completed with the receiving device update of its own reserved control and status data fields. In this manner, potentially complex DMA control may be implemented based upon a simple encoding of BRAM 2 b access events in combination with processing of encoded control data tokens residing at reserved BRAM 2 b addresses. This new DMA structure is scalable, flexible, highly compact, and applicable to broad classes of IP cores.
It has already been noted in the proposed DMA scheme the IP core 6 is effectively mapped into the processor address space in BRAM 2 b . One consequence of this is memory map information, namely memory addresses plus offsets at which specific READ/WRITE operations are to be performed, may be passed through the buffer. An example is communication of a specific buffer partition from the processor 4 to the IP core 6 via: (a) generation of memory pointers within context of a processor-resident application, (b) application of address data-type casts to the pointers, and (c) memory-map WRITE to the reserved DMA register locations. This memory map is subsequently read by the IP core FSM 10 as BRAM bit vector addresses, and may then be used to structure specific and highly complex DMA buffer operations.
According to embodiments of the present invention, STATUS, CONTROL, and INTERRUPT data fields may be extended more or less arbitrarily within the BRAM memory 2 b . The decoder will be set to recognize this area based on the ADR, CS and WEN signals received and generate an event vector in response. If the address is outside the reserved memory area, the decoder will assume it is simply data being transferred, and no event vector will be generated. STATE information at a more or less arbitrary level of detail may be shared between the RISC processor 4 and a given IP Core 6 . This provides a rich syntactical basis for construction of DMA control sequences. One possible application is management of multi-BUFFER sub-partitions within context of a multi-threaded processing model.
As shown in FIG. 8 , the resulting DMA scheme scales in a fairly straightforward manner to multiple IP cores with addition of; (a) memory-mapped, dual-port BRAM elements 2 c , and (b) DMA control (decoder) blocks 36 b on a per-IP core 6 a basis. The particular configuration shown in FIG. 8 is MASTER/SLAVE, but may be extended in obvious manner to SLAVE/MASTER, or PEER/PEER. Note the BRAM blocks 36 b do not have to be the same size. Further, the simplicity and generic nature of the DMA control envelope suggests the decoder bank 36 b may be merged into a single block. Further, instancing of the memory-mapped BRAM 2 c on a per-IP core basis addresses a DMA scaling problem in that no access contention exists at the interface port between the BRAM 2 c and the IP core 6 a . Thus, DMA buffer READ/WRITE may in principle be concurrently performed by an arbitrary collection of IP cores, at essentially full access bandwidth.
The proposed DMA implementation is straightforward and may easily be performed using existing commercially available tools. For example, the DMA arrangement may be implemented using the Embedded Developers Kit (EDK) and Integrated Software Environment (ISE) tools, both available from Xilinx, Inc. of San Jose, Calif. A flow chart for one non-limiting example is shown in FIG. 9 . In the flow chart, the following steps are performed. In step 900 , a processor plus memory-mapped BRAM blocks, (a single BRAM per IP core), are instanced in EDK. A processor software application is also created, and the partial design subsequently exported to ISE. In step 902 , DMA controllers are instanced as HDL-based IP blocks in ISE. In step 904 , selected peripheral IP core blocks are instanced in ISE. In step 906 , all components determined in steps 900 , 902 , and 904 are interconnected to form an HDL design hierarchy, with a DMA controller ports attached to appropriate BRAM ADDRESS, WEN, and CE signals, and the IP core event-vector ports. Finally, in step 908 a configuration bitstream is generated in ISE and downloaded to an FPGA, for example via Joint Test Action Group (JTAG) or other configuration port.
The DMA side-channel controller control envelope minimally includes BRAM port address, Chip Select (CS), and Write Enable (WEN) signals on input, and output in form of an encoded ‘event’ vector. The event vector triggers state machine control operations in the processor or IP core. In particular, status, control, and interrupt register data fields (commonly referred to as control signals) are all mapped to reserved BRAM addresses and associated with unique event flags. In sum, with event decoding of READ/WRITE operations at reserved BRAM addresses and execution of processing sequences based upon control vectors residing at those locations, DMA control between the processor memory controller and IP core is stripped to the barest essentials. This compact control envelope is then employed for all IP cores provided in an FPGA as basis for implementation of full-featured DMA services at each IP core. This feature serves to address a fundamental DMA system-scaling problem, namely memory subsystem performance does not significantly degrade as DMA IP cores are added.
In essence, this DMA concept leverages an ability to map multiple dual-ported BRAM instances into the processor address space. In particular, every word in BRAM is accessible to the processor, via standard memory READ/WRITE operations. The processor then exploits this capability for communication with multiple IP cores. Full support is provided for: (a) buffer partitioning; (b) rate matching, and (c) block transfer, as dictated by arbitrarily complex Processor—IP core control signals provided in conjunction with the event vectors. One useful result is the IP core Applications Programming Interface (API) is rendered in the form of simple memory READ/WRITE at the associated BRAM addresses.
Embodiments of the invention describe a Direct Memory Access (DMA) subsystem implementation useful as a high performance alternative to BUS-based, or FIFO based FPGA platform/SoC designs. In particular, superior DMA data transfer performance may be achieved within the context of a multiple IP core plus embedded processor system while simultaneously realizing: (a) performance scaling across multiple DMA clients, (b) minimal logic/memory resource consumption, (c) highly simplified/generic control interface, (d) support for MASTER/SLAVE, SLAVE/MASTER, PEER/PEER control paradigms, and (e) a highly simplified Applications Programming Interface (API).
Although the present invention has been described above with particularity, this was merely to teach one of ordinary skill in the art how to make and use the invention. Many additional modifications will fall within the scope of the invention, as that scope is defined by the following claims. | A Direct Memory Access (DMA) system is provided for simplified communication between a processor and IP cores in an FPGA. The DMA system includes use of dual-port BRAM as a buffer and a decoder as a DMA control signal identification mechanism. The DMA control signals are stored in an area of the BRAM memory recognized by the decoder using chip enable (CE), write enable (WE), and address (ADR) signals. The decoder, upon recognizing a DMA control signal, will generate an event vector. The event vector triggers a READ operation by the receiving device at the associated BRAM control data memory address. DMA control codes can be detected as sent from either the processor or the IP core or both, depending upon whether the system employs a MASTER/SLAVE, SLAVE/MASTER, or PEER/PEER control model. | 6 |
BACKGROUND OF THE INVENTION
This invention relates generally to recirculating systems for cleaning drilling muds. More particularly, the present invention relates to a desander/desilter mud cleaning system which combines the controlled multi stage use of centrifugal force and pressure for separating media of varying particle density.
As will be appreciated by those skilled in the industry, drilling muds are generally employed in the rotary drilling process as a medium for carrying solid cuttings such as sand, shale, and heavier rock particles recovered from the depths of the well to the upper surface of the earth. Because great volumes of mud are required for drilling and because the muds are generally quite expensive, it has become the common practice of those in the drilling industry to clean and reuse the drilling muds in order to maximize their economic benefit. The initial step in preparing the drilling muds for reuse involves the removal of the heavier materials recovered in drilling and the separation of the media of various density from the drilling mud. The present invention addresses itself principally to this initial stage of the cleaning process.
A number of prior art cleaning devices known to us demonstrate the employment of centrifugal force or a "cyclone" to create an interior vacuum which draws the lighter, more fluid drilling mud to the upper chambers of a suitable reservoir, leaving the heavier particles deposited at various levels therebelow. Mud-cleaning systems of this type are generally described in U.S. Pat. Nos. 2,274,503; 2,098,608; 4,216,095; and, 4,447,322.
U.S. Pat. Nos. 3,213,879 and 3,243,043 describe methods and mechanisms for regulating the discharge of solids from centrifuge separators. U.S. Pat. No. 4,462,899 describes a multiple chamber hydrocyclone cleaner assembly.
A more complex separator device which is adapted to separate gases and fine particles from the coarser materials recovered in deep rotary drilling is described by Freeman, U.S. Pat. No. 2,757,582. The Freeman device depends upon the downward, gravitational pull on the liquid medium as it passes through a vertical cone. A similarly vertically disposed cyclone separator is described in U.S. Pat. No. 2,756,878, which provides an additional outflow for separating out products of varying intermediate densities. Other relevant prior art devices known to us are presented in U.S. Pat. Nos. 2,723,750; 2,717,695; and 2,379,411, as well as my own separator invention defined in U.S. Pat. No. 4,431,535.
None of the prior art devices known to us, however, satisfactorily addresses problems commonly encountered in the desanding and desilting process. For example, "dirty" drilling mud returned to the surface may be constantly varying in the percentage, quality and content of contamination. The mud may contain at a given time a variety of recovered particles, liquid products, and gaseous materials of a wide range of density. The mud at one instant may be full of coarse sand, and shortly thereafter its content may change. Since the "quality" of the returned mud varies constantly, it is impractical to mechanically change between conventional desilters and desanders economically.
It is therefore desirable to provide multiple function separation means for distinguishing and separating out the materials of varying density from the single fluid drilling mud medium. None of the prior art devices are equipped to satisfactorily regulate the internal pressure of the various inner chambers for proper separation, which cannot be satisfactorily achieved through centrifugal force or gravity alone. By experimentation and experience with the product, it has become evident to me that a suitable separator should provide a number of independent cleaning chambers adapted to continuously process the recovered mud in such a way as to provide an output of uniform consistency notwithstanding the fact that the incoming raw or "dirty" mud may constantly vary in quality.
SUMMARY OF THE INVENTION
The present invention comprises a system for cleaning drilling muds. The preferred machine incorporates a centrifuge desander operatively connected to a series of conical desilter units to effectuate the separation of materials of varying densities and to provide for the separation out of air and gasses for increased efficiency of the cleaning operation.
The apparatus comprises six major cooperating structures, including an initial cyclone chamber, a central separator drum, a desander cone, a plurality of cooperating desilter cones, a solid waste disposal system, and a gas release. Operationally, the cleaning process occurs in three general stages as set forth in detail in the descriptive sections which follow.
Each of the various stages of the cleaning process involves the separation of the drilling mud into medium of different densities. In the initial stage, the fluid muds containing solid materials recovered from the rotary drilling process are pumped at a controlled pressure from the cleaning bed (i.e. the recirculating mud reservoir) into the initial cyclone chamber, where, under increasing centrifugal force, the fluid muds are separated into heavier sand-bearing medium, lighter, more fluid medium and freed air and gasses.
In the second stage of the process, the medium which contains the heavier waste materials is processed within a suitable chamber within the lower level of a twin compartment, central drum. A series of baffles and vents within this chamber facilitates the operation of a subsequent desander cone where heavier impurities are removed, and from which "cleansed" mud, which is still not clean enough, is recycled back to the mud reservoir bed. Later, when this mud is recirculated through the machine, it will escape this "loop" when clean enough and eventually it will be desilted and available for the drilling operation.
Lighter products initially separated in the cyclone chamber are transmitted through the larger chamber within the lower drum compartment. This latter chamber functions as a distribution manifold, and delivers the product to a plurality of similar radially spaced apart desilting cones for further processing. The combined output of the desilter cones is delivered to the upper compartment of the drum. Interior drum baffle structure facilitates gas withdrawal and escape, and properly cleansed mud is concurrently recovered through a suitable pipe.
In the third stage, freed air and gasses are discharged at controlled rates to be burned or dispersed into the environment. Removal of the excess gas and air during critical stages of the cleaning process immediately prior to subsequent to cone handling increases the efficiency of the cones and greatly decreases mud losses in the underflow discharge. The waste materials discharged from the desander and desilter cones flow downwardly through a large funnel and are deposited into a suitable waste receiving bed.
OBJECTS OF THE INVENTION
Thus a general object of the present invention is to provide a drilling mud cleaning system which will separate out particles of varying densities from a single medium.
A fundamental object of the present invention is to provide a drilling mud cleaning system which continuously outputs a substantially uniform product, notwithstanding the fact that the quality and consistency of incoming "dirty" mud may vary constantly.
A more specific object of the present invention is to provide a three-stage drilling mud cleaning system which attains more efficient operation through the cooperative employment of centrifugal force and controlled pressure.
A similar object of the present invention is to provide a mud cleaning system which effectively avoids typically encountered problems of blockage, vacuum lock, and excessive mud loss.
A related object of the present invention is to provide a drilling mud cleaning system of the character described in which mud losses are greatly reduced.
Yet another similar object of the present invention is to provide a cleaning system which provides for separation of solids, liquids, and gasses from a single fluid mud medium.
A similar related object of the present invention is to provide an improved drilling mud cleaning system which is equipped with means for regulating input and output pressure.
Yet another object of the present invention is to provide means for recycling cleansed drilling mud through the system to reduce mud losses.
A similar object of the present invention is to provide a drilling mud cleaning system in which the input pressure may be regulated to accomodate muds of varying densities and to provide more efficient operation.
Another object of the present invention is to provide an improved apparatus for cleaning drilling muds which can be easily transported and installed on site.
These and other objects and advantages of this invention, along with features of novelty appurtenant thereto, will appear or become apparent in the course of the following descriptive sections.
BRIEF DESCRIPTION OF THE DRAWINGS
In the following drawings, which form a part of the specification and which are to be construed in conjunction therewith, and in which like reference numerals have been employed throughout wherever possible to indicate like parts in the various views:
FIG. 1 is block diagram of a mud cleaning machine constructed in accordance with the best mode of the present invention, and illustrating the major stages of the mud cleaning process;
FIG. 2 is a front elevational view of the machine;
FIG. 3 is a rear elevational view of the machine;
FIG. 4 is an enlarged scale, fragmentary, longitudinal sectional view of the cyclone chamber preferably employed for initial separating;
FIG. 5 is a fragmentary sectional view of the separating drum;
FIG. 6 is an enlarged scale, fragmentary sectional view of the central drum;
FIG. 7 is a fragmentary sectional view taken generally along line 7--7 of FIG. 6;
FIG. 8 is an fragmentary sectional view taken generally along line 8--8 of FIG. 6; and,
FIG. 9 is an enlarged fragmentary view of interior dividing wall structure of the drum.
DETAILED DESCRIPTION
With reference now directed to the appended drawings, a drilling mud cleaning machine constructed in accordance with the teachings of the best mode of the present invention has been generally designated by the reference numeral 10. Machine 10 is adapted to be disposed at a conventional drilling site, and its function is to cleanse conventional drilling mud or fluids by concurrent desanding, desilting, gas separation and recirculating operations to recover the valuable drilling mud for subsequent reuse.
An overview of the apparatus is provided by FIG. 1. The "dirty" mud to be cleaned is transferred from a conventional cleaning bed or reservoir 12 (established at the drilling site) via conventional pipe 14 into a hollow cyclone chamber 20. The fluid mud and solid materials carried in suspension thereby are centrifugally rotated within chamber 20, and the mud is separated into relatively light and relatively heavy density constituents. Air and gasses freed in this initial separation stage pass into the gas release system 70, via pipe 16, T-connection 76, and pipe 77. However, a small quantity of particulates may nevertheless exit pipe 16.
After separation within chamber 20 the heavier medium, laden with solid wastes and the lighter, more fluid medium are carried into separate desander chamber 30A and desilter chamber 30B interiorly of the central drum 30 via pipes 22 and 18, respectively. As will hereinafter be described in detail, the heavier medium passing through the vented and baffled chamber 30A is transmitted to centrifugal desander cone 40, from which solid wastes are released through outlet 44 into a waste discharge funnel 64, leading to waste storage 60. The "recovered" but still-too-dirty mud outputted from desander cone 40 is returned to the reservoir bed 12 through pipes 42 and 46 for recycling and recleaning.
The lighter medium passes from chamber 30B into the desilter cones 50 where further cleaning and separation occurs. Heavier waste products are concurrently discharged from the desilters 50 via funnel 64 into the waste collector discharge system 60. Freed air and gasses released during this final stage are drawn out from the desilters 50 and released through the gas release system 70 via the upper level drum chamber 31E to be later described. The cleansed drilling mud is then carried into the collector bed, generally designated by the reference numeral 80.
With additional reference now directed to FIGS. 2-5, and 9, machine 10 is adapted to be disposed upon a suitable supporting surface 11 and it includes a rigid upright frame 11B. A flexible hose 13 is secured by expansion clamp means 13A to a rigid pipe stem 14A which is suitably flanged at 14B to rigid inlet pipe 14 which extends upwardly and tangentially, and attaches exteriorly to outer wall 20W of cylindrical cyclone chamber 20 near its outer end 20A (FIG. 4). A pressure gauge 15 (FIG. 2) is provided on the outer face of the inlet pipe 14 to display inflow pressure.
With reference to FIGS. 2 and 4, the cyclone chamber 20 is horizontally disposed and supported upon a rigid, generally rectangular frame portion 24 suitably adapted with rigid flanges 25 (FIG. 4) at each end to firmly abut and cradle the cyclone chamber 20. The support frame 24 is permanently connected by welding or the like to a rigid, vertically disposed frame stanchion 26. A tubular cross bar 27 (FIG. 2) is permanently connected by welding or the like in generally perpendicular relation to the lower end of the vertical stanchion 26. Rigid webbing 28 is welded to stanchion 26 and cross bar 27 for increased stability of the apparatus. Inlet pipe 14 is supported in a stable position generally parallel to stanchion 26 upon a planar flange 29 of generally rectangular dimensions.
Outer tubular casing 20W (FIG. 4) receives a gas outlet pipe 16, which generally coaxially penetrates its end 20A. The end 16E of pipe 16 is spaced apart from the end 18E of pipe 18, which coaxially penetrates chamber 20 at its opposite end 20B. The tangentially intersecting pipe 22 communicates with the annular void 19 defined between pipe 18 and the casing 20W. In response to the inrush of dirty mud via pipe 14, interiorly rotating "heavy" materials will be centrifugally forced into annular void 19 and out through pipe 22, while "lighter" materials will be drawn out through pipe 18. Materials outputted through pipes 18 and 22 must be further processed however.
A large, generally cylindrical material processing drum, broadly designated by the reference numeral 30, is elevated in the center of the apparatus and supported upon the desilter inlet channel 18 which extends coaxially, rearwardly out of the initial cyclone chamber 20 (FIGS. 2, 4). Further support is provided for the central drum by the rigid desander pipe 22 (FIGS. 4, 5) which extends vertically out of the cyclone chamber 20 through the lower floor 30F of drum 30. The rigid, angular mount 31 (FIGS. 2 and 3) includes a rigid, generally triangular, preferably steel plate 32 which is suitably bored to receive a crane hook or the like, is permanently connected to the outer sides of the central drum 30 by means of welding or the like to permit convenient transport and placement of the apparatus 10 at the selected drilling site.
As best illustrated in FIGS. 5-9, the generally hollow interior of the drum 30 comprises an upper level desilting chamber 31E and a lower level 31X which are separated from one another by a rigid interior floor 31G. Chamber 31E is a collection chamber for desilted mud, and the desilting cones discharge into it. lhe lower level 31K is divided into a desilter feeding chamber 30B and an adjoining desander feeding chamber 30A (FIGS. 6,7) which is divided from chamber 30B by steel compartment walls 39A and 39B. Chamber 30A is further interiorly divided into pressure reduction compartments 38A, 38B and 38C (FIG. 9) by rigid interior wall 39C and floor 39D. With reference to FIGS. 5 and 9, pipe 22 exhausts to compartment 38A (which operates at roughly 50 PSI), which is in fluid flow communication with adjacent compartment 38C via valve structure 34 provided in dividing floor 39D. This valve structure includes a replaceable plate 34A (FIG. 9) having an orifice 34B of a selected size to pass materials through adjoining hole 34C in wall 39D to communicate with chambers 38C and 38B (via orifice 37). Pressure in compartment 38B is nominally 30 PSI. Adjacent compartment 38B is similarly in fluid flow communication with compartment 38C via orifice 37 defined in partition wall 39C.
Internal pressure of the lower desander entry compartment 38B is measured by pressure gauge 33A which penetrates the wall of the desander inflow chamber. A conventional pressure gauge 33B measures pressure within the upper chamber 31E (FIG. 6) of the central drum 30, which is in the form of a large, generally annular chamber defined between the radial drum periphery 29B and the offset, central pipe 71 (FIG. 8), as will hereinafter be explained.
Suspended about the outer circumference of the central drum 30 are a large, conical desander cone 40 and a multiplicity of smaller, conical desilter cones generally designated herein by the reference numeral 50. An input to the desander cone 40 is operatively established from the central drum 30 by a pair of feed pipe 40A (FIG. 5) which extends horizontally outwardly from the outer wall 30W of the central drum 30 and are joined by conventional flanges 41 (FIG. 1) to inflow pipe 42A and further to the desander discharge pipe 42 and desander cone 40. Thus the output of chamber 30A (and compartment 38B thereof) is delivered into the desander cone 40. Although pipes 42, 46 are mechanically braced by the drum by physical attachment to the periphery thereof, the output of cone 40 is isolated from upper barrel chamber 31E. The desander apparatus 50 is described in detail in U.S. Pat. No. 4,431,535 which is hereby incorporated by reference. It essentially comprises a tri-sectional, outer coneshaped housing encasing an inner rotational centrifuge chamber.
The desilter cones, each of which is generally referenced herein by the numeral 50, comprise similar operative structure and function in a manner similar to that of the desander apparatus. As best viewed in FIG. 6, the desilter cones 50 are connected to the central drum by feed pipes 50A and 50B which are joined by conventional headers 52 to the desilter inflow 53 and discharge pipes 54 (FIG. 1). Conventional output orifice closure valves are preferably provided to regulate waste discharge from the desilters. Stability and support of the cones is provided by the structure of the underlying waste discharge apparatus generally designated herein by the reference numeral 60 (FIGS. 2 and 3).
The waste discharge structure 60 comprises a generally conical receiving pan having a rigid, vertical lip 62 about its circumference which firmly abuts the outer wall of the waste discharge outlet 44 of the desander cone 40. A rigid, vertical support wall 63 which extends from the lip 62 around approximately two-thirds of the circumference of the structure helps mount the radially spaced apart desilter cones 50. A downwardly sloping basin 64, a tubular outflow funnel 65 and a discharge spout 66 direct wastes collected from the upper outputs (i.e. the "heavy material" bottom outlet pipes of each of the conical desilters and the desander) and directs wastes to a remote storage site 69. The outflow funnel 65 terminates at its lower end in a rigid, tubular mount 67 which is adapted to be slidably mounted upon the rigid support pole 68 which supports the entire waste discharge structure 60 in a central position beneath the central drum 30 (FIGS. 2 and 3). The waste materials deposited into the system flow downwardly from the basin 64 through the funnel 65 and are guided by the discharge spout 66 into a suitable waste receiving bed 69.
The gas release system, generally designated herein by the reference numeral 70, includes a tubular chimney 72 (FIGS. 5, 6) which extends upwardly through the upper level chamber 31E of the central drum 30 and terminates at its upper end in a smaller diameter bisectional jet 73. Chimney 72 concentrically penetrates a surrounding pipe segment 71 (FIG. 6) and an annular void 74 is defined therebetween. The base of chimney 72 is spaced apart from the drum divider floor 31G. A gas inlet port 75 is preferably defined in one wall of the pipe segment 71.
The gas release system 70 is connected to the gas release pipe 16 (FIG. 4) feeding from the cyclone chamber 20 by a conventional elbow joint 76. Extending upwardly from the elbow 76 is the tubular compression canister 77 (FIG. 6) which terminates at its upper end in a conventional compression control valve 78 (FIG. 6). A conventional clamp 78A securely connects compression control valve 78 to a flexible hose 79 which terminates in a small, rigid, jet stem 79A connected to hose 79 by a conventional clamp 79B. Jet stem 79A penetrates the wall of chimney 72 and thus provides a pathway for controlled release of the air and gasses freed during the initial stage of the cleaning process. Gases swirling within pipe 72 will be released into the atmosphere through pipe 73, but mud particles will spiral downwardly within pipe 72 into volume 74. A fluid lock is created within chamber 31E and volume 74 by the volume of mud accumulating within chamber 31E and extending upwardly generally level with the top of pipe 71. With the fluid lock gas which enters pipe 72 cannot be pulled into chamber 31E.
Operationally, the cleaning process occurs in three general stages. Fluid mud containing solid materials entrained during the rotary drilling process are drawn by conventional pumps upwardly through the tubular inlet 14 into the outer end 20A of the initial cyclone chamber 20. As the mud enters the initial cyclone chamber 20 under controlled pressure, it is set in rotating motion. As centrifugal force increases within the chamber, the heaviest solid particles are slung outwardly and the lighter fluid medium and the freed air and gasses are forced to the center of the rotating mass. The rotation of the mud mass under pressure permits the creation of a relatively reduced pressure, low turbulence area in the adjacent gas release pipe 16 which coaxially penetrates the outer end 20A of the cyclone chamber 20, so that the freed air and gasses are drawn out of the center away from the rotating mud mass. The removal of freed air and gasses through the gas release system 70 greatly enhances the efficiency of the apparatus and aids to reduce substantially usable mud losses.
As mud continues to feed into the initial separator 20, the mass of solid medium is forced toward the opposite, inner end 20B which is coaxially penetrated by the rigid, tubular desilter inlet channel 18. The lighter fluid medium generally comprises the greater proportion of the mud suspension, and it is forced out of chamber 20 into channel 18, and delivered to desilter chamber 30B, which feeds the desilting cones. The heavier medium remains trapped within annular void 19 and is pushed upwardly under centrifugal force and pressure into the smaller diameter desander pipe 22. And, as previously described, gas escapes through pipe 16. Thus the initial stage of the medium separation process is completed, the materials of three varying densities separated and routed into different parts of the system.
The heavier (and still "dirty") separated medium from the cyclone chamber 20 is received by chamber 30A through the desander pipe 22. Chamber compartment 38A receives the medium first, and this heavier medium is forced through the small jet orifice 34B (FIGS. 7, 9) defined through the dividing wall 39D which separates compartment 38A from the secondary compartment 38C. Hole 37 in dividing wall 39C communicates with the desander feed section 38B. Forcing the medium to pass through these jet orifices 34B and 37 effectively reduces and regulates the pressure (i.e. within chamber 38B) at which the medium finally enters the desander cone 40 via desander inlet feed pipe 40A. Plate 34 is replaceable, and by varying the size of orifice 34B the resultant pressure differential may be varied.
The lighter, fluid material remaining from this heavier medium is drawn by vacuum pressure upwardly through the exit feed pipe 40B at the upper end of the desander cone 40 and forced through the sectional mud recovery return 46. The "cleaner" mud flows back through the mud recovery return 46 to the cleaning bed 12 to be recycled through the initial separation stage discussed in detail in the preceeding paragraphs. The solid waste materials are then released through the lower discharge orifice 44 (FIG. 1) of the desander cone 40. The solid waste materials are discharged from the desander cone 40 into the waste discharge structure 60 to complete the second stage of the mud cleaning process.
With reference again directed to FIG. 6, the third stage of the drilling mud separation and cleaning process is generally accomplished within the desilter cones 50. The lighter medium separated out during the initial stage of the process is carried under pressure from the initial cyclone chamber 20 through the pipe 18 into the desilter inflow chamber 30B in the central drum 30. This lighter medium is set in motion within the open desilter inflow chamber 30B and is thence forced through any of the multiplicity of desilter inlet feed pipes 50A which penetrate the wall of the chamber 30B and are connected to the desilter cones 50 by suitable headers 52 and pipes 53 (FIGS. 3, 6).
The rate of inflow and chamber pressure are effectively controlled by thus forcing the liquid medium to pass through the narrow inlet feed pipes 50A. The operation of the desilter cones 50 is generally similar to that of the desander cone 40 as described above, in that centrifugal force effects the further separation of the drilling mud from heavier waste particles which are released through the conventional discharge orifices (not shown) at the lower end of the cones 50 into the waste discharge system 60. The solid wastes thus discharged from the desander cone 40 and desilter cones 50 are deposited into the waste discharge basin 64, flow downwardly through the funnel 65, and are guided by the discharge spout 66 into a suitable waste receiving bed 69.
The cleansed drilling mud accumulating within level 31E flows through the tubular outflow 58 and flows downwardly into a suitable collector bed 80 (FIG. 1) to be used again in the rotary drilling process. Pipes 71 and 74 cooperate to provide a fluid lock to eliminate the gas from pipe 72 from being pulled back into chamber 31E to mix with and agitate the accumulating mud level within region 31E. When handling aerated mud, valve 78 is to be left open so that gas can be removed and vented out pipe 73, but at the same time the aforedescribed fluid lock will prevent entrance of gas while facilitating recapture of mud particles spiraling down pipe 72 through volume 74.
From the foregoing, it will be seen that this invention is one well adapted to obtain all the ends and objects herein set forth, together with other advantages which are obvious and which are inherent to the structure.
It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is within the scope of the claims.
As many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense. | A machine for cleaning drilling muds by removing entrained solids and impurities and returning cleansed and for recycling. The machine comprises a centrifuge desander operatively connected to a plurality of cooperating conical desilters to remove gases and separate materials of varying densities. Initially muds containing solid materials are pumped at a controlled pressure from the cleaning bed into an initial cyclone chamber, where, under increasing centrifugal force, the processed mud is separated into relatively heavier and lighter components, which are transmitted via separate pathways to twin chambers in the lower level compartment of a particle separating drum. The first chamber of the drum receives heavier materials and transmits them to a large desander cone where the heaviest impurities are removed; the second drum chamber receives the lighter components which are further separated and delivered to a network of desilter cones which output properly cleansed mud. The purified output of the large densander cone is transmitted directly back into the cleaning bed reservoir, and "dirty" mud is thus recycled continuously until "clean enough" to escape the loop by exiting through the desilter cones. Freed air and gasses are discharged at controlled rates to be burned or dispersed into the environment through a third stage, which is in fluid flow communication with the initial stage and the desilter stage. Through the gas removal construction disclosed, the efficiency of the various stages of the cleaning processes is increased, and drilling mud losses are minimized. | 4 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority from PCT/GB/2011/052164 filed on Nov. 8, 2011 and from GB 1019753.1, filed Nov. 22, 2010, which are hereby incorporated by reference in their entireties.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a vehicle glazing panel cut out apparatus and method.
The invention particularly relates to a technique using a cutting wire in order to effect release of the glazing panel, such as a windscreen, from its mounted position in the vehicle windscreen frame. The technique and cut-out tool of the present invention is also applicable to use on other bonded glazing panels.
2. State of the Art
Prior art is known which uses wire winder spools mounted on a single tool in order to effect cut out of a vehicle windscreen or side glass. Exemplary arrangements are disclosed in, for example U.S. Pat. No. 7,618,023 and WO2006030212.
An improved technique and apparatus have now been devised.
SUMMARY OF THE INVENTION
According to a first aspect, the present invention provides a winder unit for use with a cutting wire in cutting out a vehicle glazing panel, the winder unit having:
first and second spaced winder spools for winding cutting wire; a suction mount for mounting the unit, wherein the suction mount comprises a single suction device only.
It is preferred that the first and second winder spools are spaced to be positioned one on either side of a diameter line of the suction mount.
Beneficially, the axes of the winder spools are positioned within a space defined by the projected diameter of the skirt/membrane of the sucker mount.
In a preferred embodiment, the winder spools are mounted to the suction mount at a position over the body of the suction device.
In one embodiment, it may be preferred that the winder spools are mounted on a common deck which is secured to the single suction device.
The foregoing technical features, either alone or in combination define an arrangement which is compact and efficient to use.
It is preferred that the unit includes at least one wire guide element (preferably a rotatable guide element—such as a pulley wheel) spaced from the spools.
Desirably, first and second wire guide elements are provided, a respective guide element being positioned outwardly of each of the winder spools.
In certain embodiments, it may be preferred that the wire guide element is mounted with respect to the unit so as to be adjustable in position or orientation with respect to the winder spools.
In such an arrangement, the wire guide element may be pivotably or tiltably mounted so as to pivot or tilt with respect to the winder spools.
It may be preferred that the unit is provided with a handle spaced from the winder spools. This ensures that the winder spools can be place close to one another, because the unit can be lifted at a handle positioned other than between the winder spools.
In one embodiment, the unit is provided with a pair of substantially parallel handles each to be gripped by a separate hand of an operator.
The, or each, handle may extend transversely to a line extending between the winder spools.
In one embodiment, it is preferred that the unit includes a pump actuated suction device. According to a further aspect, the present invention provides a method of removing a vehicle glazing panel (such as a windscreen or side glass) using a winder unit as defined herein.
The invention will now be further described, in a specific embodiment, by way of example only and with reference to the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic perspective view of apparatus in accordance with the invention;
FIG. 2 is a schematic perspective exploded view of the apparatus similar to the apparatus of FIG. 1 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to the drawings, the cut out apparatus comprises a wire winder unit 1 which has a single suction mount 2 . Mounted on-board the single suction mount 2 is a pair of spaced winder spools 3 , 4 and pair of spaced rotatably mounted guide pulley wheels 5 , 6 . The single suction mount 2 enables the wire winder unit 1 to be releasably and securely mounted to the vehicle windscreen (typically on the inside of the vehicle). The winder spools 3 , 4 are spaced to be positioned one on either side of a diameter line of the suction mount.
The suction mount 2 comprises a rigid plastics cup moulding 7 and an underlaying flexible rubber sucker membrane 8 . The flexible rubber sucker membrane 8 extends beyond the periphery of the rigid plastics cup moulding 7 in order to enhance the suction capability of the suction mount 2 . A suction device actuation/release lever side handle 9 enables consistent suction to be applied and released. As an alternative, it is possible that a pump actuated suction mount 2 could be employed such as disclosed in, for example,
The suction mount 2 is formed to have integral spaced side handles 10 , 11 . The side handles 10 , 11 extend substantially parallel to one another and in a direction transverse to the direction of spacing between the winder spools 3 , 4 .
The winder spools 3 , 4 are provided on board a winder spool mounting deck 14 which is bolted to the suction mount 2 . The deck 14 carries the pair of winding spools 3 , 4 in side by side relationship such that the wire receiving reel 4 a is underslung below the deck 14 . The winder spools 3 , 4 are connected to axial winding shafts which are supported in bearings provided on the deck 14 . The winder spools 3 , 4 are driven axially rotationally either manually via a hand winder or by means of a mechanical actuator such as a motorised winding or winching tool. Drive bosses 19 are provided with female sockets (square bores) for receiving the male driving tool. Positioned outwardly of the winding spools are respective wire guide pulley wheels 5 , 6 of low friction plastics material. The pulley wheels are mounted to be rotatable about respective rotational axes. The guide pulleys rotate as the cutting wire is drawn tangentially across the pulleys as will be described. The winder spools 3 , 4 are held to rotate in one direction only (each in opposite senses) by respective ratchet mechanisms 13 . Each mechanism includes ratchet override permitting prior tightened wire to be slackened, or unwound (reverse wound) the ratchets can be overridden by pulling out the ratchet release knobs 13 .
The guide pulley wheels 5 , 6 are mounted to the rigid plastics cup moulding 7 , by means of pulley wheel mounting arms 12 , which are bolted to the rigid plastics cup moulding 7 . In one embodiment, the guide pulley wheels 5 , 6 are mounted by means of the pulley wheel mounting arms 12 in order that pulley wheel mounting arms 12 (and hence the guide pulley wheels 5 , 6 ) can be tilted about a pivot 15 with respect to the suction mount 2 and the winder spool mounting deck 14 . This enables the position of guide pulley wheels 5 , 6 to self align (tilt in direction of arrow A in figure wire winder unit 1 ) and provide a self adjustment as a result of windscreen glass curvature.
In the embodiment shown in FIG. 2 , a pair of mounting bolts 16 are used to secure the pulley wheel mounting arms 12 to the rigid plastics cup moulding 7 . In such an embodiment the pulley wheel mounting arms 12 do not pivot or tilt and accordingly, the guide pulley wheels 5 , 6 remain fixed (apart from being rotatable) with respect to the winder spool mounting deck 14 .
In use, the arrangement can be used in a generally similar manner to the winder unit described in FIGS. 9 to 1 of WO2006030212. Initially a flexible cutting wire is looped around the outside of a windscreen glazing panel to lie peripherally adjacent the bonding bead (typically a polyurethane bonding bead) which is sandwiched between the glazing panel and the support frame of the vehicle. Opposed ends of the cutting wire are fed through a pierced channel made through the bonding bead and the free ends are then each wound around a separate winder spool of the winder unit.
The glazing panel can as such be removed using a wire and the winder unit 1 only (no additional guide is required). In this technique the winder unit is initially secured to the steering wheel side of the glazing panel, positioned above the steering wheel. With the winder unit 1 in position as described, the cutting wire is looped around the outside of the windscreen to lie peripherally adjacent the bonding bead which is sandwiched between the glazing panel and the support frame of the vehicle. Opposed ends of the cutting wire are fed through a pierced channel made through the bonding bead in the corner of the windscreen below the position of the winder unit.
A length of the wire is pulled through to the interior of the vehicle and passed around pulley guide wheel 6 and secured to the reel 3 a of winder spool 3 of the winder unit. A free end length of wire is pulled through, being of length sufficient to reach the upper left hand corner of the glazing panel. Winder spool 3 is then operated to cause the wire length to cut through the bonding bead upwardly along the side of the windscreen, until the cut line has passed around the upper right hand corner of the screen. At this juncture, the unit is removed from the screen and repositioned on the glazing panel in the upper left hand corner.
Prior to repositioning the winder unit 1 , the ratchet of winder spool is released by means of the release knob 13 to permit the wire to be wound out from the winder spool 3 as it is moved across the glazing panel to be repositioned. The ratchet is subsequently re-engaged and spool 3 once again operated to wind in the wire.
Next the unit is moved around the corner of the glazing panel and through substantially a right angle, where it is secured to the glazing panel. In order to enable this to be achieved, the ratchet of spool 3 is again released and subsequently re-engaged. The end of the free length of wire is then wound around pulley 5 and connected to winder spool 4 and the spools operated either sequentially (or simultaneously) to complete the cut. The lengths of wire cross in order to complete the cut.
An important improvement over the prior art is that a single suction mount 2 only is used and that the pair of winder spools 3 , 4 are mounted on board the single suction mount 2 . The axes of the winder spools are positioned within a space defined by the projected diameter of the skirt of the sucker mount (that is the diameter of the sucker membrane 8 extends laterally beyond the position of the winder spool axes). This means that the space taken up on the windscreen by the wire winder unit 1 is reduced and also a single actuation only of the suction mount 2 is required, saving time and effort.
By mounting the pair of winder spools 3 , 4 directly over the flexible rubber sucker membrane 8 of the suction mount 2 , a suction mount 2 of large enough diameter to produce sufficient suction force can be used. In using the prior art apparatus as shown in, there is a risk that if one of the pair of spaced suction cups is not fully energised, the other has sufficient suction to hold the winder unit fixed in position when the wire is not under tension, but fails when the wire is tensioned during the winding process. | A winder unit is provided for use with cutting wire in cutting out a vehicle glazing panel. The winder unit includes first and second winder spools spaced apart from one another, where the winder spools are configured to wind the cutting wire. The winder unit further includes a suction mount for mounting the winder unit, wherein the suction mount comprises a single suction device only. And the winder unit further includes at least one wire guide element spaced from the winder spools, wherein the at least one wire guide element is mounted with respect to the winder unit so as to be adjustable in position or orientation with respect to at least one of the suction mount and the winder spools. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is related to Brewer, U.S. Provisional Patent Application No. 60/542,135, entitled “Live Animal Trap Assembly and Bucket Combination” filed on Feb. 05, 2004 and is incorporated by reference herein, with priority claimed for all commonly disclosed subject matter.
FIELD OF THE INVENTION
[0002] The present invention generally relates to the field of animal traps for live capture of animals.
RELATED ART
[0003] Animal traps of various kinds have been used throughout the history of man. In recent years there has been an increased need for traps that are used to capture animals for relocation and other purposes. The description of one such trap is contained in U.S. Pat. No. 6,609,327, issued Aug. 26, 2003 of Stoico. Other sources containing descriptions of animal traps include catalogs, manufacturer's literature, etc. that are available at sporting good stores and sports shows. The price of traps is variable, but it is desirable to keep the price as low as possible and at the same time still have a functional trap. The invention of Stoico has two doors, multiple actuation arms and springs and is fairly complex. Many of the traps in catalogs and at shows are complex and have a corresponding high cost. What is needed is a less expensive and less complex animal trap.
SUMMARY OF THE DISCLOSURE
[0004] Generally, the present invention provides a new apparatus and method for combining an inexpensive conventional bucket with a novel attachable trap assembly. In one embodiment the trap assembly mounts to the bucket with screws or rivets. The trap assembly has a gravity-actuated door that is released by a trigger rod located within the bucket and extending through a frame. The bucket rests on its side and is partially supported by the trap assembly.
[0005] Various features and advantages of the present invention will become apparent to one skilled in the art upon examination of the following detailed description, when read in conjunction with the accompanying drawings. It is intended that all such features and advantages be included herein within the scope of the present invention and protected by the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] The invention can be better understood with reference to the following drawings. The elements of the drawings are not necessarily to scale relative to each other, emphasis instead being placed upon clearly illustrating the principles of the invention. Furthermore, like reference numerals designate corresponding parts throughout the several views.
[0007] FIG. 1 illustrates an animal trap with a trap assembly coupled to a container.
[0008] FIG. 2 illustrates details of the trap assembly of FIG. 1 .
[0009] FIG. 3 illustrates a bucket that is combined with the parts shown in FIG. 2 to form the animal trap of FIG. 1 .
DETAILED DESCRIPTION
[0010] The present invention generally pertains to animal traps and uses a conventional heavy-duty bucket or other container in combination with a trap assembly 100 . The trap assembly may be fabricated with a variety of materials and is adapted to couple to a container such as a bucket as will be seen. In general, animal traps are dimensioned to correspond with the size of the animal to be trapped and a variety of baits may be used to attract the animal. Because a heavy-duty bucket, such as a high density polyethylene (“HDPE”) bucket, is generally inexpensive and tough enough to contain animals HDPE buckets are preferred as the container that is attached to the trap assembly of the present invention. Preferably the trap assembly is made of metal, chosen for high strength and low cost. Environmental factors must also be considered when selecting materials for the animal trap 100 described herein. For example, materials that are toxic or harmful in some way are considered undesirable. Any materials that have the strength and durability to contain an animal would fall within the scope of the present invention. Containers may have a variety of shapes, such as a cylindrical shape, a rectangular shape, and other known shapes.
[0011] Referring to FIG. 1 there is shown an animal trap 200 comprised of a bucket 6 and a trap assembly 100 . The bucket 6 is shown with part of its side removed for illustration purposes. The bucket 6 may be viewed more clearly in FIG. 3 . The trap assembly 100 is attached to the bucket 6 and is comprised of a door assembly 5 and a rod assembly 20 as illustrated in FIG. 1 .
[0012] In one embodiment the door assembly 5 has a door 10 attached to a frame 11 with hinges 12 . The door 10 , when not held in place by rod assembly 20 , may pivot between a horizontal position (the open position) as shown in FIG. 1 and a vertical position (the closed position) as shown in FIG. 2 . The frame 11 has an opening, preferably with a square shape, that is dimensioned slightly larger than the door 10 so that when the door is in the closed position it fits within the frame opening. Preferably the door has perforations, sized to allow fresh air in and small enough keep an animal contained. The frame 11 in one embodiment has a foot 18 on its bottom edge that rests on the ground and provides a stabilizing support for the animal trap 200 .
[0013] The door 10 of the door assembly 5 is shown in a horizontal or open position and is held in the open position by a hook 30 , generally J-shaped, on one end of a support rod 4 . The door is typically in either a fully open position as shown in FIG. 1 or in a fully closed position as shown in FIG. 2 . A carrying handle 9 is attached to the top edge of the frame 11 .
[0014] Still referring to FIG. 1 , a door lock bar 3 is shown near the top of the frame 11 and positioned under the support rod 4 . When the support rod 4 is moved in the x-direction (horizontally outward) the hook 30 of the support rod 4 no longer supports the door and gravity causes the door 10 to drop or swing down to the closed position. When the door 10 is in the closed position, gravity also pulls the lock bar 3 downward until it rests against bar stops 14 . The bar stops 14 limit the vertical drop of the lock bar 3 and thereby allow the lock bar to stay in a position that holds the door 10 closed. When the door 10 is closed and secured by the lock bar 3 , an animal is securely contained within the animal trap 200 . In one embodiment, the lock bar 3 and the bar stop 14 are attached together (when the door 10 is closed) with ties, twisted wire or some other well-known reversible connector. The handle 9 on the top of the door assembly 5 is provided as a grip for carrying the animal trap 200 . The door assembly 5 is preferably attached to the bucket 9 by screws, rivets, or other well-known means using the holes 7 on a flange 16 . The flange 16 extends horizontally from the back of the frame 11 (in the negative x-direction). The flange 16 preferably is dimensioned to fit snuggly within interior walls of the bucket 9 or other shaped container.
[0015] The rod assembly 20 is used to hold the door open using the hook on one end of the support rod 4 . The rod assembly 20 comprises the support rod 4 , an adjustment tube 2 and a trigger rod 1 . The trigger rod 1 is essentially L-shaped with one arm of the L oriented horizontally and the other arm oriented vertically. The adjustment tube 2 connects the support rod 4 to the trigger rod 1 with set screws. The adjustment tube 2 is a hollow cylinder whose interior diameter is dimensioned to accept one end of the support rod 4 and one end of the trigger rod 1 . The set screws extending with in the adjustment tube allow for adjustment of the horizontal length of the rod assembly as would be understood by those skilled in the art.
[0016] A food reservoir 8 is attached to the bottom end of the vertical leg of the trigger rod 1 . The food reservoir 8 holds bait to attract an animal and is dimensioned and shaped to move along the downward side of the bucket 9 . Preferably, the food reservoir 8 has a radius on its bottom edge that is about the same as the radius of the bucket 6 . When an animal enters the animal trap and pulls or moves the food reservoir 8 in the x-direction (outward direction) thereby moving the rod assembly 20 , the hook on the support rod 4 no longer supports the door 10 . When the door 10 pivots to a vertical position as seen in FIG. 2 then the door lock bar 3 drops downward thereby securing the door 10 in the closed position as described above.
[0017] Details of the door assembly 5 and the rod assembly 20 are shown more clearly in FIG. 2 . In FIG. 2 , the door 10 is shown in the closed position. The lock bar 3 preferably is a rod with a channel 40 on each end. In one embodiment, as shown, the channels 40 are formed by bending J-shapes in each end of the lock bar 3 . The channels are dimensioned to allow the lock bar 3 to slide freely up and down the vertical outside edges of the frame 11 . It is generally desirable that the lock bar 3 only be removable when pushed upward beyond the top edge of the frame 11 . The bar stops 14 prevent removal of the lock bar 40 from the bottom of the frame 11 .
[0018] It should be further emphasized that the above-described embodiments of the present invention, particularly, any “preferred” embodiments, are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the invention. Many variations and modifications may be made to the above-described embodiments of the invention without departing substantially from the spirit and principles of the invention. All such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims. | A live animal trap is described that uses a bucket as an animal container. A trap assembly is attached to the open end of the bucket. The trap assembly has a frame with a pivotally mounted door that is released when a food reservoir is moved towards the open end of the bucket. | 0 |
BACKGROUND OF THE INVENTION
Field of the Invention and Related Statement
The present invention concerns a tread rubber composition having excellent performance on ice and suitable to a studless tire, as well as a tire having a tread manufactured by using the rubber composition.
A spiked tire exhibits an excellent gripping force frozen road surface. Since the spiked tire has a large digging friction force, among hysteresis loss friction, adhesion friction and digging friction related to the gripping force between a tread rubber and a road surface, it exhibits an excellent gripping force on the frozen road surface.
However, use of the spiked tire has gradually been restricted legally as a countermeasure for public pollution caused by powdery dusts in recent years, and a studless tire with no spikes has been rapidly popularized. In some studless tires, the digging friction force is improved, for example, by incorporating a blowing agent or organic fibers therein thus increasing the unevenness on the surface of the tread. However, since the studless tire has lower digging friction force as compared with the spiked tire, its gripping force is still inferior to that of the spiked tire. In particular, if the road surface is ground flat by idle rotation of a tire upon starting on the frozen road surface, the gripping force of the studless tire is even more deteriorated, so that a further improvement has been demanded.
On a road surface with extremely low friction coefficient, such as a frozen road surface, the hysteresis loss friction is extremely small but adhesion friction (tract) also contributes to improvement of the gripping force, in addition to the digging friction. Therefore, it has been devised to increase the gripping force on the frozen road surface for the studless tire by increasing the other of the frictions contributing to the gripping force, that is, the tract.
As a method of improving the gripping force on the frozen road surface, there is a method of improving the tract by eliminating hydroplanes caused by thawing of the frozen road surface due to friction upon starting and braking, thereby increasing the area of contact between a tread rubber and an icy surface, or by making the rubber material softer to increase the area of contact with the road surface.
Increased unevenness on the tread surface can increase the digging friction, as well as can take up peripheral water into concave portions to eliminate hydroplanes. However, increase of the concave portions for the elimination of hydroplanning leads to a decrease in the area of contact with the icy surface, which is contrary to the improvement of the gripping force based on the increase in the area of contact, so that the effect is limited.
On the other hand, U.S. Pat. No. 4,522,970 discloses that a tread composition incorporating kaolinite clay and 3,3'-bis(trimethoxysilyl propyl)polysulfide in a certain rubber ingredient can improve wet skid resistance. However, tread rubbers for use in a studless tire in disclosed examples have an insufficient performance on ice. In addition, blending of the clay generally deteriorates the reinforcing performance of the rubber, and the rubber ingredient (butadiene and SBR) used for the tire in the disclosed examples shows large amounts of wear, which is not suitable for a tread rubber.
SUMMARY OF THE INVENTION
An object of the invention is to provide a tread rubber composition based on a diene rubber ingredient used customarily, and capable of improving the performance on ice within such a range as causing no problem in view of the reinforcing performance of a tread rubber, by improving the tract force by the elimination of hydroplanning and increase in the area of contact with a road surface.
The present inventors have developed a rubber composition of excellent hydrophobic property and water repellent property, in order to increase the area of contact between a tire and a road surface by reducing water-deposition on the surface of the tread and have accomplished the present invention.
Specifically, the tread rubber composition according to the present invention comprises a diene rubber comprising at least one rubber selected from the group consisting of natural rubber, polyisoprene and polybutadiene as a main ingredient and, based on 100 parts by weight of the diene rubber, 10 to 40 parts by weight of clay comprising kaolinite as a main clay ingredient and having an oil absorption amount of from 50 to 70 g/100 g and from 0.1 to 8 parts by weight of a silane coupling agent.
For a polymer, as a rubber ingredient in the tread rubber composition according to present invention, a diene rubber having a low glass transition point (Tg) and less curing even at a low temperature, specifically, natural rubber, polyisoprene or polybutadiene is used so as to ensure an area of contact even with a frozen road surface. The natural rubber, polyisoprene and polybutadiene may be used alone or in combination of two or more of them. If necessary, another diene polymer such as SBR may also be added.
In the tread rubber according to the present invention, a clay comprising kaolinite as a main clay ingredient and having an oil absorption amount of 50 to 70 g/100 g of the clay (hereinafter represented as a oil absorption amount of 50 g/100 g to 70 g/100 g) is blended, in order to eliminate hydroplanning between a tire surface and a road surface. The oil absorption amount used herein means an amount of oil absorbed into clay when the clay is immersed in the oil for a certain period of time, which is an indication of the state of a structure. If the oil absorption amount of the clay is less than 50 g/100 g, the reinforcing performance is insufficient when it is applied to the tread, tending to cause chipping or early wearing of the tread. On the other hand, if the oil absorption amount of the clay is more than 70 g/100 g, the size of clay coagulates is excessively small, in other words, the clay is in the form of a fine powder, making it impossible for pelletization and making handling difficult. Hard clay (oil absorption amount of about 20 g/100 to 40 g/100 g) has generally been known as a clay to be blended with the tire rubber composition. However, if the hard clay is applied to a tread rubber for a studless tire, it shows less improving effect for the performance on ice and snow and tends to cause insufficient reinforcing performance. Reduction of the rubber reinforcing performance Is not desirable since this causes deterioration of the wear resistance and deterioration of failure characteristics of the tire tread.
Any of clays capable of satisfying the foregoing requirements may be used in the present invention and clays sintered at 600° C. to 800° C. are preferred. Clays comprising kaolinite as the main ingredient sometimes have their hydro philic groups exposed on the surface or contain structured water in crystals. Then, when they are sintered at 600° C. to 800° C., they release the structured water to improve the hydrophobic property and contribute to the improvement of the water repellency of the tread rubber. Sintering at a temperature lower than 600° C. makes it difficult to release the structured water in the crystals and, on the other hand, sintering at a temperature higher than 800° C. tends to change the crystal structure of kaolinite. For further improving the water repellency of the clay, it is preferred to treat the clay with a silane coupling agent after sintering.
The content of the clay is from 10 to 40 parts by weight, preferably, from 10 to 30 parts by weight based on 100 parts by weight of the rubber ingredient. If the blending amount of the clay is more than 40 parts by weight, the reinforcing performance is deteriorated, particularly, at a low temperature, which is not preferred. On the other hand, if the blending amount of the clay is less than 10 parts by weight, no substantial improvement in the present invention for the gripping force on the frozen road surface is obtained.
Since the reinforcing performance of the rubber composition generally tends to be deteriorated by the blending of the clay, it is preferred to further blend a reinforcing agent such as a carbon black or silica in the rubber composition for use in the tread according to the present invention. In this case, the content of the clay is preferably from 15 to 80% by weight based on the total amount of the content of the reinforcing agent such as carbon black (total amount of the reinforcing agent) and the blending amount of the clay. The total amount of the reinforcing agent is preferably from 50 to 90 parts by weight based on 100 parts by weight of the rubber ingredient.
In the tread rubber composition according to the present invention, it is preferred to add a silane coupling agent for further improving the water repellency. Silane coupling agents which can be used preferably are represented by the formula X 3 SiR in which X represents an alkoxy group or a chlorine atom, R represents one of vinyl, glycide, methacryl, amino, mercapto, epoxy and imide groups, or represented by the formula:
(C.sub.n H.sub.2n+1 O).sub.3 --Si--(CH.sub.2).sub.m --S.sub.k --(CH.sub.2).sub.m --Si(C.sub.n H.sub.2n+1)O.sub.2
in which n represents an integer of 1 to 4, and m and k each represents an integer of 1 to 6. Such a silane coupling agent forms a chemical bond with organic and inorganic materials in the rubber composition respectively to combine the organic and inorganic materials at the boundary. The blending amount of the silane coupling agent is from 0.1 to 8 parts by weight, preferably, 0.1 to 5 parts by weight based on 100 parts by weight of the rubber in the rubber composition. If it is less than 0.1 parts by weight, no substantial effect can be obtained, whereas if it is more than 8 parts by weight, material cost will be increased.
The silane coupling agent may be added alone in the composition, or it may be added as a clay treating gent. Addition as the clay treating agent is more effective. Namely, if the clay is previously treated with the silane coupling agent and then blended into the rubber composition, the hydrophobic property and the water repellency of the clay can act by way of the silane coupling agent, so that hydrophobic moieties can be converted into portions having the hydrophobic property in the rubber composition (not only the rubber ingredient but also the blending agents described later), to provide the tread rubber itself with the water repellency. When the tread rubber itself is provided with the water repellency, hydroplanning between ice and the tread rubber can be suppressed and water droplets deposited at the surface of the tread rubber can be removed easily. As a result, a substantial area of contact between the tread rubber and the ice is increased to increase the tract. That is, the gripping force on the iced road surface is improved.
The rubber composition according to the present invention may further contain, in addition to the compounds described above, other customary blending agents used in rubber industry such as vulcanizer, vulcanization promoter, vulcanization promotion aid, aging inhibitor and softening agent. Further, in order to improve the hydroplane eliminating effect or digging friction to the road surface, organic fibers may be incorporated or a blowing agent may be added to cause blowing upon manufacture of the tire.
As has been described above, in the tread rubber composition according to the present invention, since a predetermined amount of the clay having the oil absorption amount within a predetermined range is blended together with the silane coupling agent, it has the water repellency and the hydrophobic property with no substantial deterioration of the reinforcing performance. In particular, when the clay is previously treated with the silane coupling agent and then blended, since the hydrophobic property of the tread rubber itself can be improved, it can contribute to the improvement of the area of contact with the icy road surface to increase the tract and shows excellent performance on ice. Further, when the clay sintered at about 600° C. is used, it can exhibit the water repellency and the hydrophobic property effectively. Further, when a reinforcing agent such as carbon black is blended in a predetermined amount, deterioration of failure characteristics can be suppressed.
Accordingly, the tread rubber composition according to the present invention is most suitable to a tread rubber composition for use in a studless tire to which a demand for the failure characteristics and wear resistance is not so severe but a demand for the braking performance on ice and snow is severe. Then, the tire having the tread manufactured by using the tread rubber composition according to the present invention has excellent performance on ice.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an explanatory view for an angle of contact; and
FIG. 2 is a view illustrating a system used for measuring the angle of contact.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be explained more specifically with reference to preferred embodiments.
Rubber compositions of Examples 1 to 5 and Comparative Examples 1 to 6 were prepared by blending polymers and various kinds of additives shown in Table 1 and further blending various kinds of blending agents (clay mainly composed of kaolinite, carbon black and silane coupling agent) each in by an amount shown in Table 2.
As the polybutadiene shown in Table 1, UBEPOLE BR 150L (trade name of products manufactured by Ube Industries Ltd.) was used. OZONON 6C (N-phenyl-N-(1,3-dimethylethyl)-p-phenylene diamine) manufactured by Seko Kagaku Co. was used as an aging inhibitor. NOCSELLER NS(N-tert-butyl-2-benzothiazyl sulfeneamide) manufactured by Ohuchi Shinko Kagaku Co. was used as a vulcanization promoter.
As the carbon black shown in Table 2, SHOWBLACK N 220 manufactured by Showa Cabot Co. was used. Three types of clays A, B and C were used as the clay. Both of clays A and B are amorphous meta-kaolin sintered at 600° C. and having the oil absorption amount of 55 g/100 g. Clay C is referred to as a hard clay having an oil absorption amount of 40 g/100 g. Both of clay B and clay C were treated with a silane coupling agent of vinyl-tri(t-methoxyethoxy) silane and contained 1% by weight of the silane coupling agent. In Example 6 and Comparative Example 2, Si69 manufactured by DEGUSSA Co. was added as the silane coupling agent. Si69 is bis(triethoxysilylpropyl)tetra-sulfene. In the preparation of the rubber compositions, a process oil was blended by an amount shown in Table 2 for making the hardness of the compositions equal to each other in each of the examples and the comparative examples.
Vulcanized rubber test pieces were prepared by using the thus prepared rubber compositions, and the failure characteristics and the angle of contact with water were evaluated by the following methods. Further, studless tires of 165R13 were manufactured by using the rubber compositions described above and the performance on ice of the tires was evaluated by the following method. The results are shown together in Table 2.
TABLE 1______________________________________ Blending amount (parts by weight)______________________________________Natural rubber 70 Polybutadiene 30 Stearic acid 3 Zinc powder 3 Aging inhibitor 1 Sulfur 1.5 Vulcanization promoter 0.5______________________________________
Evaluation Method
Failure Characteristics
Rubber tearing strength was measured according to JIS K6301. Assuming the measured value as 100 for the tearing strength of a rubber composition not containing clay and silane coupling agent (Comparative Example 1), measured values for the tearing strength of other rubber compositions were represented each by an index. A small index value shows lower failure characteristics. Since a demand for the failure characteristics on ice and snow road surface is not so severe as compared with that on usual road surface, there is no practical problem as the tread for the studless tire so long as the failure characteristics exceed about 80.
Performance on Ice
Studless tires of 165R13 (inner pressure: 2 kgf/cm 2 ) were manufactured by using the rubber compositions described above and the tires were mounted to a 1500 cc front wheel driven (FF) anti-lock braking system (ABS) car and measured under the following conditions:
Place of measurement:
Nayoro test course of Sumitomo
Rubber Industries, Ltd.
(Iced surface road)
Atmospheric temperature:-6.5° C.
Ice temperature:-4.0° C.
In the measurement, the car was caused to run at a speed of 30 km/h and then braked rapidly to determine a distance from the instance the wheels were locked till stopping of the car. Assuming the stopping distance in Comparative Example 1 as 100, stopping distances measured for other examples and comparative examples were indicated each by an index. As the index value is smaller, it shows better performance on ice.
Angle of Contact
The angle of contact means an angle θ formed at a boundary at which rubber 1 and water droplet 2 are in contact with each other in a state where the droplet 2 is deposited to the surface of the rubber 1. This represents the wettability of water to rubber. As the angle of contact is larger, the tire is less wettable and the water repellency of the rubber is excellent.
Using the system shown in FIG. 2, cosine for the angle of contact was measured for forwarding and backwarding movement to determine the angle of contact according to the following equation:
θ=cos.sup.-1(1/2×(cos θa+cos θr))
in which θa is an angle of contact upon forwarding and θr represents an angle of contact upon backwarding.
Assuming the value for the angle θ in Comparative Example 1 as 100, angles θ for other examples and comparative examples were represented each by an index. As the index value is greater, the angle of contact is larger (more blunt angle).
TABLE 2__________________________________________________________________________ Example Comparative example 1 2 3 4 5 1 2 3 4 5 6__________________________________________________________________________Process oil 0 4 8 12 6 0 0 2 16 8 4 Carbon black 50 50 50 50 50 55 10 50 50 50 50 (parts by weight) Silane coupling agent 0.1 0.2 0.3 0.4 2 -- 8 0.05 0.5 0 0 (parts by weight) Clay Clay A (parts by weight) -- -- -- -- 30 -- 80 -- -- 30 Clay B (parts by weight) 10 20 30 40 -- -- -- 5 50 -- -- Clay C (parts by weight) -- -- -- -- -- -- -- -- Clay content (wt %) 17 29 38 44 38 -- 89 9 50 38 29 Evaluation Performance on ice 96 92 90 88 92 100 86 100 87 95 102 Failure characteristics 97 94 89 81 92 100 54 99 70 80 85 Angle of contact 102 105 108 110 103 100 116 100 113 104 98__________________________________________________________________________
Evaluation
As can be seen from Table 2, rubber compositions in which clay A or clay B each having the oil absorption amount within the range of the present invention were blended by more than 10 parts by weight (examples and Comparative Examples 2, 4, 5) had excellent performance on ice as compared with a rubber composition in which the clay was not blended at all (Comparative Example 1) or the clay was blended only by an insufficient amount (Comparative Example 3) or, a rubber composition in which the clay C blended therewith had the oil absorption amount out of the range of the present invention (Comparative Example 6). On the other hand, the failure characteristics tend to be deteriorated by the blend of the clay. The deterioration of the failure characteristics could be kept within a practically allowable range at the blending amount of the clay of less than 40 parts by weight (examples), whereas the failed characteristics were reduced excessively in the rubber composition at the blending amount of the clay of more than 40 parts by weight (Comparative Examples 2, 4). Particularly, if the blending amount of the carbon black as the reinforcing agent was insufficient, deterioration of the failure characteristics was inevitable even if a great amount of silane coupling agent was blended (Comparative Example 2). Further, even if a clay having the oil absorption amount within the range of the present invention was blended by an amount within the range of the present invention, if the silane coupling agent was not blended in the rubber composition (Comparative Example 5), a problem resulted in the failure characteristics from a practical point of view. Accordingly, the performance on ice can be improved while keeping the failure characteristics within a practically allowable range by blending a clay having the oil absorption amount within the predetermined range in an amount within the predetermined range. Further, it can be seen that blend of the carbon black by more than 50% by weight is preferred for ensuring failure characteistics with safety.
Further, it can be seen from comparison between Example 3 and Example 5 that the performance on ice can be improved more by blending the silane coupling agent not alone but in a state used for the treatment of the clay.
Further, it can be seen in Examples 1-5 that the angle of contact is increased in proportion with the blending amount of the clay treated with the silane coupling agent to improve the performance on ice. It can thus be seen that the silane coupling agent bonded with the clay by previously treating the clay acts on the hydrophilic portion in the rubber composition together with the clay to effectively improve the water repellency of the tread rubber. Furthermore, it can also be seen from comparison between Example 5 and Comparative Example 5 that blending of the silane coupling agent contributes not only to the improvement of the failure characteristics together with the clay but also to the improvement of the performance on ice by the synergistic effect with the clay. | A tread rubber composition of excellent hydrophobic property and water repellency suitable to a studless tire of excellent performance on ice, comprising a diene rubber comprising at least one rubber selected from the group consisting of natural rubber, isoprene and polybutadiene as a main ingredient and, based on 100 parts by weight of the diene rubber, from 10 to 40 parts by weight of a clay comprising kaolinite as a main ingredient and having an oil absorption amount of from 50 to 70 g/100 g and 0.1 to 8 parts by weight of a silane coupling agent. | 2 |
BACKGROUND OF THE INVENTION
[0001] The present invention is directed to a diverter/singulator for closures in a closure feed system. More particularly, the present invention pertains to a diverter/singulator for a closure feed system for use in a form, fill, and seal packaging machine, in which closures are mounted to packages.
[0002] Many containers such as cartons are formed with integral spouts. For example, many known gable-top cartons feature resealable spouts mounted to one of the gable panels to facilitate dispensing contents from the carton and resealing the carton after use.
[0003] Packaging machines must mount spouts to the cartons at some point during their forming, filling, and sealing processes. To this end, packaging machines often include applicator stations, at which a spout is dispensed from a feed system, directed or diverted to an applicator and moved into contact with a carton. The applicator typically includes a sealing device, such as an ultrasonic sealing or welding head, which moves into contact with the carton while an accompanying closure rests on an anvil that also is moved into contact with the carton. Energy transmitted from the sealing device into the carton material above the spout seals the spout to the carton.
[0004] Because many modern packaging machines operate at high speeds (some at speeds up to about 14,000 packages per hour), one concern is that the spouts or closures must be dispensed at a rate commensurate with the overall speed of the packaging machine, while precisely and accurately dispensing closures for proper positioning within the applicator. Known dispensing arrangements may be subject to frequent clogs or bottlenecks in their spout feed lines, slowing the machines or requiring that they be shut down entirely in order to free obstructions. In addition, such high-speed machines often include parallel trains or lines of form, fill and seal stations. That is, the machines include two forming stations, two filling stations and two sealing stations that are side-by-side within the machine enclosure and operate in parallel. This is referred to as a dual-train form, fill and seal packaging machine.
[0005] Prior art closure feed systems generally rely on gravity, allowing spouts to fall through a single chute on to a reciprocating anvil in the applicator station. Shingling, in which the thin flanges surrounding a spout overlap one another and cause skewing, frequently cause jamming within such closure feed system, by allowing more than one closure to drop into position on the anvil. In addition, such systems require a diverter to direct or divert closures from a common supply to the individual reciprocating anvils.
[0006] United States patent application publication No. US 2002/0073648 A1 (the '648 publication), assigned to the assignee of the present invention, attempts to address the jamming problems caused by closure shingling with closure feed systems that includes a singulator with upper and lower reciprocating members, or plungers. The plungers reciprocate in an opposing manner to one another, so that when the upper plunger is retracted, the lower plunger is extended, and when the upper plunger is extended, the lower plunger is retracted. The plungers prevent closure shingling by providing physical barriers between closures in the feed system queue. Though this system prevents the blockages caused by closure shingling, it nevertheless requires a separate system for each of the form, fill and seal trains. Moreover, additional space is required to house the reciprocating plungers, the other components for each of the singulators.
[0007] Accordingly, there exists a need for a simple closure feed system that prevents closure jamming and bottlenecks. Desirably, such a closure feed system dispenses a single closure at a time for receipt by a closure applicator. More desirably, such a system requires little space and a minimum of mechanical parts. Most desirably, such a system singulates the closures or spouts by alternately sliding spouts from a common chute into two separate chutes to accomplish diverting the closures (to the two trains of the dual train form, fill and seal machine) in a unit common with the singulating function.
BRIEF SUMMARY OF THE INVENTION
[0008] A closure feed system for use on an associated dual train form, fill, and seal packaging machine for feeding, diverting and singulating closures from a common closure storage region to respective (train-dedicated) closure applicators includes an upper chute, first and second lower chutes, and a diverter/singulator. The upper chute conveys closures from the storage region to the diverter/singulator, and defines an upper conveyance path. The first and second lower chutes convey separated closures from the diverter/singulator to the applicator, and define first and second lower conveyance paths, respectively.
[0009] The diverter/singulator includes a reciprocating plate that has first and second main closure-holding grooves. The plate is configured for sliding between the upper and lower chutes, so that when the first groove is aligned with (e.g., located under) the upper chute the second groove is aligned with (e.g., over) the second lower chute, and when the second groove is aligned with (e.g., located under) the upper chute the first groove is aligned with (e.g., over) the first lower chute.
[0010] In a preferred embodiment, a first minor groove lies within the first main groove, and a second minor groove lies within the second main groove. The minor grooves accommodate an aligning pin, such as that that can be used on an orientationally sensitive closure. A cylinder, most preferably a pneumatic cylinder, is used to reciprocate the plate.
[0011] The closure feed system can include a frame for carrying the upper chute, the diverter/singulator, and the first and second lower chutes together. Preferably, the plate slides within a guide on the frame. The frame can also include a lidded aperture positioned under the upper chute, to allow the discharge of a queue of closures from the upper chute.
[0012] A dual train form, fill, and seal packaging machine for forming, filling, and sealing packages in two parallel trains that feature a flanged, carton-mounted closure is also disclosed. The machine includes a carton magazine, a carton erection station, a closure applicator station, two filling stations, and two top sealing stations. The closure applicator station includes a closure storage region and two train-dedicated closure applicators, as well as an upper chute, first and second lower chutes, and a diverter/singulator. The upper chute conveys closures from the storage region to a diverter/singulator, and defines an upper conveyance path. The first and second lower chutes convey separated closures from the diverter/singulator to the respective applicators, and define first and second lower conveyance paths, respectively.
[0013] These and other features and advantages of the present invention will be apparent from the following detailed description, in conjunction with the appended claims.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0014] The benefits and advantages of the present invention will become more readily apparent to those of ordinary skill in the relevant art after reviewing the following detailed description and accompanying drawings, wherein:
[0015] FIG. 1 is a perspective view of an exemplary form, fill, and seal packaging machine having a closure feed system embodying the principles of the present invention;
[0016] FIG. 2 is a front view of a closure feed system having a closure diverter/singulator embodying the principles of the present invention, the system shown with closures positioned within the upper chute and the first lower chute;
[0017] FIG. 3 is a side view of the closure feed system of FIG. 2 , as seen from the right-hand side of FIG. 2 ;
[0018] FIG. 4 is a top view of the closure feed system of FIG. 2 ;
[0019] FIG. 5 is a bottom view of the closure feed system of FIG. 2 ; and
[0020] FIG. 6 illustrates an exemplary closure suitable for use with the present closure feed system.
DETAILED DESCRIPTION OF THE INVENTION
[0021] 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 with the understanding that the present disclosure is to be considered an exemplification of the invention and is not intended to limit the invention to the specific embodiment illustrated.
[0022] It should be further understood that the title of this section of this specification, namely, “Detailed Description Of The Invention”, relates to a requirement of the United States Patent Office, and does not imply, nor should be inferred to limit the subject matter disclosed herein.
[0023] Referring to the figures and in particular to FIG. 1 , there is shown a known form, fill, and seal packaging machine 10 . The packaging machine 10 includes a closure feed system, indicated generally at 12 , embodying the principles of the present invention. The form, fill, and seal packaging machine 10 includes a carton magazine 14 for storing flat, folded cartons prior to erection. The machine 10 further includes a carton erection station 16 , a bottom flap sealing station 18 , and a closure applicator station 20 . The closure applicator station 20 preferably includes a closure storage region 22 , a closure applicator 24 , and the closure feed system 12 . Subsequent to closure application, cartons may be sterilized, filled at a filling station 25 , and sealed at a top sealing station 26 to form a well-known gable-top shape. Finally, cartons are off-loaded from the machine 10 . The construction and design of an exemplary machine is disclosed in Katsumata, U.S. Pat. No. 6,012,267, which patent is assigned to the assignee of the present invention, and which patent is incorporated herein by reference for purposes of that patent's disclosure of such a machine. The illustrated machine is a dual-train machine. That is, the machine includes two forming stations (as illustrated by the two mandrel wheels 27 a, 27 b ), two filling stations 25 a,b and two sealing stations 26 a,b that are side-by-side within the machine 10 enclosure and operate in parallel.
[0024] As shown in FIG. 1 , closures 28 (the closures are not seen in FIG. 1 ) are fed from a common closure storage unit or region 22 , such as a bin, into the common closure feed system 12 . As seen in FIGS. 2-5 , the closure feed system 12 , which functions to feed closures 28 to both of the operating form, fill and seal trains, includes a plurality of rails 30 , 32 , and 34 that define an upper chute 36 and first and second lower chutes 38 , 40 respectively for the closures 28 . A typical closure 28 , as illustrated in FIG. 6 , includes a spout 42 that extends upwardly from one side 44 of a flange 46 . The flange 46 has a diameter d f that is substantially larger than a diameter d s of the spout 42 .
[0025] Returning to FIGS. 2-5 , the upper chute 36 defines an upper conveyance path 48 , and the first and second lower chutes 38 , 40 define first and second lower conveyance paths 50 , 52 respectively. Closures 28 maintain a desired orientation while moving through the upper and lower conveyance paths 48 , 50 , 52 of the upper and lower chutes 36 , 38 , 40 because sides of their flanges 46 are bound by narrow openings or gaps (see, e.g., gap 35 in FIG. 3 ) between adjacent pairs of rails 30 , 32 , 34 of the upper and lower chutes. The spouts 42 of the closures 28 extend through larger openings or gaps between opposing pairs of the rails 30 , 32 , 34 (see, e.g., opening 33 in FIG. 2 ).
[0026] The upper chute 36 guides the closures 28 from the storage unit or region 22 to a diverter/singulator 54 . After being separated by the diverter/singulator 54 , the closures 28 are directed through the first and second lower chutes 38 , 40 to their respective applicators (one for each train, as indicated generally at 24 ). A frame 56 preferably holds the upper chute 36 , the first and second lower chutes 38 , 40 , and the diverter/singulator 54 mounted together. The diverter/singulator 54 includes a reciprocating plate 58 , which has first and second main closure-holding grooves 60 , 62 . It will be appreciated by those skilled in the art that the present diverter/singulator permits using a single component to diverter closures 28 to each of the trains (the a train and the b train) and, at the same time, singulates the closures 28 to separate the closures 28 from one another.
[0027] The plate 58 is configured for sliding between the lower chutes 38 , 40 , so that when the first main groove 60 is under the upper chute 36 (for receiving a closure), the second main groove 62 is aligned over the second lower chute 40 , and when the second main groove 62 is under the upper chute 36 (for receiving a closure), the first main groove 60 is aligned over the first lower chute 38 . A first minor groove 64 preferably lies within the first main groove 60 , and a second minor groove 66 may lie within the second main groove 62 . The main grooves 60 , 62 are dimensioned to accommodate the closure spout 46 . For those systems that may be used to transport an orientationally sensitive closure having, for example, an aligning pin 47 extending from the rear of the flange 46 , the minor grooves 64 , 65 , 66 accommodate the pin 47 and maintain the orientation of the closure 28 as it traverses through the chutes 36 , 38 , 40 .
[0028] As described above, one of the problems encountered in known closure feed systems is that closure flanges tend to shingle as the closures travel through chutes, held between the rails. To this end, the present closure feed system 12 overcomes these problems by using a diverter/singulator 54 to physically separate closures 28 along two lower conveyance paths 50 , 52 . In that the physical separation of the closures 28 occurs substantially in the plane parallel to the plane of the flanges 46 , damage to the flanges 46 (due to “forced” separation) is prevented.
[0029] Operation of the closure feed system 12 is simple and straightforward. Closures 28 enter the upper conveyance path 48 through the upper chute 36 , their flanges 46 confined between adjacent pairs of rails 30 . The closure spouts 42 extend through the larger opening or gap between opposing pairs of the rails 30 . After a closure 28 has traveled through the upper chute 36 , it reaches the diverter/singulator 54 .
[0030] The reciprocating plate 58 of the diverter/singulator 54 laterally slides between the upper chute 36 and the lower chutes 38 , 40 . The sliding of the plate 58 can be limited by a guide 68 located on the frame 56 . The illustrated plate 58 is driven by a cylinder 70 , such as the exemplary pneumatic cylinder. For this description, it will be assumed that the first main groove 60 of the plate 58 is initially located under the upper chute 36 , but the closure feed system 12 may commence operation with the plate 58 in any position along the guide 68 .
[0031] A first closure 28 a exits the upper chute 36 into the first main groove 60 of the plate 58 . Sides of the first main groove 60 confine the flanges 46 of the first closure 28 a, much like the adjacent pairs of rails 30 of the upper chute 36 . The plate 58 then laterally slides, moving the first main groove 60 into a position over the first lower chute 38 . When the first main groove 60 is in place over the first lower chute 38 , the first closure 28 a falls out of the first main groove and into the first lower conveyance path 50 . The main grooves 60 , 62 are spaced from one another so that when the first main groove 60 is aligned over the first lower chute 38 , the second main groove 62 is located under the upper chute 36 . Concurrently, a second closure 28 b falls out of the upper chute 36 and into the second main groove 62 of the plate 58 .
[0032] Again, in those instances in which a closure with an aligning (orienting) pin 47 is used, the pin 47 is aligned with minor groove 65 in the upper chute 36 and, as the closure 28 falls though the upper chute 36 and is diverted by the plate 58 , the pin 47 remains aligned and “falls” into minor groove 64 , in first lower chute 38 . The pin 47 remains in the 12 o'clock position (by virtue of the eccentric location of the pin 47 and gravity acting on the closure 28 ), thus maintaining the orientation of the closure 28 .
[0033] Next, the plate 58 laterally slides again, this time moving the second main groove 62 into a position over the second lower chute 40 . When the second main groove 62 is in place over the second lower chute 40 , the second closure 28 falls out of the second main groove and into the second lower conveyance path 52 . As the second closure 28 b exits the second main groove 62 , a third closure 28 c drops into the first main groove 60 from the upper chute 36 . The plate 58 reciprocates, and the process begins anew. And, if an orientationally sensitive closure is used, the pin traverse into minor groove 66 in second lower chute 40 .
[0034] In addition, the frame 56 can include a lidded aperture (not shown), located directly under the upper chute 36 . This aperture permits closure feed system operators to empty the upper chute 36 of its queue of closures 28 to perform maintenance on the system, when the reciprocating plate 58 is slid fully to one side.
[0035] All patents referred to herein, are hereby incorporated herein by reference, whether or not specifically done so within the text of this disclosure.
[0036] In the present disclosure, the words “a” or “an” are to be taken to include both the singular and the plural. Conversely, any reference to plural items shall, where appropriate, include the singular.
[0037] From the foregoing it will be observed that numerous modifications and variations can be effectuated without departing from the true spirit and scope of the novel concepts of the present invention. It is to be understood that no limitation with respect to the specific embodiments illustrated 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. | A closure feed system for use on an associated dual train form, fill, and seal packaging machine for feeding, diverting and singulating closures from a common closure storage region to a closure applicator includes an upper chute for conveying the closures from the storage region to a diverter/singulator, two lower chutes for conveying separated closures from the diverter/singulator to respective applicators, and a diverter/singulator for diverting and separating the closures. The upper chute defines an upper conveyance path, while the two lower chutes define two lower conveyance paths to their respective applicators. The diverter/singulator includes a reciprocating plate with two closure-holding grooves. As the plate slides between the upper and lower chutes, the grooves alternately align with the upper chute, or with the first or second lower chutes. A form, fill, and seal packaging machine including the closure feed system is also disclosed. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the papermaking arts. More specifically, the present invention relates to through-air-drying (TAD) fabrics used in the manufacture of bulk tissue and towel, and of nonwoven articles and fabrics.
2. Description of the Prior Art
Soft, absorbent disposable paper products, such as facial tissue, bath tissue and paper toweling, are a pervasive feature of contemporary life in modern industrialized societies. While there are numerous methods for manufacturing such products, in general terms, their manufacture begins with the formation of a cellulosic fibrous web in the forming section of a paper machine. The cellulosic fibrous web is formed by depositing a fibrous slurry, that is, an aqueous dispersion of cellulose fibers, onto a moving forming fabric in the forming section. A large amount of water is drained from the slurry through the forming fabric, leaving the cellulosic fibrous web on the surface of the forming fabric.
The cellulosic fibrous web is then transferred to a through-air-drying (TAD) fabric or belt by means of an air flow, brought about by vacuum or suction, which deflects the web and forces it to conform, at least in part, to the topography of the TAD fabric or belt. Downstream from the transfer point, the web, carried on the TAD fabric or belt, passes through a through-air dryer, where a flow of heated air, directed against the web and through the TAD fabric or belt, dries the web to a desired degree. Finally, downstream from the through-air dryer, the web may be adhered to the surface of a Yankee dryer and imprinted thereon by the surface of the TAD fabric or belt, for further and complete drying. The fully dried web is then removed from the surface of the Yankee dryer with a doctor blade, which foreshortens or crepes the web and increases its bulk. The foreshortened web is then wound onto rolls for subsequent processing, including packaging into a form suitable for shipment to and purchase by consumers.
As noted above, there are many methods for manufacturing bulk tissue products, and the foregoing description should be understood to be an outline of the general steps shared by some of the methods. For example, the use of a Yankee dryer is not always required, as, in a given situation, foreshortening may not be desired, or other means, such as “wet creping”, may have already been taken to foreshorten the web.
It should be appreciated that TAD fabrics may take the form of endless loops on the paper machine and function in the manner of conveyors. It should further be appreciated that paper manufacture is a continuous process which proceeds at considerable speeds. That is to say, the fibrous slurry is continuously deposited onto the forming fabric in the forming section, while a newly manufactured paper sheet is continuously wound onto rolls after it is dried.
Those skilled in the art will appreciate that fabrics are created by weaving, and have a weave pattern which repeats in both the warp or machine direction (MD) and the weft or cross-machine direction (CD). Woven fabrics take many different forms. For example, they may be woven endless, or flat woven and subsequently rendered into endless form with a seam. It will also be appreciated that the resulting fabric must be uniform in appearance; that is, there are no abrupt changes in the weave pattern to result in undesirable characteristics in the formed paper sheet. In addition, any pattern marking imparted to the formed tissue will impact the characteristics of the paper.
Contemporary papermaking fabrics are produced in a wide variety of styles designed to meet the requirements of the paper machines on which they are installed for the paper grades being manufactured. Generally, they comprise a base fabric woven from monofilament and may be single-layered or multi-layered. The yarns are typically extruded from any one of several synthetic polymeric resins, such as polyamide and polyester resins, used for this purpose by those of ordinary skill in the paper machine clothing arts.
The present application is concerned, at least in part, with the TAD fabrics or belts used on the through-air dryer of a bulk tissue machine although it may have other applications beyond this. However, the present application is primarily concerned with a TAD fabric.
such fabric may also have application in the forming section of a bulk tissue or towel machine to form cellulosic fibrous webs having discrete regions of relatively low basis weight in a continuous background of relatively high basis weight. Fabrics of this kind may also be used to manufacture nonwoven articles and fabrics, which have discrete regions in which the density of fibers is less than that in adjacent regions whereby the topography of the nonwoven article is changed, by processes such as hydroentanglement.
The properties of absorbency, strength, softness, and aesthetic appearance are important for many products when used for their intended purpose, particularly when the fibrous cellulosic products are facial or toilet tissue, paper towels, sanitary napkins or diapers.
Bulk, cross directional tensile, absorbency, and softness are particularly important characteristics when producing sheets of tissue, napkin, and towel paper. To produce a paper product having these characteristics, a fabric will often be constructed so that the top surface exhibits topographical variations. These topographical variations are often measured as plane differences between strands in the surface of the fabric. For example, a plane difference is typically measured as the difference in height between a raised weft or warp yarn strand or as the difference in height between MD knuckles and CD knuckles in the plane of the fabric's surface. Often, the fabric surface will exhibit pockets in which case plane differences may be measured as a pocket depth.
Additionally, drying capability of an industrial fabric is very essential for its use in processes such as TAD. Typically, a standard TAD fabric design in the papermaking industry for making paper towel, which is a 5-shed, 3×2 weave pattern. This design exhibits higher sheet caliper and absorbency, which allows lower sheet basis weight. The other design that is typically used in toilet tissue production is a 5-shed, 4×1 weave pattern which has demonstrated to result in a higher sheet softness. Both designs have proven to be robust in the hot, humid, TAD environment with better sheet properties. Fabric designers realize that pocket depth formed by the weave pattern is also important so multilayer thicker fabrics have been tried. However, these multilayer designs pose some serious drawbacks, such as increased fabric water content as they generally carry more water, which results in higher drying time. The primary mechanism for producing low density high caliper tissue webs with the TAD process is the pocket depth of the fabric. Therefore, it is the pocket depth of the fabric that dictates the caliper of the tissue web. A close study of the designs discussed above showed that both warp and weft yarns are primarily responsible for the creation of the depth of the pocket, thus limiting sheet caliper generation. Particularly, in single layer designs, the weft yarns show better control of pocket depth than the warp yarns. It is therefore observed that changing the profile of the weft yarns to a triangle or substantially triangular shaped cross-section instead of the conventional round yarns results in an increase of pocket depth, leading to higher sheet caliper and other desirable sheet characteristics.
The present invention provides an improved TAD fabric which exhibits favorable characteristics for the formation of tissue paper and related products.
SUMMARY OF THE INVENTION
Accordingly, the present invention is a TAD fabric, although it may find application in the forming, pressing and drying sections of a paper machine. As such, it is a papermaker's fabric which comprises a plurality of warp yarns interwoven with a plurality of weft yarns.
The present invention is preferably a TAD fabric comprising a plurality of warp yarns interwoven with a plurality of weft yarns to produce a paper-side surface pattern characterized by pockets of higher depth and volume for the same mesh and count. In the fabric according to the present invention, the weft yarns have a triangular cross-section or substantially triangular shaped cross-section and are oriented with their flat surface facing a machine side surface of the fabric. The points interlacing with the warp as they pass over and under the triangular shaped weft yarns produce increased pocket depth and volume in the TAD fabric.
It is therefore an object of the present invention to increase pocket depth and pocket volume of an industrial fabric in order to improve sheet properties such as sheet caliper, bulk and absorbency in TAD or other sheet forming type processes that utilize a TAD or structured fabric to imprint a pattern into the sheet.
It is another object of the present invention to increase the air permeability of the fabric and thus a more efficient operation.
It is a further object of the present invention to improve sheet drying rate and therefore reduce energy consumption.
It is yet another object of the present invention to improve the cleanability of the fabric.
The present invention will now be described in more complete detail with frequent reference being made to the drawing figures, which are identified below.
BRIEF DESCRIPTION OF THE DRAWING
For a more complete understanding of the invention, reference is made to the following description and accompanying drawings, in which:
FIG. 1A shows a paper side view and a surface depth view highlighting the relative pocket sizes on the paper side surface of a preferred embodiment of the present invention.
FIGS. 1B and 1C show cross-sectional views of a fabric incorporating the teachings of the present invention;
FIG. 1D shows a cross-sectional view of a standard TAD fabric; and
FIG. 2 shows a “house” shaped cross-section of a yarn.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention is preferably a TAD fabric having improved pocket depth and pocket volume on the paper side surface of the fabric. The pocket sizes are a function of the weave pattern, mesh count, and yarns used in the pattern. Pocket sizes can be characterized by an MD/CD dimension and/or by a pocket depth. The pockets are formed/bounded by weft yarns and warp yarns which are raised from the base plane of the fabric surface, produced by the weave pattern utilized. Pocket size and depth affect resultant sheet properties such as absorbency amongst others.
FIG. 1A shows a paper side view and a surface depth view highlighting the relative pocket sizes on the paper side surface of a preferred embodiment of the present invention. As shown in FIG. 1A a fabric 50 according to this embodiment may be formed using weft yarns 20 having a triangular cross-section. While we refer to weft yarns as having a triangular cross-section in reality the cross-section would be that shown in FIG. 1B . As can be seen therein the weft yarns 20 have a somewhat or substantially triangular cross-section with slightly rounded edges 22 . While an equilateral triangular shape is shown having sides 24 , other triangular shapes suitable for the purpose may also provide the desired results. In FIG. 1A the triangular weft yarns 20 are shown to run horizontally and the warp yarns 10 run vertically. Weft yarns 20 may be oriented within fabric 50 in a manner such that a flat surface or side 24 of the triangle is facing the machine side of fabric 50 and a pointed side of the triangle is facing the paper or surface side of fabric 50 , with the points interlacing with the warp yarns 10 as they pass over and under the triangular weft yarns 20 producing increased pocket depth. FIG. 1C also shows the warp yarn 10 contour for the fabric pattern according to this embodiment. Note as to warp yarns 10 they are shown having a circular cross-section. Other shaped cross-sections suitable for the purpose are possible. As seen in this contour, the fabric 50 has deeper pockets 30 , 40 , which are correspondingly highlighted on the paper side surface of fabric 50 . It can be observed that the raised weft yarns 20 and raised warp yarns 10 indicated in the paper side surface of the fabric 50 form the pockets 30 , 40 at points where they interweave with each other or points interlacing with the warp as they pass over and under the triangular weft yarns 20 , producing increased pocket depths.
Orientation of the triangular weft yarns in this manner (flat surface facing the machine side) will also greatly change the bottleneck profile for both the 5-shed weave designs discussed in the background of the invention. This means, for a given mesh and count, the air permeability of the fabric will also increase. Therefore, by keeping the same mesh and count, the fabric according to the present invention will maintain its robustness in the hot, humid TAD environment, as well as result in increased sheet caliper and absorbency or softness, overcoming the drawbacks of the prior art.
In this regard for point of comparison, there is shown in FIG. 1D a cross-sectional view of a standard TAD fabric woven in the same weave pattern as that shown in FIG. 1B with, however, using yarns having circular cross-section yarns. The weft yarns have been designated 20 ′ and the warp yarns designated 10 ′. If one compares the pocket areas formed on FIG. 1D at 30 ′ and 40 ′ to the pockets 30 and 40 in FIG. 1B one can see that the pockets created are larger in the latter due to the substantially triangular shaped cross-section yarns. This can be seen, for example, in the open area between adjacent yarns which has been designated “X” in FIG. 1B and “Y” in FIG. 1D . Accordingly for the same linear density of yarns, larger pockets are formed in the fabric shown in FIG. 1B with the attendant advantages.
Note the fabric according to the present invention may be formed using any weave pattern, such as for example, plain, twill, sheet surface having floats weft or warp dominant or combinations thereof. The present invention is intended to cover other fabric patterns having different sizes and shapes of pockets, different pocket depths, and different yarn contours. Accordingly, the present invention should not be construed as being limited to the preferred embodiment disclosed above.
The fabric according to the present invention preferably comprises only monofilament yarns, preferably of polyester, nylon, polyamide, or other polymers. Any combination of polymers for any of the yarns can be used as will be appreciated by one of ordinary skill in the art. The CD yarns of the fabric may have a triangular cross-sectional yarns of different sizes and may alternate with yarns having different non-triangular cross-sections such as circular or other shapes. Such alternation can be single or in pairs or other combinations of yarns in even or odd numbers in a manner suitable for the purpose Similarly, the MD yarns may have a circular cross-section with one or more different diameters. Further, in addition to triangular and circular cross-sectional shapes, other shapes are envisioned such as the “house” shaped yarn 60 shown in FIG. 2 . Moreover some of the yarns, including the MD yarns may have other cross-sectional shapes such as a rectangular cross-sectional shape or a non-round cross-sectional shape such as triangular or substantially triangular.
Modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the scope of the present invention. The claims to follow should be construed to cover such situations. | A through-air-drying (TAD) fabric for producing tissue paper and related products on a papermaking machine comprising a plurality of warp yarns interwoven with a plurality of weft yarns to produce pockets on a paper-side surface of the fabric. The weft yarns have a substantially triangular cross-section and are oriented with their flat surface facing a machine side surface of the fabric. The points interlacing with the warp as they pass over and under the weft yarns produce an increased pocket depth and volume in the TAD fabric. | 3 |
FIELD OF THE INVENTION
The present disclosure generally relates to vise pads useful for accurate alignment of work pieces in a vise containing apparatus such as milling machines.
BACKGROUND OF THE INVENTION
One of ordinary skill in the art understands that performing meticulous processes and procedures on a work piece requires accurate alignment when fixing such a work piece is necessary. Conventional vises as illustrated in FIG. 1 includes a main body 1 having a vise jaw 3 (a claw for clamping a work piece), a moving element 2 having a vise jaw which corresponds to the vise jaw 3 and a screw bar 5 for transport of the moving element back and forth.
Problematically, when mounting and fixing a work piece on such a vise, the vise jaw at the moving element may clamp a work piece 6 at a slant. This results in inaccurate fixation of a work piece when parallel clamping is required. Improper clamping is caused by the clearance between the female screw of the moving element and the male screw of the screw bar. This makes it difficult to correctly mount and fix a work piece just by clamping the moving element in one step.
A vise clamp operator must therefore inspect the alignment of a work piece by determining whether the vise jaw is flush with the outer surface of a work piece before final clamping with full force. The operator typically uses a hammer to strike at the head of the vise jaw to align a work piece with test plates placed underneath the work piece. Downward hammering of the work piece against the test plates ensures parallel alignment. Only after this laborious process can an operator apply final clamping.
Such manual adjustment greatly increases processing time per work piece. The inefficiency is particularly noticeable in a mass production system in which a number of work items of the same size with the same processing item and position are processed.
Therefore, there is an unmet need for an apparatus which significantly reduces the difficulty and time required for accurate clamping of a work piece in a vise.
SUMMARY OF THE INVENTION
This and other objects of the present invention are achieved by the novel vise pads for accurately aligning work pieces. The vise pads of the present disclosure include two major outside pieces as illustrated by FIG. 3 . One is internal 11 and has at least two cam grooves 11 a , 11 b formed lengthwise over the outer surface. At least two cam grooves 14 a , 14 b are also located crosswise and perpendicular to the longitudinal cam grooves. This internal member contains drilled grooves 16 . The other member is external 20 and has at least two cam grooves 21 a , 21 b formed lengthwise over the inner surface. At least two cam grooves 24 a , 24 b are similarly located crosswise and perpendicular to the longitudinal cam grooves. The outer member includes drilled screw grooves 22 .
At least two wedge bars 32 a , 32 b , 33 are held parallel to each other in the present vise pads by two or more connectors 31 a , 31 b . The connectors each have at least two rounded holes that the wedges bars fit through. The connectors with the wedge bars form a wedge bar-connector combination as illustrated by FIG. 4 . At least two bolts are coupled to the screw grooves through the bolt grooves and maintain a coupled state of the internal and external members. The present vise pad is assembled by bring the internal member into contact with the external member such that the respective longitudinal cam grooves face together. The facing together of the pieces causes insert-gripping of the wedge bar-connector combination. Screwing of the at least two bolts through the bolt grooves secures the internal and external members with the wedge bar-connector combination to form the present vise pads.
An operator may put the respective vise pads in the vise jaws at the main body side and the moving element side. Then a work piece can be inserted between the pads and the moving element clamped with full force without manual parallel adjustment with a hammer. In the event the external element is not closely attached to the vise jaw or when the internal member is not alignment parallel, the internal member of the present vise pad slightly moves in lengthwise direction within the clearance range between the female screw of the main body and the male screw of the screw bar. This movement prevents slanting of a work piece. Mere clamping of a work piece by the moving element allows easy and accurate fixation of a work piece.
Over time however, the movement and rubbing of the wedge bars of the vise pads against the cam grooves during fixation of a work piece causes wear which reduces alignment efficiency over time. Further, the entry of metal dust and other fine foreign objects caused by sawing or other operation on a work piece can further cause wearing of the wedge bars or inefficiency of the movement of the internal member of the adjusting vise pads.
In the present vise pads, the wedge bars are held parallel to each other by two or more connectors 31 a , 31 b . The connectors touch the internal and external members of the vise pad but the wedge bars substantially do not in one embodiment. The wedge bars can move within the connectors which have holes through which the wedge bars fit. Compared to the wedge bars placed directly onto the entire length of the cam grooves, the wedge bars touch at the connector holes. Thus, wedge bar friction is reduced, especially if the holes of the connectors contain bearings.
Furthermore, elastomeric bars 30 a , 30 b may be placed in the outer cam grooves to provide a seal when the internal and external members of the vise pads are put together. This seal reduces the entry of metal dust which may result from sawing or drilling of a work piece. Such reduction of impurities prolongs the life of the present vise pads.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a work piece incorrectly clamped in a conventional vise.
FIG. 2 illustrates a vise pad not containing a wedge bar-connector combination.
FIG. 3 illustrates an exploded view of the present vise pad having a wedge bar-connector combination and elastomeric bars.
FIG. 4 illustrates a wedge bar-connector combination separated from the internal and external members.
FIG. 5 illustrates a cross-sectional view of a vise pad in the assembled state.
FIG. 6 a illustrates a work piece positioned before clamping in a vise.
FIG. 6 b illustrates a work-piece clamped between vise pads.
DETAILED DESCRIPTION OF THE INVENTION
The present disclosure is generally related to a vise pad useful for accurate work piece alignment. The present vise pad comprises an internal member 10 which has at least two cam grooves 11 a , 11 b formed longitudinally over the outer surface of the internal member, at least two cam grooves 14 a , 14 b formed crosswise and perpendicular to the at least two longitudinal cam grooves and a plurality of drilled screw grooves 16 . “Internal” or “inner” refers to the side of the vise pad which faces or is nearest a mounted work piece.
The present vise pad also includes an external member 20 comprising at least two cam grooves 21 a , 21 b formed longitudinally over the inner surface of the external member, at least two cam grooves formed crosswise and perpendicular 24 a , 24 b to the at least two longitudinal cam grooves 21 a , 21 b and a plurality of drilled bolt grooves 22 corresponding to the plurality of screw grooves 16 . “External” or “outer” refers to the side of the vise pad which is further away from the mounted work piece than the internal member which is closer to the mounted work piece.
The present vise pad further includes at least two wedge bars 32 a , 32 b , 33 held parallel to each other by two or more connectors 31 a , 31 b each having at least two rounded holes wherein the wedge bars fit through corresponding rounded holes of the connectors and forms a wedge bar-connector combination as shown by FIG. 4 . At least two bolts 40 are coupled to the screw grooves through the bolt grooves to maintain a coupled state of the internal and external members. The vise pad is assembled by bringing the internal member into contact with the external member so that the respective longitudinal cam grooves face together and insert-grips the wedge bar-connector combination, and screwing the at least two bolts through the at least two bolt grooves into the at least two screw grooves.
The internal member 10 is a precisely processed thick plate of a hexahedron or parallel-piped rectangle which allows for close fixing to the outer surface of a work piece. The cam grooves 21 a , 21 b , 21 c are configured to allow the internal member to move slightly in one direction within the cam grooves using a wedge bar as a mandrel. The present cam grooves have an arc shape of a partial circle. The bolt groove 16 is configured to maintain an assembled state by joining the external member 20 with a bolt and is drilled to penetrate through the plate surface of the internal member around four edges of the internal member without invading the region of the cam grooves.
The external member supports the internal member and this allows the internal member to slightly move upwardly and/or downwardly when fixing and clamping a work piece against the main body and vise jaw of the movement element of a vise. The external member also is a precisely processed thick plate of a hexahedron or rectangular which is parallel-piped for close fixation to the outer surface of the work piece. The external member is formed with longitudinal cam grooves on the same location as the cam grooves in the portion of the outer surface of the internal member. A plurality of bolts are drilled on a free space between the upper and lower cam grooves.
The screw groove is configured to maintain the assembled state of the vise pad A by inserting a bolt 40 and is drilled to penetrate through the plate surface of the external member 20 at the same location as the bolt groove 12 around four edges of the internal member 10 without invading the region of the cam grooves.
A wedge bar-connector combination ( FIG. 4 ) is inserted between the cam grooves 14 a , 14 b , 24 a , 24 b of the internal and external members and functions as a mandrel for allowing the internal member to slight move with respect to the external member. Wedge bar is annular and the wedge bar-connector connector combination has a thickness such that the internal and external members do not contact each other.
The upward and downward movement of the internal and external members corresponds to a given clearance between the male screw and the female screw groove. The bolt 40 functions as a bar-shaped elastomer for allowing the inner member to return to the original state upon release of the clamping forces against a work piece.
The present vise pad as illustrated by FIG. 3 is different from the vise pad of FIG. 2 . FIG. 2 shows no wedge bar-connector combination. The inner member 100 and outer member 200 has cam grooves 110 a , 110 b , 210 a , 210 b , wedge bars 300 , bolt grooves 120 and screw grooves 220 . The wedge bars directly contact the length of the cam grooves. In contrast, the present vise as illustrated by FIG. 3 has wedge bars that contact the inner and outer members via the connectors. Thus, friction is reduced.
Alternatively, the present wedge bar-connector combination may have at least three wedge bars held parallel to each other by two or more of the connectors. FIG. 3 illustrates an embodiment which has three wedge bars 32 a , 32 b , 33 . The center wedge bar 33 is shorter than the outer wedge bars 32 a , 32 b.
In one embodiment the inner and outer members of the present vise pad are made of steel. It is within the scope and teaching of the present disclosure to include others materials which may be used to fashion the inner and outer members, especially metallic materials.
Various numbers of screws bolts may be coupled to the screw grooves through the bolt grooves. This number may be, but not limited to: two, four or six. FIG. 3 illustrates an embodiment where six bolts are used.
In one embodiment, the at least three wedge bars are in contact with the connectors but substantially not in contact with the surface of at least three cam grooves of the internal member and the surface of at least three cam grooves. Such lack of contact promotes longer life of the vise pad by reducing friction between the wedge bars and inner and external members.
Referring to the wedge bar-connector as illustrated by FIG. 4 , the holes of the connector may be formed, in one embodiment, by friction reducing bearing. Such bearing will promote movement of the wedge bars through the holes and reduction of friction will result in longer life. Additionally, the combination may be lubricated with a lubricant such as an oil-based lubricant.
In another embodiment, a vise pad for accurate work piece alignment comprises an internal member 10 comprising at least five cam grooves 11 a , 11 b , 11 c , 13 a , 13 b formed longitudinally over the outer surface of the internal member, at least two cam grooves formed crosswise and perpendicular to the at least two longitudinal cam grooves 14 a , 14 b and a plurality of drilled screw grooves 16 ; an external member 20 comprising at least five cam grooves 21 a , 21 b , 21 c , 23 a , 23 b formed longitudinally over the inner surface of the external member, at least two cam grooves 24 a , 24 b formed crosswise and perpendicular to the at least five longitudinal cam grooves, and a plurality of drilled screw grooves 22 corresponding to the plurality of bolt grooves; at least three wedge bars 32 a , 32 b , 33 held parallel to each other by two or more connectors 31 a , 31 b each having at least three rounded holes wherein the wedge bars fit through corresponding rounded holes of the connectors, thereby forming a wedge bar-connector combination; at least two elastomeric bars 30 a , 30 b inserted between the two outermost cam grooves of the internal member and the two outermost cam grooves of the external member; at least two bolts 40 to the screw grooves 22 through the bolt grooves 12 to maintain coupled state of the internal and external members; and the pad is assembled by bringing the internal member into contact with the external member such that the respective longitudinal cam grooves face together, inserting-gripping the wedge bar-connector combination, and screwing the at least two bolts through the at least two screw grooves into the at least two bolt grooves.
The two inserted elastomeric bars provide a seal between the internal and external members while still allowing movement of these members when clamping a vise. The seal reduces entry of impurities such as metal particle dust resulting treatment of a work piece such as sawing or drilling. The elastomeric may be made of, but not limited to, silicone or rubber.
FIG. 6 a illustrates mounting of a work piece in a vise jaw using the present vise pads. Moving element 2 is in a widened position. The vise pads A, A′ are mounted on the respective vise jaw. A work piece 6 is put on a jig 7 located between the vice pads. As illustrated by FIG. 6 b , a screw bar moves the moving element toward the main body so that the pads grip a work piece 6 . The jig is a vise only jib on which a work piece is put horizontally and has its width smaller than that of the work pieces so that the pads grip the work piece without difficulty.
During initial operation a work piece may not be gripped tightly as the internal member may not be closely attached to the outer surface of the work piece. In such a case, the moving element 2 is fastened more tightly. Generally, the external element of the respective vise pads A, A′ do not move. The internal member moves slightly upward within the aforementioned clearance range between the screw groove and bolt using the wedge bar-connector combination as a mandrel in accordance with a fastening pressure provided by the moving element.
When machining operation is completed for a work piece then the moving element is moved back to the returned state illustrated by FIG. 6 a . The internal member and the wedge bar-connector combination are released from the fastening pressure applied to the work piece. The vise pads are returned to their initial positions by the repelling force that was stored when the bolt was forcibly wrenched by final clamping pressure.
Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.
The terms “a,” “an,” “the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.
Grouping of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.
Certain embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intended for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.
Furthermore, numerous references have been made to patents and printed publications throughout this specification. Each of the above-cited references and printed publications are individually incorporated by reference in their entirety.
In closing, it is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described. | The present disclosure general relates to vise pads which provide accurate alignment of work pieces in a vise. The movement of internal members of these pads eliminates the need for manual adjustment such as with the use of a hammer to ensure alignment. The vise pads include wedge bars in combination with connectors which reduce friction and thus provide for longer life and efficient operation. In another embodiment, the vise pads include elastomeric bars which act as sealant to reduce entry of dust resulting from machining of a work piece. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not applicable.
STATEMENT REGARDING FEDERALLY SPONSORED-RESEARCH OR DEVELOPMENT
[0002] Not applicable.
INCORPORATION BY REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC
[0003] Not Applicable.
FIELD OF THE INVENTION
[0004] The invention disclosed broadly relates to the field of cooling devices for microelectronics and more specifically relates to passive cooling heat sinks.
BACKGROUND OF THE INVENTION
[0005] Electronic chips such as microprocessor chips generate much heat. As processing power goes up, the chips produce more heat which could damage the electronic circuits in the chip; therefore it is important to cool the chips. Many cooling methods have been developed for directly cooling hot chips, heat sinks being one such method. Generally, heat sinks fall into two categories: active heat sinks and passive heat sinks. Active heat sinks cool a chip using a fan or other active devices to move heat away from the chip. Passive heat sinks perform the cooling function without a fan, instead relying on ambient conditions provided by design to cool the chip.
[0006] Active heat sinks, because they employ a fan or other mechanism, require that some energy be expended in order to cool the chip. Additionally, the introduction of a moving part (the fan) to the cooling device increases the possible failure mechanisms. Some passive heat sinks address these problems by using a cooling fluid to cool the hot chips rather than a fan. The use of fluid is not without its problems. In one of the latest developments in passive heat sink technology, the Heatlane™ heat pipe device (Heatlane is a trademark of TS Heatronics Co., Ltd.) relies on an unstable, oscillatory exchange of fluid and gas back and forth within the evaporation section of the device. This is problematic because hot fluid and gas might return into the evaporation section. Also, with the Heatlane™, energy needs to be expended to cool the chip by way of a fan blowing air through the air heat exchanger. Heat pipes use a wick to return the fluid to the evaporation section. This technology has reached its limits in modern systems—multiple heat pipes need to be used on single chips because not enough coolant is available in a single pipe.
[0007] Therefore, there is a need for a better passive cooling method and apparatus for chips that generate more heat.
SUMMARY OF THE INVENTION
[0008] Briefly, according to an embodiment of the invention, a cooling system for a heat-generating device includes: coolant fluid; an evaporator for holding the coolant fluid and for heating the coolant fluid; said evaporator in close proximity to the heat-generating device for removing unwanted heat. The cooling system also includes a plurality of tubes for providing a flow path for the coolant fluid and gases produced by the evaporator; a heat exchanger through which the tubes pass for cooling the coolant fluid and gas. The heat exchanger includes: a reservoir, a coolant, and a heating element for heating the gas so that it expands and pushes coolant fluid back to the evaporator. The heating element may be located inside the reservoir.
[0009] Additionally, the cooling system according to an embodiment of the invention may include check valves, gas traps, and a coolant return tube. The cooling system may also include a baffle disposed within the evaporator far from the tubes.
[0010] A method according to an embodiment of the invention provides the steps of: heating coolant fluid contained in an evaporator in close proximity to the device; evaporating the coolant fluid to release gases used to pump hot coolant fluid and gases out of the evaporator and into the heat exchanger; transferring heat from the coolant fluid and gases to the heat exchanger in one or more tubes; collecting condensed coolant fluid and cooled gas in the reservoir of the heat exchanger; heating the cooled gas and fluid with the heating element; and returning the condensed coolant fluid back to the evaporator using the generated heated gas.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] To describe the foregoing and other exemplary purposes, aspects, and advantages, the following detailed description of an exemplary embodiment of the invention with reference to the drawings, in which:
[0012] FIG. 1 shows a cooling system with its heating system in the up cycle, according to an embodiment of the invention;
[0013] FIG. 2 shows the cooling system with its heating system in the down cycle, according to an embodiment of the invention;
[0014] FIG. 3 shows a gas trap according to an embodiment of the invention;
[0015] FIG. 4 shows a cooling system using only one tube, according to an embodiment of the invention;
[0016] FIG. 5 shows a dual tube design according to an embodiment of the invention;
[0017] FIG. 6 shows a coaxial return pump design, according to an embodiment of the invention;
[0018] FIG. 7 shows the cooling system of FIG. 1 without the check valves and third tube, according to another embodiment of the present invention; and
[0019] FIG. 8 is a flowchart representing the steps for carrying out the cooling method according to an embodiment of the present invention.
DETAILED DESCRIPTION
[0020] We describe a cooling system for heat-generating devices, such as electronic chips. In particular, a two-phase system in which a coolant is boiled offers an attractive method of moving large amounts of heat away from a hot chip. This provides a novel method of guaranteeing the circulation of the coolant, assuring that the evaporator never boils dry. This is in contrast to heat pipes, which use a wick to return the fluid to the evaporation section.
[0021] Referring to FIG. 8 , the process begins at step 805 when a heat-generating device conducts heat through its surface or an interface material to an evaporator filled with a liquid coolant fluid. This direct heating of the coolant in the evaporator causes vaporization of the coolant in the evaporator in step 810 , absorbing heat through the heat of vaporization of the coolant. The hot coolant gases and entrained fluid are rapidly pumped out of the evaporator into a heat exchanger in step 820 . The “pump” effect occurs because the vaporized gas acts as a pump, forcing the hot gas and entrained fluid up through the heat exchanger. The vaporized coolant and hot liquid is forced under pressure to bubble through the coolant in the heat exchanger, transferring its heat to the coolant and to the metal tubes of the heat exchanger. In step 830 , the coolant is cooled, and once cooled, the chilled, condensed coolant and cool gas are collected in a reservoir.
[0022] Next, in step 840 , when either the coolant level is too low in the evaporator, or the coolant temperature is too high, a heating element is activated in the condensed coolant and gas in the reservoir. This causes gases in the heat exchanger to be generated, heated, and expanded in step 850 . The expanding gases push the condensed coolant which is very rapidly re-injected into the evaporator through a tube. An external sensor can be used to determine when the temperature is too high. This injection of coolant requires very little energy, or heat, added to the system. It returns condensed fluid to where it is needed, right to the surface interface of the heat-generating device, such as a chip. In step 860 , the heating element is quickly deactivated, and the cycle repeats with the hot, gaseous coolant and entrained hot fluid pumped out of the evaporator to the heat exchanger.
[0023] We now describe in more detail the operation of the cooling system in the “Up” cycle wherein the coolant flows up to the heat exchanger. FIG. 1 shows a cooling system 100 according to an embodiment of the invention. The cycle begins with the system 100 in a quasi-equilibrium state with a coolant 103 vaporizing in the evaporator 106 and gas being pushed through the coolant 103 trapped in the heat exchanger pipes 102 , 104 . The heating element 105 is off at this point.
[0024] The evaporator 106 is positioned in good thermal contact with (in close proximity to) a chip 101 or other heat-generating device. The evaporator 106 may be a chamber with metal heat conductors running through it, or it might be fine metal tubes as in a steam generator. The evaporator 106 should be optimized to boil as much coolant as possible as quickly as possible. Special coatings and structures can be designed, optimized for the coolant, which is understood in the literature of boiling. The evaporator surface might be flat with a special coating, or be further optimized with a finned or pin structure for more surface area within the boiler.
[0025] As the chip 101 heats up, unwanted heat emanating from the chip 101 heats a liquid coolant 103 in the evaporator 106 . The coolant or cooling fluid 103 is preferably chosen to have a high heat of vaporization and a low boiling point. The coolant should also have a high vapor pressure to make the pumping feature work well. And it should boil at a temperature low enough to cool the chip. Examples of the coolant 103 may be one of the following: 1) water at a pressure lower than one atmosphere—although water has a very low vapor pressure and may not work well; 2) butane; 3) any commercial refrigerant; 4) methyl chloride; 5) ammonia at eight (8) bar of pressure; 6) ammonia-hydrogen mix (used in refrigeration); 7) 3M's HFE-7000, with a boiling point of 34 degrees Celsius; 8) Methanol at 100 mm Hg pressure, boiling at room temperature; or 9) liquid carbon dioxide. It should be noted that other fluids with good vapor pressure, low boiling point, and good environmental properties can and may be used in an embodiment of the invention.
[0026] As the liquid coolant 103 heats, some of it vaporizes. For example, methanol at a pressure of 100 mm Hg boils immediately at room temperature and builds pressure rapidly. HFE-7000 boils at about 34 degrees Celsius at one atmosphere, cool enough to cool a heated chip 101 . HFE-7000 is not flammable, is not a green house gas, and is non-toxic; therefore, it is well suited for use in this application. The lower density of the heated gases and the pressure exerted by the gases cause it to rise up and additionally entrain some fluid 103 into the heat exchanger 108 . The vaporized gas acts as a pump, forcing the hot gas and the entrained fluid 103 up through the heat exchanger pipes 102 and 104 . Both gas and fluid are simultaneously transferred to the heat exchanger 108 in this way.
[0027] By moving both hot gas and fluid 103 , large amounts of heat may be transferred more efficiently than by using fluid alone. As the hot gas forces its way through the fluid 103 , bubbling up through the coolant 103 in the heat exchanger pipes 102 and 104 , some fluid is necessarily moved up toward a reservoir in the heat exchanger 108 . This is similar to a coffee percolator with hot gas bubbling through columns of fluid. The pumping of the gas will occur as it moves from the high pressure of the evaporator 106 to the lower pressure in the exchanger 108 . The optimal fill ratio (how much liquid coolant vs. gas) depends upon the system and can be determined by experimentation. Both the pressure differential and the coffee percolator-like “bubble pump” mechanism driven by gravity push hot coolant into the heat exchanger 108 .
[0028] Rather than two tubes (pipes), however, just one tube could be used. In the alternative, a dozen or more tubes could be employed. The tubes 102 and 104 in the example of FIG. 1 are preferably thin-walled and of a small diameter, approximately one-eighth of one inch to three-eighths of an inch (⅛″ to ⅜″) in order to conduct heat efficiently.
[0029] The hot fluid and gas 103 is directed up to the cooler areas of the heat exchanger 108 where it is cooled and condensed Then some of the cooled, condensed fluid 103 collects in the heat exchanger reservoir 110 . The reservoir 110 is a cool chamber or collection of tubes, preferably metal tubes. The chamber 110 remains cool because it is disposed within or in proximity to the heat exchanger 110 , or radiator. Unlike the Heatlane™, the system 100 allows hot bubbles or slugs of gas to be forced through the coolant 103 in the heat exchanger 108 . This hot gas is forced under pressure toward the reservoir 110 , where it can cool and condense on its way by transferring its heat either to the coolant 103 or directly to the tube's walls in the exchanger 110 .
[0030] The cooling system 100 requires only one active element—a heating element, wire, or cartridge heater, 105 , used intermittently to return the cooled, condensed fluid 103 back to the evaporator 106 . The fluid 103 can be returned through a third tube 112 . The third tube 112 is a return tube, returning the cooled liquid 103 to the evaporator 106 . If the return tube 112 is long enough and high enough, gravity alone would ensure that cold fluid 103 would return to the evaporator 106 . However, in this embodiment we focus on a design for microprocessors, necessitating a small size. Heating the cooled gas or boiling some coolant causes the gas to expand, thereby moving (injecting) the coolant 103 back to the evaporator 106 . This requires very little energy—a small fraction of the total energy being given off by the chip 101 . Heating the gas quickly in the reservoir 110 does not heat the coolant liquid (anywhere) appreciably. The gas is generated and heated just enough to move the liquid 103 through the return tube 112 .
[0031] In this embodiment we may have two passively moving parts, the opening and closing of the check valves 114 and 116 which restrict the flow of liquid. In this example the check valves are of the ball-type. The passive check valves 114 and 116 may be of the ball variety shown, but any type will work. The check valves 114 , 116 improve the efficiency of the device, but the system 100 works without them if the return tube 112 is closed off. This type of valve is passive, analogous to the valves which operate in a heart. An active valve could be used but it would be costly, more subject to failure, and would require a control mechanism. Note that these are an optimization to the system 100 but are not required. The system 100 as presented operates without any moving parts or valves as shown in FIG. 7 . Check valves are required only for an embodiment employing a return tube. For example, the prototype in FIG. 4 has no valves.
[0032] The Heatlane™ device mentioned earlier relies on an unstable, oscillatory exchange of fluid and gas back and forth with the evaporation section of the device. The system 100 is designed so that there is a unidirectional flow of heat from the evaporator 106 to the heat exchanger 108 . The system 100 cools by boiling a liquid which boils at a low temperature. The hot gas generated is uniformly pushed through the heat exchanger to be cooled and condensed.
[0033] Therefore, unlike the Heatlane™ device, the system 100 uses a nearly unidirectional flow of hot gas and fluid to the colder section of the system 100 . This system 100 does not require gravity to operate, only that the entrances and exits of the reservoirs be placed to make sense with respect to gravity. In fact the one-way check valves 114 and 116 are not required. They are placed in the device for improved efficiency. Refer to FIG. 7 where a system 700 is shown without the valves 114 , 116 , and without the third tube. Without the third tube 112 and check valves 114 , 116 , coolant could be blown back through the heat exchanger 108 , warming up the coldest fluid, and returning much of the liquid coolant 103 back to the evaporator 106 . This would result in an average warmer coolant 103 temperature in the evaporator 106 compared with the embodiment previously discussed, but it would still provide cooling. (An embodiment without the third tube 112 and check valves 114 , 116 has been demonstrated and measured with methanol and HFE- 7000 as examples.) See FIG. 4 for an illustration of a coolant system with only one tube.
[0034] This system 100 uses a heater 105 to drive the cycle. The heater 105 can be a coil of tungsten or titanium heating wire, but more likely is a heater cartridge having sufficient surface area and a proper coating to heat a volume of fluid quickly, and is used intermittently in a pulsed fashion to return the cooled, condensed fluid 103 back to the evaporator 106 . The heater 105 can also double as a heat sensor with a built-in thermocouple or fluid detector if a closed loop control is implemented. Alternatively, the heater 105 can be activated periodically, without regard to the status of cooling, or it can be activated by some other external sensor or trigger event. Some examples are: the fluid level in the evaporator falling below a minimum threshold or a temperature sensor reaching a maximum threshold temperature. There are other simple methods for activating the heater 105 . One option is if the chip is a microprocessor, its temperature sensors can detect that the boiler is going dry and request more coolant 103 —just as it requests that the fan controllers spin faster today in personal computers
[0035] The “Down” cycle of the system 100 is shown in FIG. 2 wherein cooled, condensed coolant 103 is returned to the evaporator 106 . The heating element 105 is turned on (or is in its intermittent “on” phase). This generates heat which causes the gas to expand and “push” the cooled coolant 103 back to the evaporator 106 . The coolant 103 rapidly flows down the return tube 112 to fill the evaporator 106 again. Immediately, the hot fluid 103 in the evaporator 106 may be pumped to the heat exchanger 1 10 . Moving hot fluid out of the evaporator enhances the cooling power of evaporation alone. With the return of cool fluid to the evaporator, the total system pressure drops, and coolant 103 begins boiling in the evaporator 106 immediately. It is not intended that the heater 105 do anything other than generate hot gas to force the coolant to return to the evaporator 106 . The check valve 116 is automatically in the closed position, prohibiting the flow of the coolant 103 out of the radiator 104 back into the evaporator 106 .
[0036] Referring now to FIG. 3 there is shown an illustration of a gas trap 300 that can be used with the system 100 . The gas trap 300 helps stand coolant up in the exchanger tubing, especially if wide diameter tubing is used. The gas trap 300 keeps fluid from flowing back by gravity. It is useful if the tubes are of a large diameter, but it is generally not necessary. Gas pressure will hold the column of fluid up if provided with a trap. Without the trap 300 , gas might fill the tube enough to allow the free fall of fluid back, which is undesirable. Each Up tube 102 , 104 might have a trap, or all up tubes can be fed from a single large pipe with a trap.
[0037] Referring to FIG. 4 there is shown a coolant system 400 using only one tube 440 , according to another embodiment of the present invention. The tube 440 is approximately ⅜″ in diameter and is disposed inside of a Lytron™ heat exchanger 410 and filled with approximately 0.5 L of liquid methanol 420 . Each end of the tube 440 is inserted into boro-silica view tubes 450 of a thicker diameter than the tubing 440 . Each of the two boro-silica tubes 450 are attached to a chamber containing a three-inch long, 3 / 8 inch diameter stainless heater cartridge 430 . In this demonstration, one heater cartridge simulates the heat of a chip and is run continuously at a few hundred watts of power. The other is pulsed periodically and acts as the return pump.
[0038] FIG. 5 is a cross-section image of two tubes in a dual tube design 500 . One tube 540 conducts the heated liquid and gas to the exchanger 108 while the other tube 560 (the return tube) returns the cooled liquid and gas to the evaporator 106 . The pulse pump action is the same as described earlier; a heating element in a reservoir, with check valves fore and aft. FIG. 6 shows co-axial tubing according to another embodiment of the present invention. The tubing of FIG. 6 has the external appearance of a single tube, but is co-axial as shown. This co-axial tubing implementation may be used in an embodiment such as that shown in FIG. 1 with the exception being the return tube is co-axial with the “up” tube. This co-axial system may be easier to deploy.
[0039] Referring to FIG. 4 , most of the heat is dissipated in the first tube 420 running up into the heat exchanger, especially inside the exchanger 410 . Heat dissipation drops off rapidly in a dry tube as described in “Heat and Mass Transport,” Incroppera and DeWitt Textbook, Wiley, 2002, p 612. Looking at FIG. 4 , it is best that much of the tubing contain liquid coolant, especially in the left-most tube 420 leading up from the evaporator 106 . The heat transfer is best if bubbles of hot gas rise through the liquid coolant 103 . Heat transfer and dissipation drop off rapidly if the tube becomes dry, containing only gas. In a prototype example as in FIG. 4 , at less than 150 watts, gravity alone does most of the work and the pump 490 does almost no pumping. At greater than 200 watts, vigorous entrainment of the coolant 103 with rising gas slugs spills and condenses into the return pump reservoir 490 . At greater than 300 watts the system is close to Critical Heat Flux (CHF) and becomes difficult to operate. This system works by “pool boiling,” just as in a tea kettle. The CHF is the point beyond which pool boiling fails to occur, and the chip heat becomes insulated by a layer of gas. A simple example of CHF is that if you turned the heat up high enough under a tea kettle, the bottom will melt out, even though there is liquid in the kettle. The layer of steam between the bottom of the kettle and the water inside insulates the heat source and pool boiling stops.
[0040] In this methanol test, the pressure will never exceed one atmosphere and will usually remain well below one atmosphere. Within the parameters of the test, the CHF was somewhere around 300 Watts, and cooling was not sustainable. Known methods of improving the boiler could easily raise this maximum flux.
[0041] A preferred pump system is shown in FIG. 6 . A coaxial return pump design 600 shows a pulse pump 680 disposed within the return tube 560 . The return tube 560 is placed inside the “up” tube 540 . The pulse pump 680 is identical to the heating element pump previously described, situated to return coolant from the reservoir in the radiator back to the evaporator. The pump 680 , like the pump in FIG. 5 , is placed where the condensed coolant 103 is within the return tube 560 . This coaxial implementation may be simpler and more efficient than the system of FIG. 5 and the one-tube system of FIG. 4 .
[0042] Therefore, while there have been described what are presently considered to be the preferred embodiments, it will understood by those skilled in the art that other modifications can be made within the spirit of the invention. | A cooling system for a heat-generating device includes: coolant fluid; an evaporator for holding the coolant fluid and for heating the coolant fluid; said evaporator in close proximity to the heat-generating device for removing unwanted heat. The cooling system also includes a plurality of tubes for providing a flow path for the coolant fluid and gases produced by the evaporator; a heat exchanger through which the tubes pass for cooling the coolant fluid. The heat exchanger includes: a reservoir, a coolant, and a heating element for heating the gas so that it expands and pushes cool coolant fluid back to the evaporator. The heating element may be located inside the reservoir. | 7 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims priority to U.S. provisional application Ser. No. 61/264,089, filed Nov. 24, 2009, the entire contents of which is incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] This application is directed to beverage tap handles and, more particularly, to a tap handle having a liquid filled chamber.
[0003] In many establishments that serve beverages, such as restaurants, sports bars, and taverns, it is common for a beer or soda tap handle to include some indicia identifying the brand of beverage associated with the tap handle. Initially, the indicia may simply have been in the form of the brand name of the beverage on a generic tap handle. Increasingly, however, beverage producers such as brewers have provided elaborate tap handles that are specially shaped or that include pictures and other objects reflective of the brand of the beverage with the intent of differentiating the beverage tap handle from a slew of beverage tap handles at the dispensing station of the establishment. As a result, a consumer, when viewing the various tap handles at the dispensing station can readily identify the selection of available beverages by viewing the tap handles at the dispensing station.
SUMMARY OF THE INVENTION
[0004] The present invention provides a tap handle having a chamber that can be filled with liquid, which may be colored to represent a beverage associated with the tap handle. The material of the handle may be transparent or semi-transparent, allowing a consumer to readily identify a characteristic of the beverage, such as whether it is a dark or light beer. The body of the handle may be formed in the shape of a bottle, a glass, or any other ornamental design. The body of the handle may also include an insert in the lower portion for connecting the handle onto the tap. Alternately, the body may be secured to a base that, in turn, connects to the tap. The chamber may also include particles that float on top of the liquid and that resemble foam, such that the liquid inside the chamber resembles beer or any other liquid, such as soda, that can be dispensed via a tap.
[0005] According to a first embodiment of the present invention, a handle for a tap faucet includes a first housing defining a generally hollow cavity and includes an opening in communication with the cavity. A liquid is disposed within the hollow cavity, and a cover is connected to the first housing to seal the opening. A base is coupled to the first housing and configured to operably connect the first housing to the tap faucet. The handle may further include a plurality of floating particles disposed within the hollow cavity, which resemble foam. Thus, it is a feature of this invention that the tap handle provide a visual indication of the beverage dispensed by the tap faucet.
[0006] According to another aspect of the invention, the handle may also include a second housing defining a volume. Each of the first and second housings may be elongated, and the second housing is contained within the cavity of the first housing. An identifier may also be contained within the second housing indicating at least one of the beverage manufacturer or beverage brand name to be dispensed by the faucet. The handle may further include a recess formed at a first end of the cavity in the first housing and a tab extending from a first end of the second housing. The tab engages the recess to retain the second housing in alignment with the first housing. The second housing may also include a receiving member extending from a second end of the second housing and the cover may include an engaging member extending into the cavity. The engaging member operably engages the receiving member to further retain the second housing in alignment with the first housing.
[0007] These and other objects, advantages, and features of the invention will become apparent to those skilled in the art from the detailed description and the accompanying drawings. It should be understood, however, that the detailed description and accompanying drawings, while indicating preferred embodiments of the present invention, are given by way of illustration and not of limitation. Many changes and modifications may be made within the scope of the present invention without departing from the spirit thereof, and the invention includes all such modifications.
BRIEF DESCRIPTION OF THE DRAWING(S)
[0008] Various exemplary embodiments of the subject matter disclosed herein are illustrated in the accompanying drawings in which like reference numerals represent like parts throughout, and in which:
[0009] FIG. 1 is a perspective view of an embodiment of the tap handle according to the present invention connected to a tap faucet;
[0010] FIG. 2 is a perspective view from the side and top of the tap handle of FIG. 1 ;
[0011] FIG. 3 is a top plan view of the tap handle of FIG. 2 ;
[0012] FIG. 4 is a side elevation view of the tap handle of FIG. 2 ;
[0013] FIG. 5 is a cross-sectional view of the tap handle of FIG. 2 taken at 5 - 5 as shown in FIG. 4 ;
[0014] FIG. 6 is a perspective view from the side and top of another embodiment of the tap handle according to the present invention;
[0015] FIG. 7 is a top plan view of the tap handle of FIG. 6 ;
[0016] FIG. 8 is a side elevation view of the tap handle of FIG. 6 ; and
[0017] FIG. 9 is a cross-sectional view of the tap handle of FIG. 6 taken at 9 - 9 as shown in FIG. 8 .
[0018] In describing the representative embodiments of the invention which are illustrated in the drawings, specific terminology will be resorted to for the sake of clarity. However, it is not intended that the invention be limited to the specific terms so selected and it is understood that each specific term includes all technical equivalents which operate in a similar manner to accomplish a similar purpose. For example, the word “connected,” “attached,” or terms similar thereto are often used. They are not limited to direct connection but include connection through other elements where such connection is recognized as being equivalent by those skilled in the art.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Specific embodiments of the present invention will now be further described by the following, non-limiting examples which will serve to illustrate various features of the invention. With reference to the drawing figures in which like reference numerals designate like parts throughout the disclosure, a representative embodiment of the present invention is shown in FIG. 1 as a tap handle 20 connected to a tap faucet 15 .
[0020] Referring initially to FIGS. 1-5 , the tap handle 20 is connected to the tap faucet 15 from which a beverage is dispensed. The tap handle 20 includes a first housing 22 which includes a generally hollow cavity 24 . The housing 22 may be in the form of an elongated container made from a transparent material, such as an acrylic material. The acrylic material may be transparent or semi-transparent, and in any event has sufficient transparency to enable a liquid 28 contained within the housing 22 to be visible through the housing 22 . The housing 22 is transparent so that the color of the liquid 28 contained in the housing 22 is discernable. Optionally, the material of the housing 22 may be clear, green, amber, or any other desired color. In another embodiment, the color of the housing 22 may correspond to the color of glass used by the manufacturer to package the particular beverage when being dispensed in bottles. The material of the housing 22 may be made of a material that is readily washable and can easily be kept clean and sanitary.
[0021] The first housing 22 is formed by any plastic molding process, for example, by blow molding or an injection molding process, to resemble any desired shape. As illustrated in FIGS. 1-5 , the first housing 22 may be formed to generally resemble a pilsner glass. Optionally, the housing 22 may be formed to resemble a bottle as may be used for retail sales of the product, or may have a shape resembling a logo or other indicia associated with a particular brand of beverage. In still other embodiments, the first housing 22 may be formed to resemble a beer mug or may be formed in more traditional or ornamental shapes for tap handles.
[0022] The first housing 22 is formed with an opening 26 located at one end of the housing 22 . The opening 26 is in fluid communication with the cavity 24 within the housing 22 , permitting the cavity 24 to be filled, at least in part, by a liquid 28 . In one embodiment, the liquid 28 may be the same liquid dispensed by the tap faucet 15 . Optionally, the liquid 28 may be clear or a clear liquid such as water or oil that is colored to resemble the beverage being dispensed at the tap faucet 15 . The liquid 28 may partly or entirely fill the first housing 22 . According to one embodiment, the liquid 28 is added to the cavity 24 up to a suitable level corresponding to the shape of the housing 22 , leaving a space at the top of the cavity 24 . For example, the tap handle 20 illustrated in FIGS. 1-5 resembles a pilsner glass and a suitable volume of liquid 28 is added to the cavity 24 such that the tap handle 20 resembles a full glass.
[0023] A cover 30 is included to seal the opening 26 in the first housing 22 and retain the liquid 28 within the housing 22 . The cover 30 may be made from the same material as the first housing 22 and, similarly, may be transparent or semi-transparent, clear, green, amber, or any other desired color corresponding to the housing 22 . The cover 30 may alternatively be formed of a different material that the first housing 22 , and may or may not have transparent properties. For example, in an embodiment in which floating particles are at the upper portion of the cavity 24 , as explained below, the cover 30 may be formed of an opaque material having the same color as the floating particles. The cover 30 may be securely joined with the first housing 22 , for example, by vibration, friction, laser, heat, or ultrasonic welding, by adhesive, or by any other manner known to one skilled in the art. Optionally, the cover 30 may be removably connected to the housing 22 , for example, by a threaded or snap connection.
[0024] Many beverages served from a tap faucet 15 include carbonation, causing bubbles or foam to form in or on the beverage. Consequently, floating particles 34 may also be inserted into the cavity 24 to resemble the bubbles or foam of the dispensed beverage. In one embodiment, the floating particles 34 may be made of a foam material and substantially float on the liquid 28 contained within the cavity 24 . Optionally, a portion of the floating particles 34 may be suspended within the liquid 28 . In other embodiments, the floating particles 34 may be made of any suitable material and in any suitable shape or size and may be an identifier of the manufacturer or brand name of the beverage dispensed from the tap faucet 15 .
[0025] The tap handle 20 may also include a second housing 50 contained within the cavity 24 of the first housing 22 . According to one embodiment, the second housing 50 is generally cylindrical and tapered corresponding to the form of the first housing 22 . A recess 36 may be formed at a first end 38 of the cavity and a complementary tab 54 may extend from a first end 56 of the second housing 50 . The tab 55 is inserted into the recess 36 to align the first end 56 of the second housing 50 with respect to the first end 38 of the first housing 22 . It can readily be appreciated that the tab 54 and recess 36 may be reversed, such that the tab is on the first housing 22 and the recess is on the second housing 50 . The second housing 50 may be centrally positioned within the cavity 24 of the first housing 22 . The second housing 50 may further include a receiving member 58 extending from a second end 60 of the housing 50 , and the cover 30 includes an engaging member 40 extending into the cavity 24 . The engaging member 40 operably connects with the receiving member 58 to align the second end 60 of the second housing 50 to the cover 30 . It can readily be appreciated that the engaging member 40 and the receiving member 58 may be reversed, such that the engaging member is on the second housing 50 and the receiving member is on the cover 30 . In alternate embodiments, the second housing 50 may be of any suitable shape and be aligned with the first housing 22 in any orientation according to the requirements of the tap handle 20 .
[0026] The second housing 50 defines a volume 52 which, in a first embodiment, contains air. Inserting the second housing 50 into the first housing 22 reduces the volume of liquid 28 required to fill the cavity 24 and, consequently, reduces the weight of the tap handle 20 . The second housing 50 may also be made from an acrylic material similarly to the first housing 22 . It is contemplated that the second housing 50 may be transparent to minimize visibility within the liquid 28 or, optionally, it may be opaque and include a design related to, for example, the brand or the manufacturer of the beverage being dispensed. In still other embodiments, objects may be inserted into the volume 52 which may, for example, identify the brand or the manufacturer of the beverage being dispensed. The second housing 50 may be formed by any plastic molding process, for example, by blow molding or an injection molding process, in any desired shape. The second housing 50 may be of unitary construction, if, for example, the volume 52 is to contain air, or of multiple part construction, if, for example, an object or objects are to be inserted into the volume 52 .
[0027] The tap handle 20 further includes a base 32 configured to operably connect the handle 20 to the tap faucet 15 . The base 32 may be made from metal, such as brass or stainless steel, but may be any other suitable material as desired. The base 32 is joined to the first housing 22 for example by an adhesive or a threaded connection, or by any suitable method according to the materials used for each of the base 32 and the first housing 22 . Optionally, the base 32 may be integrally molded with the first housing 22 . Referring to FIG. 5 , the base 32 includes a first mating portion 70 and a second mating portion 80 . The first mating portion 70 and the second mating portion 80 may be two separate pieces or may be integrally formed as a single member.
[0028] The first mating portion 70 is configured to connect the base 32 to the tap faucet 15 . The first mating portion 70 includes an aperture 72 , which may include a threaded interior such that the tap handle 20 engages a threaded stud (not shown) extending from the tap faucet 15 . The threaded interior may be integral to the surface of the aperture 72 or, optionally a ferrule having a smooth exterior surface and a threaded interior surface may be inserted into the aperture 72 .
[0029] The second mating portion 80 is configured to connect the base 32 to the first housing 22 . A lower surface 82 of the second mating portion 80 is adjacent to the first mating portion 70 . An outer surface 84 is connected to the lower surface 82 at a first end 86 and extends away from the first mating portion 70 . The outer surface 84 may be generally cylindrical and taper outward as it extends from the first end 86 to a second end 88 . The second mating portion 80 may be open at the second end 88 of the outer surface and configured to connect to the first housing 22 . A volume 90 may be defined between the first housing 22 and the lower and outer surfaces, 82 and 84 respectively, of the second mating portion 80 . Optionally, the second mating portion 80 may be formed from a solid member. It is further contemplated that a lighting element may be included within the volume 90 to emit light into the first housing 22 . The lighting element may include, for example, a power source, such as a battery, an illumination source, such as a light-emitting diode (LED), and electrical components to control the LED. Further, the second mating portion 80 may be removably connected to the first housing 22 , to provide access to the lighting element.
[0030] Referring next to FIGS. 6-9 , another embodiment of the tap handle 20 similarly includes a first housing 22 with a generally hollow cavity 24 . An opening 26 is formed at one end of the housing 22 , permitting the cavity 24 to be filled, at least in part, by a liquid 28 . Floating particles 34 may also be inserted into the cavity 24 that substantially float on the surface of the liquid 28 , remain suspended in the liquid 28 , or a combination thereof. The tap handle also includes a cover 30 to seal the opening 26 in the first housing 22 .
[0031] The cover 30 , according to the embodiment illustrated in FIGS. 6-9 , is integrally formed with the second housing 140 . The outer periphery 132 of the cover 30 is complementary to the opening 26 in the first housing 22 , providing a sealing connection to the first housing 22 . An opening 134 is formed in the cover 30 , which defines an inner periphery 136 of the cover 30 . The inner periphery 136 is connected to the second housing 140 and the cover 30 may be integrally formed with the second housing 140 . When the cover 30 is connected to the first housing 22 , the second housing 140 extends into the first housing 22 . A volume 142 is defined within the second housing 140 and is in communication with the opening 134 in the cover 30 . Thus, the volume 142 may be accessible to receive objects inserted therein. The objects may include indicia identifying either the brand or the manufacturer of the beverage dispensed by the faucet 15 . Optionally, a cap 100 may be included to cover the opening 134 . The cap 100 may be secured to the either the cover 30 or the first housing 22 by vibration, friction, laser, heat, or ultrasonic welding, by adhesive, or by any other manner known to one skilled in the art. Optionally, the cover 30 may be removably connected to the cover 30 or housing 22 , for example, by a threaded or snap connection.
[0032] The tap handle 20 may further include at least one identifier. The identifier may be a label, a decal, or a symbol or text painted, etched, or integrally formed on the first or second housing, 22 or 50 respectively. The identifier provides to a consumer an indication of the beverage being dispensed by the tap faucet 15 on which the tap handle 20 is connected.
[0033] In operation, a tap handle 20 is selected corresponding to a beverage being dispensed by a tap faucet 15 . The tap handle 20 is typically secured to the tap faucet 15 by screwing the base 32 of the tap handle 20 to a stud extending from the tap faucet 15 . The tap handle 20 is pulled forward to open the faucet 15 and start the flow of the beverage to be dispensed, in a manner as is well known. The tap handle 20 is pushed backwards to close the faucet 15 and stop the flow of the beverage.
[0034] The tap handle 20 allows a consumer to readily identify a desired beverage, and also provides a tap handle that can readily be identified by the consumer and distinguished from other tap handles. The first housing 22 may be molded in a shape familiar to the consumer, such as a bottle used to market the product in retail sales or some other shape that a producer may wish to employ in order to identify its product. Each of the first and second housings, 22 and 50 respectively, and the liquid 28 may be colored to resemble the color of the bottle used for retail sales or color of the beverage being dispensed. Alternately, the liquid 28 may be that of the beverage associated with the tap handle.
[0035] In addition, identifiers, for example, labels may be applied to the tap handle 20 that resemble the labels used on the bottle for retail sales. The resulting tap handle 20 has the familiar appearance of the packaging used for retail sales, and a consumer may readily identify the beverage being dispensed from the faucet 15 . Identifiers may also be included within cavity 24 of the first housing 22 or within the volume 52 defined by the second housing. The identifiers may be objects resembling, for example, animals, logos, or other features indicative of the beverage dispensed from the tap handle 20 .
[0036] The tap handle 20 also attracts a consumer's attention. As the handle is pulled forward and pushed backwards, the liquid 28 within the tap handle will move within the first housing 22 . The motion of the liquid 28 similarly induces motion in the floating particles 34 floating on or suspended within the liquid 28 . The motion of the liquid 28 and particles 34 attracts the attention of a consumer. The unique visual impression provided by the liquid within the interior of the tap handle is further enhanced when light is emitted upwardly from the base into the liquid.
[0037] It should be understood that the invention is not limited in its application to the details of construction and arrangements of the components set forth herein. The invention is capable of other embodiments and of being practiced or carried out in various ways. Variations and modifications of the foregoing are within the scope of the present invention. It also being understood that the invention disclosed and defined herein extends to all alternative combinations of two or more of the individual features mentioned or evident from the text and/or drawings. All of these different combinations constitute various alternative aspects of the present invention. The embodiments described herein explain the best modes known for practicing the invention and will enable others skilled in the art to utilize the invention | A tap handle includes a chamber that can be filled with liquid, which may be colored to represent a beverage associated with the tap handle. The material of the handle may be transparent or semi-transparent, allowing a consumer to readily identify a characteristic of the beverage, such as whether it is a dark or light beer. The body of the handle may be formed in the shape of a bottle, a glass, or any other ornamental design. The body of the handle may also include an insert in the lower portion for connecting the handle onto the tap. Alternately, the body may be secured to a fitting that, in turn, connects to the tap. The chamber may also include particles that float to top of the liquid, such that the liquid inside the chamber resembles beer or any other liquid, such as soda, that can be dispensed via a tap. | 8 |
[0001] This application claims priority from U.S. Patent Application No. 61/674,624, titled “Recovery of Base Metals from Sulphide Ores and Concentrates,” filed on Jul. 23, 2012, and which is incorporated herein by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] This invention relates to the recovery of base metals from sulphide ores and concentrates.
[0003] Conventional processing of base metals sulphide ores includes flotation and pyrometallurgical techniques as smelting of concentrates.
[0004] U.S. Pat. No. 4,283,017 describes a selective flotation of cubanite and chalcopyrite from copper/nickel mineralized rock. The disadvantage of this process consists in the ore beneficiation process, which requires high energy consume in order to reach very fine particles. The present invention can be fed with coarse particles.
[0005] U.S. Pat. No. 3,919,079 describes a process of flotation of sulphide minerals from sulphide bearing ore. The disadvantage of this process consists in the flotation process which use complex reagents: Dispersant, Collector, Alkali, Floculants. The complex reagents used in the flotation can cause environmental impact due to chemical oxygen demand for the decomposition of these reagents. The present invention does not require complex reagents.
[0006] U.S. Pat. No. 5,281,252 describes a conversion of non-ferrous sulfides which requires the insufflation of the copper sulphide particles and this process requires a complex control of agitation levels and contact of solid/liquid. Further, it requires the control of the internal atmosphere to ensure the reduction of the copper and the power supply for the reaction.
[0007] U.S. Pat. No. 4,308,058 describes a process for the oxidation of molten low-iron metal matte to produce raw metal. This process, however, requires multiple furnace operations as well as high temperatures (>1000° C.) which involves high energy consumption.
[0008] However these conventional processes become very expensive when dealing with low grade material and ores with high impurities content like chlorine and fluorine. Another problem with pyrometallurgical processing is the high capital of costs of a new plant, environmental, issues and high energy consumption.
[0009] Usually, when dealing with low grade material and ores with high impurities content, the gases resulting (dust; CO 2 ; NOx; H 2 O) from the process must be treated before sending the SO 2 to a sulphuric acid plant. Alternative methods comprise burning the concentrate.
BRIEF DESCRIPTION OF THE INVENTION
[0010] In light of the above described problems and unmet needs, the present invention provides an advantageous and effective a process of indirect and selective sulfation of base metals in the form of sulfides. This process can be applied for both concentrates or for low-grade sulfide ores; the greater focus being on the latter. Low-grade sulfide ores usually do not reach the desired content in the concentrate; and when they hit it, big losses happen. Impurities are the major problem. For this reason, the process described herein had been proposed.
[0011] More specifically, the present invention discloses a recovery of base metals from sulphide ores and concentrates, which comprises mixing the base metal's ore with ferric salts whose ratios are between 50% and 200% to base metals, heating the said mixture to temperatures between 400° C. and 600° C. for a period of 2 to 8 hours; adding water to form a pulp, then stirring and filtering the pulp.
[0012] Additional advantages and novel features of these aspects of the invention will be set forth in part in the description that follows, and in part will become more apparent to those skilled in the art upon examination of the following or upon learning by practice of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0013] The following detailed description does not intend to, in any way, limit the scope, applicability or configuration of the invention. More exactly, the following description provides the necessary understanding for implementing the exemplary modalities. When using the teachings provided herein, those skilled in the art will recognize suitable alternatives that can be used, without extrapolating the scope of the present invention.
[0014] The process of the present invention involves mixing the ore, concentrate or other sulphide material containing base metals with ferric sulfate or chloride in a screw mixer. The salt can come in a hydrated or anhydrous form. The mixture may have a ratio of 1:0.001 to 1:1000 of the sulphide material and the anhydrous salt. If a hydrated salt is used, the ratios may be changed proportionally.
[0015] Preferred ratios are between 50% and 200% to base metals considering the stoichiometry, preferably between 90 and 120% for the anhydrous form. It is a particularly attractive process once the deposit of the sulphide content is low and the concentration by flotation does not produce a concentrate of good quality. It is also effective if the concentration of fluorine and chlorine are above the specification limits.
[0016] This final mixture is later taken to a kiln, a furnace or any other equipment known by those skilled in the art, providing enough heat to reach temperatures preferably between 400° C. and 600° C., more preferably between 400° C. and 500° C. at atmospheric pressure in any kind of mixing apparatus. At that temperature, the following reaction occurs for a generic base metal sulphide:
[0000] 3 MS+Fe 2 (SO 4 ) 3 +4.5 O 2 =3 NiSO 4 +Fe 2 O 3 +3 SO 2
[0000] (where M represents a base metal).
[0017] Base metals are preferably copper, nickel and zinc, more preferably nickel.
[0018] Ferric sulfate is used as an example, as ferric chloride may also be used, changing reaction stoichiometry. Residence time is estimated to be preferably between 2 and 8 hours, more preferably for a period of 5 to 6 hours.
[0019] The production of ferric sulfate can be done in several ways by those skilled in the art.
[0020] Alternatively, oxide material can also be added to this mixture, providing the following reaction:
[0000] MS+3 MO+Fe 2 (SO 4 ) 3 +2 O 2 =4 NiSO 4 +Fe 2 O 3
[0000] (where M represents a base metal).
[0021] Base metals are preferably copper, nickel and zinc, more preferably nickel.
[0022] The above reaction would capture SO 2 , avoiding gas scrubbing. To capture fluorine or chlorine in solid form, a borate source such as, for example, boric acid, amorphous silica or any other reagent known by those skilled in the art can be added.
[0023] The final product from the kiln is taken to a dissolution stage, in order to solubilize most or all of the base metal salts. It is mixed with water to form a pulp of 10%-33% solids, preferably between 20% and 30%. The pulp should be kept under stirring for a period of 1-5 hours, preferably between 2 and 4 hours. From that point, any downstream choice, such as filtering, also known by those skilled in the art, can be selected for further processing and purification of the base metals.
[0024] Therefore, aspects of the process of the present invention involve mixing the salt (e.g. ferric chloride or sulfate) with a Ni concentrate at a temperature between 400° C. and 600° C. and for a period of 2 to 8 hours.
[0025] In a preferred embodiment of the present invention, mixing the salt (e.g. ferric chloride or sulfate) with a Ni concentrate is at a temperature between 400° C. and 500° C. and for a period of 5 to 6 hours, obtaining the Ni sulfates or chlorides that are taken to the dissolution stage. According to various aspects, the Ni sulfates and chlorides may be taken directly to the dissolution stage. The process enables the achievement of a very stable residue (hematite) and the rapid dissolution of salts.
[0026] It is estimated that the efficiency is between 80 and 95%
[0027] Optionally, conventional downstream processes such as production of MHP and electrolysis can be used after the present process in view to obtain the product of any kind of interest.
[0028] The user sets whether to produce a high purity, such as electrolytic nickel, or an intermediate product as MHP. These options are not exhaustive, but only examples of downstream. This downstream would be greatly simplified, since the step of removing impurities from solution (such as Fe and Al) is no longer necessary.
[0029] The advantages of the process of the present invention maybe numerous and may include one or more of:
better deposit exploration including deposits of low-sulfide which would not be economically viable for conventional flotation processes; reduced acid consumption; better settling properties of pulp; reduced consumption of flocculants; high levels of fluorine and chlorine would be no problem in the process of the present invention; This process is selective for the base metals. Thus, impurities such as iron and aluminum are not dissolved and these impurities in the conventional process downstream produce hydroxides which are very bulky and hard to decanting. As these elements are stable oxides (in the case of iron, are expected to stabilize as hematite), both the amount of solids formed would be lower as the ease of decanting of solid would be faster, thereby reducing the consumption of flocculants; The acidity of the solution obtained is low, reducing the need for neutralization. Below, are shown the thermodynamic data of the reactions proposed (for nickel and copper).
3CuS+Fe2(SO4)3+4.502(g)=3CuSO4+Fe2O3+3SO2(g)
[0000] T deltaH deltaS deltaG C. kcal cal/K kcal K Log(K) 0.000 −304.425 −64.106 −286.915 3.820E+229 229.582 100.000 −304.796 −65.321 −280.422 1.793E+164 164.254 200.000 −304.640 −64.969 −273.900 3.357E+126 126.526 300.000 −304.226 −64.181 −267.440 9.707E+101 101.987 400.000 −303.612 −63.198 −261.071 5.863E+084 84.768 500.000 −302.857 −62.154 −254.803 1.077E+072 72.032 600.000 −301.954 −61.058 −248.641 1.739E+062 62.240 700.000 −300.882 −59.895 −242.596 3.066E+054 54.487 800.000 −300.560 −59.577 −236.625 1.561E+048 48.193 900.000 −300.441 −59.470 −230.674 9.473E+042 42.976 1000.000 −300.432 −59.462 −224.728 3.803E+038 38.580
NiS+3NiO+Fe2(SO4)3+2O2(g)=4NiSO4+Fe2O3
[0000] T deltaH deltaS deltaG C. kcal cal/K kcal K Log(K) 0.000 −220.408 −93.107 −194.976 1.034E+156 156.015 100.000 −220.330 −92.921 −185.656 5.570E+108 108.746 200.000 −220.086 −92.330 −176.400 3.066E+081 81.487 300.000 −219.978 −92.150 −167.162 5.578E+063 63.746 400.000 −220.766 −93.311 −157.954 1.935E+051 51.287 500.000 −219.711 −91.854 −148.695 1.086E+042 42.036 600.000 −218.366 −90.221 −139.589 8.751E+034 34.942 700.000 −216.651 −88.363 −130.660 2.219E+029 29.346 800.000 −215.462 −87.199 −121.884 6.669E+024 24.824 900.000 −214.234 −86.106 −113.219 1.241E+021 21.094 1000.000 −220.102 −90.782 −104.524 8.792E+017 17.944
CuS+3CuO+Fe2(SO4)3+2O2(g)=4CuSO4+Fe2O3
[0000]
T
deltaH
deltaS
deltaG
C.
kcal
cal/K
kcal
K
Log(K)
0.000
−191.154
−92.312
−165.939
6.034E+132
132.781
100.000
−191.055
−92.055
−156.704
6.132E+091
91.788
200.000
−190.411
−90.547
−147.568
1.472E+068
68.168
300.000
−189.440
−88.694
−138.605
7.182E+052
52.856
400.000
−188.215
−86.730
−129.833
1.432E+042
42.156
500.000
−186.776
−84.740
−121.260
1.905E+034
34.280
600.000
−185.114
−82.721
−112.886
1.810E+028
28.258
700.000
−183.215
−80.662
−104.719
3.309E+023
23.520
800.000
−181.998
−79.469
−96.716
4.989E+019
19.698
900.000
−180.917
−78.506
−88.818
3.528E+016
16.548
1000.000
−179.881
−77.658
−81.011
8.082E+013
13.907
[0038] As can be seeing, the data above show that the reactions are thermodynamically favorable.
EXAMPLE 1
[0039] Jaguar ore, having the composition described in the table below, was mixed to ferric sulfate in the proportion of 200 grams of ore to 2.5 grams of anhydrous ferric sulfate (stoichiometric). After proper homogenization, the mixture was subjected to temperatures of 500° C. for 3 hours. After complete cooling of the material, water was added to form a pulp of 30% solids and the mixture was stirred for 1 hour.
[0040] The pulp was filtered and samples of the residue and of the PLS were sent for chemical analysis. Results indicated 85% nickel extraction, 77% copper extraction and 88% of cobalt extraction. Iron and other impurities were below 1%, with the exception of manganese, which obtained 97% extraction.
[0000]
Elemento
Cu
S
Al
Ca
Co
Fe
Mg
Ni
P
Si
Zn
K
Na
Unidade
%
%
%
%
%
%
%
%
%
%
%
%
%
Análise
0.092
4,230
3,097
1,552
0.059
34,025
4,628
0.952
0.387
10,200
0.649
0.278
0.085
Ag
Hg
Ba
Bi
Cd
Cr
Mn
Mo
Pb
Sn
Ti
V
Sb
LOI
ppm
ppb
%
%
%
%
%
%
%
%
%
%
ppm
%
2,127
<50
<0.01
<0.03
<0.01
<0.01
0.04
<0.01
<0.01
0.093
0.642
0.025
6,622
4,006
EXAMPLE 2
[0041] Jaguar ore, having the composition described in the table below, was mixed to ferric sulfate in the proportion of 200 grams of ore to 2.5 grams of anhydrous ferric sulfate (120% of the stoichiometric). After proper homogenization, the mixture was subjected to temperatures of 600° C. for 2 hours. After complete cooling of the material, water was added to form a pulp of 30% solids and the mixture was stirred for 1 hour. The pulp was filtered and samples of the residue and of the PLS were sent for chemical analysis. Results indicated 92% nickel extraction, 79% copper extraction and 93% of cobalt extraction. Iron and other impurities were below 1%, with the exception of manganese, which obtained 99% extraction.
[0000]
Elemento
Cu
S
Al
Ca
Co
Fe
Mg
Ni
P
Si
Zn
K
Na
Unidade
%
%
%
%
%
%
%
%
%
%
%
%
%
Análise
0.133
5,332
3,141
6,267
0.038
17,410
4,762
1.261
2067
16,453
1081
1
0.561
Ag
Hg
Ba
Bi
Cd
Cr
Mn
Mo
Pb
Sn
Ti
V
Sb
LOI
ppm
ppb
%
%
%
%
%
%
%
%
%
%
ppm
%
5,711
<50
<0.01
<0.03
<0.01
<0.01
0.089
<0.01
0.38
0.278
0.084
0.017
5,937
4,949
EXAMPLE 3
[0042] Jaguar ore, having the composition described in the table below, was mixed to ferric sulfate in the proportion of 200 grams of ore to 2.5 grams of anhydrous ferric sulfate (130% of the stoichiometric). After proper homogenization, the mixture was subjected to temperatures of 600° C. for 2 hours. After complete cooling of the material, water was added to form a pulp of 30% solids and the mixture was stirred for 1 hour. The pulp was filtered and samples of the residue and of the PLS were sent for chemical analysis. Results indicated 98% nickel extraction, 82% copper extraction and 94% of cobalt extraction. Iron and other impurities were below 1%, with the exception of manganese, which obtained 99% extraction.
[0000]
Elemento
Cu
S
Al
Ca
Co
Fe
Mg
Ni
P
Si
Zn
K
Na
Unidade
%
%
%
%
%
%
%
%
%
%
%
%
%
Análise
0.133
5,332
3,141
6,267
0.038
17,410
4,762
1.261
2067
16,453
1081
1
0.561
Ag
Hg
Ba
Bi
Cd
Cr
Mn
Mo
Pb
Sn
Ti
V
Sb
LOI
ppm
ppb
%
%
%
%
%
%
%
%
%
%
ppm
%
5,711
<50
<0.01
<0.03
<0.01
<0.01
0.089
<0.01
0.038
0.278
0.084
0.017
5,937
4,949 | The present invention discloses a new recovery of base metals from sulphide ores and concentrates, which comprises mixing the base metal's ore with ferric salts, heating the said mixture; adding water to form a pulp, stirring and filtering the pulp. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of provisional application Serial No. 60/182,159, filed Feb. 14, 2000, and is a continuation-in-part of application Ser. No. 09/448,985, filed Nov. 24, 1999, which claims the benefit of provisional application No. 60/147,888, filed Aug. 9, 1999. The contents of each of these applications are incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to a novel crystalline form of sertraline hydrochloride, and reproducible methods for its preparation.
BACKGROUND OF THE INVENTION
Sertraline hydrochloride, (1S-cis)-4-(3,4dichlorophenyl)-1,2,3,4-tetrahydro-N-methyl-1-naphthalenamine hydrochloride, having the formula
is approved, under the trademark Zoloft®, by the U.S. Food and Drug Administration, for the treatment of depression, obsessive-compulsive disorder and panic disorder.
U.S. Pat. No. 4,536,518 (“the '518 patent”) describes the preparation of sertraline hydrochloride with a melting point of 243-245° C. by treating an ethyl acetate/ether solution of the free base with gaseous hydrogen chloride. The solid state properties of the sertraline hydrochloride so produced are not otherwise disclosed.
U.S. Pat. No. 5,734,083 describes the preparation of a form of sertraline hydrochloride denominated polymorph “T1.”
According to U.S. Pat. No. 5,248,699 (“the '699 patent”), the sertraline hydrochloride produced by the method of the '518 patent has a crystalline form denominated “Form II.” The '699 patent discloses four other polymorphs of sertraline hydrochloride designated Forms I, III, IV, and V, and characterizes them by single crystal x-ray analysis, powder x-ray diffraction, infra-red spectroscopy, and differential scanning calorimetry. The '699 patent reports that Form II is produced by rapid crystallization of sertraline hydrochloride from an organic solvent, including isopropyl alcohol, ethyl acetate or hexane, and generally describes methods for making sertraline hydrochloride Forms I-V. According to this patent, the preferential formation of Forms I, II or IV in an acidic solution consisting of isopropyl alcohol, hexane, acetone, methyl isobutyl ketone, glacial acetic acid or, preferably, ethyl acetate, depends on the rapidity of crystallization. The only method described in this patent for making Forms II and IV is by the rapid crystallization of sertraline hydrochloride from an organic solvent such as those listed above.
The experimental procedure for the preparation of sertraline hydrochloride described in the '518 patent, was repeated in the laboratory. According to the '699 patent, the '518 procedure produces sertraline hydrochloride Form II. Four experiments were performed according to the description in the '518 patent. By following the procedures described in the '699 patent for preparation of sertraline hydrochloride Form II, we were unable to obtain sertraline hydrochloride Form II. Thus there remains a need for reproducible methods for the preparation of sertraline hydrochloride Form II.
SUMMARY OF THE INVENTION
The present invention relates to a process for making sertraline hydrochloride Form II comprising the steps of dissolving sertraline base or sertraline mandelate in an organic solvent to form a solution; adding hydrogen chloride to the solution; heating the solution to a temperature between about room temperature and about reflux for a time sufficient to induce the formation of sertraline hydrochloride Form II; and isolating sertraline hydrochloride Form II.
The present invention also relates to a process for making sertraline hydrochloride Form II comprising the steps of dissolving sertraline hydrochloride in dimethylformamide, cyclohexanol, acetone or a mixture thereof; heating the solution for a time sufficient to effect transformation to sertraline hydrochloride Form II; and isolating sertraline hydrochloride Form II.
The present invention further relates to a process for making sertraline hydrochloride Form II comprising the steps of granulating sertraline hydrochloride Form V in ethanol or methanol; and stirring the mixture of sertraline hydrochloride Form V and ethanol or methanol for a time sufficient to induce transformation to sertraline hydrochloride Form II.
The present invention still further relates to a process for making a mixture of sertraline hydrochloride Form II and Form V comprising the steps of heating sertraline hydrochloride ethanolate Form VI at up to 1 atmosphere pressure; and isolating a mixture of sertraline hydrochloride Form II and Form V.
The present invention still further relates to a process for making sertraline hydrochloride Form II comprising the steps of suspending a water or solvent adduct of sertraline hydrochloride in a solvent selected from the group consisting of acetone, t-butyl-methyl ether, cyclohexane, n-butanol, and ethyl acetate such that a slurry is formed, for a time sufficient to effect transformation to sertraline hydrochloride Form II; and filtering the slurry to isolate sertraline hydrochloride Form II.
The present invention still further relates to sertraline hydrochloride Form II, characterized by an x-ray powder diffraction pattern comprising peaks at about 5.5, 11.0, 12.5, 13.2, 14.7, 16.4, 17.3, 18.1, 19.1, 20.5, 21.9, 22.8, 23.8, 24.5, 25.9, 27.5, and 28.0 degrees two theta; pharmaceutical compositions for the treatment of depression comprising sertraline hydrochloride Form II together with a pharmaceutically acceptable carrier, and a method for treating depression comprising the step of administering to a subject in need of such treatment a therapeutically effective amount of the such a pharmaceutical composition.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a characteristic x-ray powder diffraction spectrum of sertraline hydrochloride prepared by the methods of U.S. Pat. No. 4,536,518.
FIG. 2 is a characteristic x-ray powder diffraction spectrum of sertraline hydrochloride prepared by the methods of U.S. Pat. No. 5,248,699.
FIG. 3 is a characteristic x-ray powder diffraction spectrum of sertraline hydrochloride Form II prepared by the methods of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Form II from Sertraline Base or Sertraline Mandelate
The present invention provides new processes for making sertraline hydrochloride Form II from sertraline base or sertraline mandelate. Sertraline base may be made by methods known in the art, including the methods of the '518 patent. Sertraline base is dissolved in a suitable solvent. Suitable solvents include ethyl acetate, acetone, t-methyl-butyl ether, isopropyl alcohol, n-butanol, t-butanol, iso-butanol, hexane, and cyclohexane, and mixtures thereof The pH of the sertraline base solution is lowered by the addition of hydrogen chloride, which may result in a temperature increase. As used herein, “hydrogen chloride” includes both gaseous hydrogen chloride and aqueous hydrogen chloride (i.e. hydrochloric acid). Hydrogen chloride also may be added as a solution with an organic solvent, such as a solution of isopropyl alcohol and hydrogen chloride, n-butanol and hydrogen chloride, acetone and hydrogen chloride, or the like. The solution of sertraline base or sertraline mandelate in the solvent is heated to a temperature between about room temperature and the reflux temperature of the solvent and maintained at that temperature for a period of time sufficient to effect the transformation to sertraline hydrochloride Form II. Preferably the solution is heated to a temperature between about 45° C. and the reflux temperature of the solvent. Most preferably the solution is heated to at or about the reflux temperature of the solvent. Upon cooling of the mixture, for example to room temperature, sertraline hydrochloride Form II is isolated by filtration.
In a preferred variation of this method, the solution of sertraline base or sertraline mandelate in a solvent is heated to the reflux temperature of the solvent. The mixture is refluxed for a time sufficient to effect the transformation to sertraline hydrochloride Form II. Preferably the mixture is refluxed for about 1 to 4 hours.
Numerous experiments were performed in an attempt to repeat the procedure described in U.S. Pat. No. 4,536,518 for preparing Form II wherein sertraline base was dissolved in ethyl acetate, ether was added and the solution was acidified with gaseous hydrogen chloride. The material obtained after filtration and air drying was sertraline hydrochloride amorphous, not Form II as was expected. These experiments are set forth in Examples 13-16 below.
The x-ray powder diffraction graphs for the products of each of these experiments are equivalent, containing peaks at 11.0, 12.0, 15.4, 16.2, 22.4, 22.9 degree two-theta (See FIG. 1 for a representative example). FIG. 1 does not contain the typical peaks of sertraline hydrochloride Form II, indicating an absence of sertraline hydrochloride Form II in those samples. Thus, none of these experiments, which follow the procedure described in the '518 patent for preparation of sertraline hydrochloride Form II, leads to sertraline hydrochloride Form II.
The '699 patent provides experimental procedures for preparation of sertraline hydrochloride. The '699 patent does not provide experimental procedure for preparation of sertraline hydrochloride Form II, but it is mentioned that sertraline hydrochloride Form II may be prepared by “rapid crystallization” from the same solvents.
The procedure of the '699 patent was repeated in an attempt to prepare sertraline hydrochloride form 11 from ethyl acetate. In a trial of the methods according to the '699 patent: An aqueous solution of sodium hydroxide, 10%, was added to a slurry of sertraline mandelate crystals (44.6 g) in ethyl acetate (290 mL), until complete dissolution. The organic phase was separated and the aqueous phase was extracted with ethyl acetate (280 mL) and combined with the organic phase. The resulting organic solution was washed with water (5×100 mL) then with brine (100 mL) and concentrated on a rotavapor to a volume of 356 mL. The concentrated solution was cooled to 58° C. and seeded with sertraline hydrochloride Form II. Concentrated hydrochloric acid (32%, 8.1 mL) was added to this solution. The solution was then rapidly cooled to 30° C. over 5 minutes. A heavy gel was obtained and the stirring was continued overnight. The solid was filtrated, washed with ethyl acetate and dried at 50° C. The dried solid, sertraline hydrochloride, was not sertraline hydrochloride Form II, as shown by the x-ray diffraction pattern of FIG. 2 .
By following the procedures described in the '699 patent for preparation of sertraline hydrochloride Form II, we did not obtain sertraline hydrochloride Form II. It is thus apparent that neither the '699 patent nor the '518 patent disclose a useful method for the preparation of sertraline hydrochloride Form II.
Form II from Sertraline Hydrochloride
The present invention also provides new processes for making sertraline hydrochloride Form II from sertraline hydrochloride Form V by granulation. In the conversion of sertraline hydrochloride Form V to sertraline hydrochloride Form II, sertraline hydrochloride Form V is combined with a small amount of ethanol or methanol. The mixture of sertraline hydrochloride Form V and ethanol or methanol is stirred for at least a period of at least a few hours, up to several days, preferably about two days, to induce the transformation of Form V to Form II. Sertraline hydrochloride Form II is then isolated by filtration.
The present invention also provides new processes for making sertraline hydrochloride Form II by recrystallization of sertraline hydrochloride under heating conditions. In the conversion of sertraline hydrochloride to sertraline hydrochloride Form II, sertraline hydrochloride is dissolved in a suitable organic solvent. The solution is then heated for a time sufficient to effect transformation to sertraline hydrochloride Form II. Suitable solvents include dimethylformamide, cyclohexanol and acetone. Dimethylformamide is preferred. The suspension may be heated to a temperature between about 70° C. and 120° C. Sertraline hydrochloride Form II is then isolated by filtration.
The present invention provides new processes for making sertraline hydrochloride Form II from sertraline hydrochloride Form VI, Form VII or Form VIII by reslurry in organic solvents at temperatures between 25-80° C., followed by drying. Sertraline hydrochloride Form VI may be made following the methods of Examples 2 and 3. Sertraline hydrochloride Form VII is a water adduct and may be made by the methods of Examples 19 and 20. Sertraline hydrochloride Form VIII may be made by the methods of Examples 17 and 18. The methods provided in the present invention have advantages over the rapid recrystallization method of U.S. Pat. No. 5,248,699. The method of the present invention does not require complete dissolution of sertraline hydrochloride, controlling the rate of heating or cooling of a sertraline solution, or controlling the rate of crystallization. The present method utilizes less solvent than the method of the '699 patent, since the sertraline hydrochloride starting material need not be completely dissolved.
In the conversion of sertraline hydrochloride Form VI, Form VII or Form VIII to sertraline hydrochloride Form II, according to the present invention, sertraline hydrochloride Form VI, Form VII water adduct, or Form VIII is combined with an aprotic organic solvent to form a slurry. Suitable solvents include n-butanol, acetone, t-butyl-methyl ether (MTBE), ethyl acetate and cyclohexane. The conversion may take place at room temperature, but preferably the sertraline hydrochloride Form VI, Form VII water adduct, or VIII and solvent are heated to temperatures between 25° C. and 80° C. About 1 to about 10 volumes of solvent are preferred, based on the weight of the sertraline hydrochloride starting material. See Examples 8 (3 volumes of solvent) and 9 (5 volumes of solvent) below. Smaller amounts of solvent will also effect the transformation, albeit in some instances more slowly. The reaction is carried out for a time sufficient to convert the Form VI, Form VII or Form VIII to Form VI. We have not observed any further conversion of Form II upon treatment under these conditions for times longer than the minimum time necessary to effect the transformation.
The present invention also provides new processes for making a mixture of sertraline hydrochloride Form II and sertraline hydrochloride Form V. In this embodiment of the present invention, sertraline hydrochloride Form VI is heated to induce the transformation of sertraline hydrochloride Form VI to a mixture of both sertraline hydrochloride Form II and sertraline hydrochloride Form V. In this embodiment of the present invention, the heating of sertraline hydrochloride Form VI may be done under reduced pressure or atmospheric pressure.
Pharmaceutical Compositions Containing Sertraline Hydrochloride Polymorphs
In accordance with the present invention, sertraline hydrochloride Form II as prepared by the new methods disclosed herein may be used in pharmaceutical compositions that are particularly useful for the treatment of depression, obesity, chemical dependencies or addictions, premature ejaculation, obsessive-compulsive disorder and panic disorder. Such compositions comprise at least one of the new crystalline forms of sertraline hydrochloride with pharmaceutically acceptable carriers and/or excipients known to one of skill in the art.
For example, these compositions may be prepared as medicaments to be administered orally, parenterally, rectally, transdermally, bucally, or nasally. Suitable forms for oral administration include tablets, compressed or coated pills, dragees, sachets, hard or gelatin capsules, sub-lingual tablets, syrups and suspensions. Suitable forms of parenteral administration include an aqueous or non-aqueous solution or emulsion, while for rectal administration suitable forms for administration include suppositories with hydrophilic or hydrophobic vehicle. For topical administration the invention provides suitable transdermal delivery systems known in the art, and for nasal delivery there are provided suitable aerosol delivery systems known in the art.
Suitable non-toxic pharmaceutically acceptable carriers and/or excipients will be apparent to those skilled in the art of pharmaceutical formulation, and are discussed in detail in the tet entitled Remington's Pharmaceutical Science , 17 th edition (1985), the contents of which are incorporated herein by reference. Obviously, the choice of suitable carriers will depend on the exact nature of the particular dosage form, e.g. for a liquid dosage form, whether the composition is to be formulated into a solution, suspension, gel, etc, or for a solid dosage form, whether the composition is to be formulated into a tablet, capsule, caplet or other solid form, and whether the dosage form is to be an immediate- or controlled-release product.
Experimental Details
The powder X-ray diffraction patterns were obtained by methods known in the art using a Philips X-ray powder diffractometer, Goniometer model 1050/70 at a scanning speed of 2° per minute, with a Cu radiation of λ=1.5418 Å
EXAMPLES
The present invention will now be further explained in the following examples. However, the present invention should not be construed as limited thereby. One of ordinary skill in the art will understand how to vary the exemplified preparations to obtain the desired results.
Example 1
Preparation of Sertraline Base
Sertraline mandelate was prepared according to procedures in U.S. Pat. No. 5,248,699. Sertraline mandelate (5 g) was stirred at room temperature with 50 mL ethyl acetate. Aqueous sodium hydroxide was added dropwise until the sertraline mandelate was completely neutralized. The phases were separated and the organic phase was dried over MgSO 4 and filtered. The solvent was removed under reduced pressure resulting sertraline base as an oil (3.2 g).
Example 2
Preparation of Sertraline Hydrochloride Ethanolate Form VI by Reslurry of Form I
Sertraline hydrochloride Form I (1 g) and absolute ethanol (20 mL) were stirred at room temperature for 24 hours. Filtration of the mixture yielded sertraline hydrochloride ethanolate Form VI.
Example 3
Preparation of Sertraline Hydrochloride Ethanolate Form VI by Reslurry of Form V
Sertraline hydrochloride Form V (1 g) and ethanol absolute (20 mL) were stirred at room temperature for 24 hrs. Filtration of the mixture yielded sertraline hydrochloride ethanolate Form VI.
Example 4
Preparation of Sertraline Hydrochloride Form II
Sertraline base (3 g) was dissolved in acetone (10 mL). Isopropanol containing hydrogen chloride (20 mL) was added to the solution until the pH is ˜2. The stirring was continued overnight at room temperature. The resulting solid was filtered, washed with acetone and dried to yield sertraline hydrochloride Form II (2.61 g, yield 77.6%).
Example 5
Preparation of Sertraline Hydrochloride Form II in n-Butanol
HCl (g) was bubbled through a solution of sertraline base (33 g) in n-butanol (264 mL). The temperature rose to about 45° C. A gel-like solid was formed. The addition of HCl (g) was continued until pH 0.5 was reached. Then the stirring was continued at room temperature for 2.5 h. During the stirring the solid became a fine crystalline solid. The solid was filtered, washed with n-butanol (2×10 mL) and dried at 80° C. for 24 h. The product is sertraline hydrochloride Form II. The x-ray powder diffraction spectrum obtained is FIG. 3 .
Example 6
Preparation of Sertraline Hydrochloride Form II
Sertraline hydrochloride Form V (10 g) was suspended in dimethylformamide (DMF) (30 mL). Heating was started and at about 70° C. a clear solution is obtained. The solution was cooled to room temperature and the solid was filtered. After drying at 80° C. for 24 hrs., sertraline hydrochloride Form II was obtained (6.6 g, yield 66%).
Example 7
Preparation of Sertraline Hydrochloride Form II by Granulation of Form V
Sertraline hydrochloride Form V (2 g) and absolute ethanol (0.5 mL) were stirred in a rotavapor at room temperature for 2 days. At the end of two days, the material contained sertraline hydrochloride Form II.
Example 8
Preparation of Sertraline Hydrochloride Form II from Form VI
A slurry of sertraline hydrochloride Form VI (50 g) and t-butyl-methyl ether (150 mL) were heated to reflux and the reflux was continued for 1 hour. The slurry was then allowed to cool to room temperature and filtered. The solid was washed with t-butyl-methyl ether (50 mL) and dried in a reactor under vacuum of 30 mm Hg with stirring. The dried solid so obtained is sertraline hydrochloride Form II (38.26 g: yield 86.7%).
Example 9
Preparation of Sertraline Hydrochloride Form II from Form VI
Sertraline hydrochloride Form VI (25 g) was stirred with acetone (250 mL) at room temperature for 2 hours. The solid material was filtered and washed twice with acetone (25 mL). The wet solid was dried in a vacuum agitated drier to afford sertraline hydrochloride Form II (20.09 g: yield 98.6%).
Example 10
Preparation of Sertraline Hydrochloride Form II and Sertraline Hydrochloride Form V by Drying Form VI
Sertraline hydrochloride ethanolate Form VI was dried at 105° C. under vacuum (<10 mm Hg) over 24 hours. The resulting dried material was sertraline hydrochloride Form II mixed with sertraline hydrochloride Form V.
Example 11
Preparation of Sertraline Hydrochloride Form II from Sertraline Mandelate in n-Butanol
Sertraline mandelate (20 g) and n-butanol were stirred at room temperature. The mixture was acidified with hydrogen chloride until pH 0 was reached. During the acidification the temperature of the reaction mixture rose to ˜50° C. After the natural cooling to room temperature, the mixture was stirred at room temperature for two hours. The solid was filtrated, washed with n-butanol and dried at 80° C. to afford sertraline hydrochloride Form II (9.02 g).
Example 12
Preparation of Sertraline Hydrochloride Form I from Sertraline Hydrochloride Form VIII
Sertraline hydrochloride Form VIII (13 g) was heated in acetone (130 mL) at reflux for 1 hour. The slurry was than cooled to room temperature and the solid was filtrated and washed with acetone (2×10 mL). After drying sertraline hydrochloride Form II was obtained (7.9 g).
Example 13
An aqueous sodium hydroxide solution, 10%, was added drop-wise to a slurry of sertraline mandelate crystals (10 g) in ethyl acetate (650 mL), until complete dissolution was obtained (25 mL). After separation of the phases, the organic phase was washed with water (300 mL) and then dried with MgSO 4 . The organic solution was diluted with ether (690 mL) and gaseous hydrochloric acid was bubbled through the solution until pH 1.3 was reached. The addition of hydrogen chloride resulted in a temperature increase to about 30° C. The resulting slurry of sertraline was stirred at room temperature overnight. The solid was then isolated by filtration, washed twice with ether (2×20 mL) and air dried. The dried solid, sertraline hydrochloride, was not sertraline hydrochloride Form II, as shown in FIG. 1 .
Example 14
An aqueous sodium hydroxide solution, 10%, was added drop-wise to a slurry of sertraline mandelate crystals (15 g) in ethyl acetate (810 mL), until complete dissolution was obtained (35 mL). The organic and aqueous phases were separated and, the organic phase was dried over MgSO 4 The organic solution was then diluted with ether (820 mL) and gaseous hydrogen chloride (2.36 g, 2 eq.) was bubbled through the solution until pH 1.5 was reached. The temperature was about 25° C. The slurry was stirred at room temperature overnight. The solid was filtrated, washed with ether (2×15 mL) and air-dried. The dried solid, sertraline hydrochloride, was not sertraline hydrochloride Form II.
Example 15
An aqueous sodium hydroxide solution, 10%, was added drop-wise to a slurry of sertraline mandelate crystals (15 g) in ethyl acetate (810 mL), until complete dissolution was obtained. The organic and aqueous phases were separated and the organic phase was dried over MgSO 4 and diluted with an equal volume of ether (820 mL). Gaseous hydrochloric acid (4.82 g) was bubbled through the solution until pH 1 was reached. The slurry was stirred at room temperature overnight. The solid was filtrated, washed with ether (2×15 mL) and air-dried. The dried solid, sertraline hydrochloride, was not sertraline hydrochloride Form II.
Example 16
An aqueous sodium hydroxide solution, 10%, was added drop-wise to a slurry of sertraline mandelate crystals (15 g) in ethyl acetate (810 mL), until complete dissolution is obtained. The phases were separated and the organic phase was dried over MgSO 4 and diluted with an equal volume of ether (820 mL). Gaseous hydrogen chloride was slowly bubbled through the solution (over about 3 hours) until pH 1.5 was reached. The slurry was stirred at room temperature over night. The dried solid, sertraline hydrochloride, was not sertraline hydrochloride Form II.
Example 17
Preparation of Sertraline Hydrochloride Form VIII
Sertraline base (2.7 g) was suspended in 27 mL of water. This mixture was heated to 80° C. and treated with hydrochloric acid until about pH 1 was reached. A clear solution was obtained which on cooling gave a precipitate. After 2 hours stirring at room temperature the solid was isolated by filtration. This solid was characterized by powder x-ray diffraction and found to be sertraline hydrochloride Form VIII.
Example 18
Preparation of Sertraline Hydrochloride Form VIII
Sertraline hydrochloride ethanolate (Form VI) (40 g) was stirred with water (80 mL) for 1 hour at room temperature. The slurry was filtrated and washed with water to yield sertraline hydrochloride hydrate Form VIII.
Example 19
Preparation of Sertraline Hydrochloride Form VII
Sertraline hydrochloride Form V (1.003 g) was stirred for 24 hours at room temperature in 20 mL water (HPLC grade). At the end of the stirring the mixture looked like a jelly suspension. The suspension was filtrated and the compound obtained was kept at cold conditions (4° C.) until analyzed by x-ray diffraction.
Example 20
Preparation of Sertraline Hydrochloride Form VII from Form VI
A solution of sertraline hydrochloride ethanolate (Form VI) (40 g) in water (400 mL) was heated at 80° C. and complete dissolution of sertraline hydrochloride ethanolate (Form VI) was obtained. The pH was adjusted to about 1 and the solution was allowed to cool to room temperature and then stirred for 2 additional hours. The solid was isolated by filtration and washed with water to yield sertraline hydrochloride Form VII.
Although certain presently preferred embodiments of the invention have been described herein, it will be apparent to those skilled in the art to which the invention pertains that variations and modifications of the described embodiments may be made without departing from the spirit and scope of the invention. Accordingly, it is intended that the invention be limited only to the extent required by the appended claims and the applicable rules of law. | The present invention is directed to Form II of sertraline hydrochloride and novel methods for its preparation. According to the present invention, sertraline hydrochloride Form II may be produced directly form sertraline base or sertraline mandelate. It may also be produced from sertraline hydrochloride solvate and hydrate forms, and crystallized from new solvent systems. Pharmaceutical compositions containing sertraline hydrochloride Form II and methods of treatment using such pharmaceutical compositions are also disclosed. | 2 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates broadly to apparatus and methods for investigating subsurface earth formations. More particularly, this invention relates to borehole tools and methods for making hydraulic property measurements of an earth formation surrounding a borehole, and in particular apparatus and methods for generating appropriate pressure-pressure response functions in homogeneous and heterogeneous formations.
[0003] 2. State of the Art
[0004] The determination of permeability (fluid mobility) and other hydraulic properties of formations surrounding boreholes is very useful in gauging the producibility of formations, and in obtaining an overall understanding of the structure of the formations. For the reservoir engineer, permeability is generally considered a fundamental reservoir property, the determination of which is at least equal in importance with the determination of porosity, fluid saturations, and formation pressure. When obtainable, cores of the formation provide important data concerning permeability. However, cores are difficult and expensive to obtain, and core analysis is time consuming and provides information about very small sample volumes. In addition, cores, when brought to the surface, may not adequately represent downhole conditions. Thus, in situ determinations of permeability which can quickly provide horizontal and vertical determinations of permeabilities over larger portions of the formation are highly desirable.
[0005] Existing techniques for making permeability determinations can be classified into indirect and direct methods. In indirect methods, permeability is determined from empirical correlations which attempt to express permeability in terms of other measured formation parameters, such as porosity, saturation, or mineralogy. A direct measurement technique involves actual measurement of fluid flow, pressure, etc. and determination of permeability from these measurements.
[0006] Suggestions regarding a direct in situ determination of permeability via the injection or withdrawal of fluid into or from the formation and the measurement of pressures resulting therefrom date back at least to U.S. Pat. No. 2,747,401 to Doll (1956). In the Doll patent there is disclosed a method and apparatus for determining hydraulic characteristics, including permeability, fluid pressure, and hydraulic anisotropy, of formations surrounding a borehole. A pressure gradient is obtained in the formations by pressing or pushing a probe against the borehole wall. Pressure differences between different points are then used to obtain indications of hydraulic characteristics of the formations. In an embodiment disclosed in the patent, a pair of spaced probes are pressed against the formation, and a pressure gradient is generated by injecting a fluid into the formation at one of the probes (a source probe) at a constant flow rate. The other probe (a measurement probe) is coupled to a pressure responsive device. Pressure is measured at the measurement probe before and after injection of the fluid at the source probe. The permeability of the formation is then obtained using a formula in which permeability is proportional to viscosity times flow rate divided by the change in pressure. The patent points out that the pressure gradient can also be obtained by extracting fluid from the formation and that measurements can be made in more than one direction; e.g., vertical and horizontal, to obtain indications of both vertical and horizontal hydraulic characteristics.
[0007] Different devices have been used for making direct measurements of permeability. For example, devices whose primary use has been for sampling formation fluids, have also been used with some success in estimating formation permeability. Formation testing devices which can take repeated samples are disclosed, for example, in U.S. Pat. Nos. 3,780,575 to Urbanosky and 3,952,588 to Whitten, both of which are hereby incorporated by reference herein in their entireties. In these devices, a hydraulic pump provides pressure for the operation of various hydraulic systems in the device. Sample chambers are provided in the tool to take samples of formation fluid by withdrawing hydraulically operated pistons. Pressure transducers are provided to monitor pressure as the fluid is withdrawn, and pressure can be continuously recorded. So-called pre-test chambers are also typically provided and are operated to permit more reliable flow during the subsequent fluid withdrawal. Filters can also be provided to filter sand and other particulate matter, and pistons can be provided to clean the filters, such as when the tool is retracted.
[0008] One type of formation testing device includes an elongated body and a setting arm activated by setting pistons which are used to controllably urge the body of the device against a side of the borehole wall at a selected depth. The side of the device that is urged against the borehole wall includes a packer which surrounds a probe. As the setting arm extends, the probe is inserted against the formation, and the packer then sets the probe in position and forms a seal around the probe, whereupon the fluids can be withdrawn from the formation during pre-test and the actual test.
[0009] The primary technique presently used for in situ determination of permeability is the “drawdown” method where a probe of a formation testing tool is placed against the borehole wall, and the pressure inside the tool (e.g., at a chamber) is brought below the pressure of the formation, thereby inducing fluids to flow into the formation testing tool. By measuring pressures and/or fluid flow rates at and/or away from the probe, and processing those measurements, determinations regarding permeability are obtained. These determinations, however, have typically been subject to large errors. Among the reasons for error include the fact that if fluid is extracted at a fixed flow rate which is independent of permeability, as is typically done, in low permeability formations the pressure drop tends to be too large, and solution gas and/or water vapor forms and can make the results uninterpretable. Indeed, liberation of gas during drawdown provides anomalous pressure and fluid flow rate readings. Another source of error is the damage to the formation (i.e., pores can be clogged by migrating fines) which occurs when the fluid flow rate towards the probe is caused to be too large. See, e.g., T. S. Ramakrishnan et al., “A Laboratory Investigation of Permeability in Hemispherical Flow with Application to Formation Testers”, SPE Form. Eval. 10, pp. 99-108 (1995).
[0010] More recent patent disclosures of permeability testing tools include U.S. Pat. No. 4,742,459 to Lasseter, and U.S. Pat. No. 4,860,581 to Zimmerman et al. (both of which are hereby incorporated by reference herein in their entireties) which further develop the draw-down techniques. In the Lasseter patent, a logging device is provided having a source probe, a horizontal observation probe which is azimuthally displaced on the borehole wall with respect to the source probe position, and a vertical observation probe which is vertically displaced on the borehole wall with respect to the source probe position. The source probe is provided with means for withdrawing fluid at a substantially constant rate or pressure, while the vertical and horizontal probes, as well as the source probe, are provided with means for measuring formation pressure response as a function of time. According to the method for determining permeability, a transient pressure change is established in the formation by withdrawing fluid from the formation at the source probe location. The formation pressure response is then measured at the vertical and horizontal probes. By selecting a trial permeability value, theoretical formation pressure responses can be derived as a function of time at the probe locations. The theoretical formation pressure responses are then compared with the actually measured pressure responses in an iterative manner, with the difference being used as feedback to modify the trial value, until the difference is negligible.
[0011] The Zimmerman et al. patent mentions that in the drawdown method, it is essential to limit the pressure reduction so as to prevent gas liberation. In order to prevent gas liberation, Zimmerman et al. propose a flow controller which regulates the rate of fluid flow into the tool.
[0012] Additional progress in in situ permeability measurement is represented by U.S. Pat. No. 5,269,180 to Dave et al., U.S. Pat. No. 5,335,542 to Ramakrishnan et al., and U.S. Pat. No. 5,247,830 to Goode, all of which are hereby incorporated by reference herein in their entireties. In the Dave et al. patent, borehole tools, procedures, and interpretation methods are disclosed which rely on the injection of both water and oil into the formation whereby endpoint effective permeability determinations can be made. In the Ramakrishnan et al. patent, a tool which integrates hydraulic and electromagnetic measurements (images) is disclosed. In the Goode patent, methods are disclosed for making horizontal and vertical permeability measurements without the necessity for measuring flow rate into or out of the borehole tool. In particular, an interpretation scheme is presented in which the change in pressure at the vertical observation probe is related to the change in pressure at the horizontal probe through a convolutional integral. The kernel function G in this integral is independent of the flowrate at the sink probe. This scheme is called pressure-pressure deconvolution, and it eliminates the need for knowing the tool storage volume (i.e., the volume of fluid in the tool connected to the formation) and the formation damage at the sink probe. However, the problem of storage at the observation probes remains and can be a source of error in the interpretation because the local flow at each observation probe causes a pressure change that cannot be neglected. Thus, even with these inventions which have advanced the art significantly, the accuracy and scope of the information obtained is not to the level desired.
SUMMARY OF THE INVENTION
[0013] It is therefore an object of the invention to provide apparatus and methods for conducting accurate measurements of hydraulic properties of an earth formation.
[0014] It is another object of the invention to provide apparatus and methods for generating appropriate pressure-pressure response functions in homogeneous and heterogeneous formations.
[0015] It is a further object of the invention to provide methods and apparatus for eliminating storage effects in pressure-pressure deconvolutional analysis.
[0016] It is an additional object of the invention to provide a modified pressure-pressure deconvolution for improved stability.
[0017] Another object of the invention is to provide apparatus and methods eliminating storage effects without requiring additional testing of the formation.
[0018] In accord with the objects of the invention, the effects of storage on the interpretation of data obtained at the observation probes can be eliminated by controlling the storage volumes relative to the observation probes. For a homogeneous medium, the effect of storage on the interpretation of data from the observation probes may be eliminated by causing the flow line volumes connected to each observation probe to be equal to each other. For a heterogeneous medium, the effect of storage on the interpretation of data from the observation probes may be eliminated by causing the flow line volumes to vary in proportion to the permeabilities of the strata of the heterogeneous medium adjacent the probes. The borehole tool of the invention is therefore provided with means for conducting flow line volume adjustment. Thus, where the vertical observation probe is located in one stratum (layer) of the formation having a first permeability and the horizontal observation probe is located in another stratum having a second permeability, based on local drawdown permeabilities estimated in pretest procedures, the flow line volumes connected to the respective observation probes are adjusted in order to remove the effect of storage on the interpretation of data during testing.
[0019] Additional objects and advantages of the invention will become apparent to those skilled in the art upon reference to the detailed description taken in conjunction with the provided figures.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] [0020]FIG. 1 is a diagram, partially in schematic form, of an apparatus in accordance with an embodiment of the invention which can be used to practice an embodiment of the method of the invention;
[0021] [0021]FIG. 2 is a diagram, partially in schematic form, of portions of the logging device of FIG. 1;
[0022] [0022]FIG. 3 is a graph showing three plots of the pressure-pressure response function for a homogeneous medium at different storage ratios; and
[0023] [0023]FIG. 4 is a graph showing four plots of the pressure-pressure response function for a heterogeneous medium at different storage ratios.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] An apparatus 100 for investigating subsurface formations 31 traversed by a borehole 32 is seen in FIG. 1. Typically, the borehole 32 is filled with a drilling fluid or mud which contains finely divided solids in suspension. The investigating apparatus or logging device 100 is suspended in the borehole 32 on an armored multiconductor cable 33 , the length of which substantially determines the depth of the device 100 . A known depth gauge apparatus (not shown) is provided to measure cable displacement over a sheave wheel (not shown) and thus record the depth of the logging device 100 in the borehole 32 . The cable length is controlled by suitable means at the surface such as a drum and winch mechanism (not shown). Circuitry 51 , shown at the surface of the formation, although portions thereof may be downhole, represents control, communication and preprocessing circuitry for the logging apparatus. This circuitry may be of known type, and is not, per se a novel feature of the present invention.
[0025] The preferred logging device 100 has an elongated body 121 which encloses the downhole portion of the device controls, chambers, measurement means, etc. Arms 122 and 123 are mounted on pistons 125 which extend, under control from the surface, to set the tool. Mounted on the arm 122 are a source probe 160 , and spaced above and vertically therefrom, a vertical observation probe 170 . Mounted on the arm 123 is a horizontal observation probe 180 . The arm may also contain a further measuring device, such as an electrical microresistivity device at the position 190 . Conduits 61 , 71 , and 81 are provided and are slidably mounted in body 121 for communication between the probes 160 , 170 , and 180 , respectively, and the body 121 .
[0026] As is disclosed in previously incorporated U.S. Pat. No. 4,742,459, the source probe 160 preferably comprises either a fluid sink or a fluid source which includes a packer 161 with a fluid-carrying line that communicates with the formation when the packer is set. The present invention is not dependent on use of a particular type of mechanical means for withdrawing fluid from or injecting fluid into the formations, as any of numerous such device well known in the art may be utilized.
[0027] As seen in FIG. 2, a pretest chamber 169 is accessed via a valve 163 . A controlled flow system with chambers 164 is accessible via valve 165 . The control of sample dump to the borehole is via valve 167 . In addition, valve 166 a is provided along with sample chambers 166 b to permit storage of samples to be brought to the surface of the formation. A pressure measurement device 162 such as a strain gauge type of pressure meter is provided to monitor pressure at the probe. In accord with the preferred embodiment of the invention, and as described in previously incorporated U.S. Pat. No. 5,247,830 to Goode, no flow rate meter is required as flow rate is not used in making determinations of the hydraulic properties of the formation according to the preferred embodiment of the invention.
[0028] The vertical observation probe 170 comprises a packer 171 with an observation port or probe that engages the borehole, and communicates via fluid conduit (also called “flow line”) 177 with a pretest chamber 172 via a valve 173 . A high resolution high-accuracy pressure meter 175 , such as of the quartz piezoelectric type, is preferably provided to monitor the pressure at the probe. Extending from flow line 177 are a plurality of branch flow lines 177 a - 177 n . Each branch flow line is coupled to the main flow line 177 via valves 173 a - 173 n . In this manner, as will be discussed in greater detail hereinafter, the fluid storage volume associated with the probe 170 may be adjusted. Each branch flow line 177 a - 177 n may be a dead-end line, and if desired, each branch flow line 177 a - 177 n may be of equal size and hold an equal volume of fluid. Alternatively, the flow lines may hold different amounts of fluid, and/or one or more of the flow lines may be coupled to a fluid chamber (not shown) which can hold a substantial amount of fluid. As another alternative, a single branch flow line may be provided with multiple valves in series along the branch flow line. In this manner, valves may be opened in sequence to provide a desired storage volume for the probe. In any event, it is desirable that the storage volume fluidly coupled to the probe be adjustable by means of the branch flow line(s) so that the storage volume can be increased by a factor of ten or even one hundred relative to the storage volume when all branch flow lines are closed. Depending upon the arrangement of the branch flow line(s), (i.e., whether multiple branch flow lines are used and whether they are all equal in volume), the step may be larger or smaller. Thus, for example, using eleven branch flow lines ( 177 a - 177 k ) having storage volumes equal to {fraction (1/16)}, ⅛, ¼, ½, 1, 2, 4, 8, 16, 32, and 64 times the storage volume of flow line 177 , and by controlling the valves which couple and decouple the branch flow line to the main flow line, the total storage for the probe may be increased in steps of 6.25% to an amount over one hundred times (10,000%) the storage volume of the probe.
[0029] According to the preferred embodiment of the invention, the flow lines 177 a - 177 n (and preferably main flow line 177 ) are either filled (primed) with a liquid such as water or oil prior to placing the tool in the borehole, or the flow lines are provided with additional valves (not shown) which permit the lines to be flushed with reservoir fluid or with fluid carried downwhole (as described in the previously incorporated Dave et al. U.S. Pat. No. 5,269,180). Where the flow lines are filled with liquid prior to placement downhole, according to the preferred embodiment of the invention, it is preferred that the main flow line 177 still be provided with an additional valve to permit flushing of the main flow line.
[0030] The horizontal observation probe 180 is of similar construction to the vertical observation probe and includes a packer 181 with an observation port or probe that engages the borehole and communicates via a fluid conduit 187 with the pretest chamber 182 and valve 183 . A pressure measuring means 184 is also coupled to the fluid conduit 187 . Preferably, the fluid conduit 187 is of exactly the same storage capacity as the fluid conduit 177 associated with probe 170 . In addition, the fluid conduit 187 is also preferably provided with a plurality of branch flow lines 187 a - 187 n which are coupled thereto via valves 183 a - 183 n . In this manner, as will be discussed in greater detail hereinafter, the fluid storage volume associated with the probe 180 may be adjusted. Despite the preference of a quartz piezoelectric type pressure meter, the present invention is not dependent on use of a particular device for taking pressure measurements, as many such devices (e.g., a strain gauge or sapphire sensor) are well known in the art.
[0031] As with branch flow lines 177 a - 177 n , branch flow lines 187 a - 187 n (and preferably main flow line 187 ) are either filled with a liquid such as water or oil prior to placing the tool in the borehole, or the flow lines are provided with additional valves (not shown) which permit the lines to be flushed with reservoir fluid or with fluid carried downwhole. In this manner, the fluids contained in each of the probes 170 , 180 are matched.
[0032] The mechanical elements of the system are controlled from the surface of the earth hydraulically and electrically in a known fashion. Likewise, the pressure at the source probe and the observation probes are monitored and transmitted to the surface of the earth for recording in known manners.
[0033] The signal outputs of block 51 are illustrated as being available to processor 500 which, in the present embodiment, is implemented by a general purpose digital computer. It will be understood, however, that a suitable special purpose digital or analog computer could alternatively be employed. Also, it will be recognized that the processor may be at a remote location and receive inputs by transmission of previously recorded signals. The outputs of the computing module 500 are values or value-representative signals for formation hydraulic properties, developed in accordance with techniques described hereinbelow. These signals are recorded as a function of depth on recorder 90 , which generically represents graphic, electrical and other conventional storage techniques.
[0034] In operation, at a depth level at which measurements are to be taken, the pistons 125 are extended and the tool is set. Under control from the surface, a pretest is then performed at the source probe 160 and the observation probes 170 and 180 . The function of the pretest is to flush out mud or mud cake from between the source and observation probes and the formation so as to ensure good hydraulic seals and communication with the formation. During pretest, the fluid lines of the borehole tool are generally flushed to remove borehole fluid and mud. However, for purposes of the present invention, the pretest may also function in a manner well known in the art to obtain an estimate of permeabilities of the formation adjacent each of the probes. See, e.g., “RFT: Essentials of Pressure Test Interpretation”, Schlumberger, 1981.
[0035] Based on the rough estimates of the formation permeability adjacent the observation probes 170 , 180 , the relative fluid storage of flow lines 177 , 187 may be adjusted by opening appropriate valves chosen from valves 173 a - 173 n and 183 a - 183 n . In particular, if the estimates of formation permeability adjacent the observation probes 170 , 180 indicate that the tool is located in a homogeneous formation or a homogeneous portion of the formation (i.e., the estimates are equal), none of the valves 173 a - 173 n and 183 a - 183 n are opened as flow lines 177 and 187 are designed to have the same storage capacity. Thus, according to the invention, the storage effects on the pressure-pressure deconvolution will be effectively canceled as will be discussed in detail hereinafter. However, if the permeability estimates resulting from the pretest indicate that the tool is in a heterogeneous portion of the formation (i.e., the estimates are different), according to the invention, one or more of valves 173 a - 173 n and 183 a - 183 n are opened so that the ratio of the storage capacities of the flow lines 177 and 187 (including the branch flow lines in fluid communication therewith) is substantially equal to the ratio of the permeability estimates.
[0036] It should be appreciated that because the process of pretesting can cause different types of fluids to enter flow lines 177 and 187 , it may be desirable to flush flow lines 177 and 187 with formation fluids or fluids carried downhole before opening any of valves 173 a - 173 n or 183 a - 183 n and continuing.
[0037] The pretest (and any flushing) is followed by a withdrawal (“drawdown”) of the formation fluids into the sink probe line of the borehole tool. Drawdown is done at a constant flow rate if possible, and pressure measurements are typically taken at the source probe 160 and at observation probes 170 and 180 . Drawdown is accomplished by opening valve 165 and initiating the pressure controlled subsystem 164 to withdraw fluid from the formation. Fluid is withdrawn or injected at a substantially controlled pressure or rate. The valve is then closed at the time designated as the shut-in time. During this time, and for a predetermined time after shut-in time, the pressure at the source probe and at each observation probe is measured by the respective pressure gauges and sent to the surface of the earth where the measured pressures are recorded. Flow due to the compression of the fluid in the tool continues following shut-in. Typically, although not necessarily, pressure signals are sampled at a period of 0.1 seconds, converted to digital form, and sent to the surface for recording. Accordingly, there is available at the surface a record of the pressure as a function of time at the source probe and each of the observation probes. There are various available devices and techniques for withdrawing fluid from the formations at substantially constant pressure; examples being set forth in U.S. Pat. No. 4,507,957 or 4,513,612. In addition, there are various available techniques for interpreting the data resulting from the drawdown tests. According to the invention, the preferred methods for interpreting the data are set forth in previously incorporated U.S. Pat. No. 5,247,830 to Goode.
[0038] If, based on measurements obtained during drawdown, it is desired to take fluid samples, the source probe is activated by opening valve 166 a and fluid is withdrawn from the formation for a given time or until a particular amount of fluid has been withdrawn. No flow rate measurement is made. Pressure measurements at the source probe as well as at the observation probes are taken during sampling, and these measurements are sent uphole as hereinbefore indicated with respect to the measurements made during drawdown.
[0039] It should be noted that before sampling, if desired, a pumping module (not shown) may be used to pump fluids via the probe (sink) into the borehole, and at a desired time, divert the flow into a sampling chamber.
[0040] Having described the apparatus and procedure of the invention, an understanding of the underlying theoretical basis of the invention is in order. The convolution integral is widely used for solving time-dependent boundary value problems in variable rate well test analysis. For the pressure response p v (t) at the vertical observation probe 170 , the convolution integral can be written as:
p v ( t ) = ∫ 0 t q s ( τ ) G vs ( t - τ ) τ + ∫ 0 t q v ( τ ) G vv ( t - τ ) r + ∫ 0 t q h ( τ ) G vh ( t - τ ) τ , ( 1 )
[0041] where G represents the response functions with the first subscript denoting the observation point and the second subscript denoting the source, q represents actual flowrates, and the subscripts s, v, and h denoting the sink probe 160 , vertical probe 170 and horizontal probe 180 respectively. No specification of G is made other than requiring that the response be linear.
[0042] For a slightly compressible fluid of isothermal compressibility c, the law of mass conservation yields:
q v ( t ) = - c V v p v t ,
q h ( t ) = - c V h p h t , and
q s ( t ) - q ( t ) = - c V s p s t ( 2 )
[0043] where V is the tool volume and q(t) is the imposed drawdown rate at the sink. Substituting the equalities of equations (2) into equation (1) results in:
p v ( t ) = ∫ 0 t q s ( τ ) G vs ( t - τ ) τ - ∫ 0 t c V s p s τ G vs ( t - τ ) t - ∫ 0 t c V v p v τ G vv ( t - τ ) - ∫ 0 t c V h p h τ G vh ( t - τ ) t . ( 3 )
[0044] Similar expressions may be written for the pressure responses p h (t) and p s (t).
[0045] The following dimensionless variables may now be defined:
p vD = p v k l Q μ p hD = p h k d Q μ p sD = p v k r p Q μ t D = t k φμ c l 2 q D = q Q
[0046] with the following dimensionless response function being
G vsD = G vs μ k l φμ c l 2 k G hsD = G hs μ k d φμ c l 2 k G vhD = G vh μ k l φμ c l 2 k and G ssD , vvD , hhD = G ss , vv , hh μ k r p φμ c l 2 k
[0047] In the above expressions, Q is a characteristic rate, l is the distance between the sink and the vertical probe, d is an effective distance between the horizontal probe and the sink as defined in detail hereinafter, and r p is the probe radius. A characteristic permeability k has been chosen for the purpose of nondimensionalization.
[0048] Substituting the above dimensionless parameters into equation (3) and simplifying yields:
P vD ( t D ) = ∫ 0 t D q D ( τ ) G vsD ( t D - τ ) τ - [ V s φ l 2 r p ] ∫ 0 t D p sD τ G vsD ( t D - τ ) τ - [ V v φ l 2 r p ] ∫ 0 t D p vD τ G vvD ( t D - τ ) τ - [ V h φ l 2 d ] ∫ 0 t D p hD τ G vhD ( t D - τ ) τ . ( 4 )
[0049] If the nondimensional storage related constants are denoted by κ, then κ s =V s /φl 2 r p , κ h =V h /φl 2 r p , κ v =V v /φl 2 r p , δ=r p /d, and ε=r p /l. It is useful to note that r p /l and r p /d are much smaller than 1.
[0050] Laplace transformation of equation (4) with t D →s D gives
{overscore (p)} vD ( s D )= {overscore (G)} vsD ( s D ) {overscore (q)} D ( s D )− s D k s {overscore (G)} vsD ( s D ) {overscore (p)} sD ( s D )− s D k v {overscore (G)} vvD ( s D ) {overscore (p)} vD ( s D )−δs D κ h {overscore (G)} vhD ( s D ) {overscore (p)} hD ( s D ) (5)
[0051] where the transformed variables are denoted by the elevated bar ({overscore ( )}). Rearranging equation (5) yields
{overscore (p)} sD [s D k s G vsD ]+{overscore (p)} hD [δs D k h G vhD ]+{overscore (p)} vD [1+ s D k v G vvD ]={overscore (G)} vsD {overscore (q)} D (6)
[0052] Similar expressions for the horizontal and sink probes are:
p _ sD [ s D κ s G hsD ] + p _ hD [ 1 + s D κ h G _ hhD ] + p _ vD [ ɛ 2 δ s D κ v G _ hvD ] = G _ hsD q _ D ( 7 )
and {overscore (p)} sD [1+ s D κ s G ssD ]+{overscore (p)} hD [δ 2 s D kh {overscore (G)} shD ]+{overscore (p)} vD [ε 2 s D kv {overscore (G)} vsD ]={overscore (G)} ssD {overscore (q)} D (8)
[0053] By neglecting terms on the order of (δ), (ε), (δ 2 ), and (ε 2 ), in equations 6, 7, and 8 and explicitly solving for observation probe pressures, the following is obtained:
p _ vD = G _ vsD q _ D [ 1 + s D κ v G _ vvD ] [ 1 + s D κ s G _ ssD ] and ( 9 ) p _ hD = G _ hsD q _ D [ 1 + s D κ h G _ hhD ] [ 1 + s D κ s G _ ssD ] ( 10 )
[0054] Dividing equation (9) by equation (10) yields:
p _ vD p _ hD = G _ vsD G _ hsD [ 1 + s D κ h G _ hhD ] [ 1 + s D κ v G _ vvD ] ( 11 )
[0055] For testing of a formation with a multiprobe module such has been described herein, equation (11) suggests that the effect of storage volume connected to the vertical and the horizontal observation probes will cancel out if κ h =κ v and {overscore (G)} hhD ={overscore (G)} vvD . The condition {overscore (G)} hhD ={overscore (G)}vvD is satisfied if the vertical and the horizontal probes are geometrically similar and are set in a medium of similar properties (e.g., in a homogeneous medium). Even in a layered medium of alternating permeabilities the condition is met if both of the probes are set in similar streaks. If the layering is extremely fine, but the medium behaves as a homogeneous anisotropic medium in all the length scales of interest, the condition of {overscore (G)} hhD ={overscore (G)} vvD is met as well. The requirement that κ h =κ v or (V v =V h ) means that the flow line volume connected to the observation probes should be equal. Thus, according to the invention, flow lines 177 and 187 are preferably chosen to be of equal length and diameter so that the storage volume between the probe 171 and valve 173 is equal to the storage volume between probe 181 and valve 183 .
[0056] With κ h =κ v , equation (11) reduces to
p _ vD p _ hD = G _ vsD G _ hsD ( 12 )
[0057] With
G _ = G _ vsD G _ hsD ,
[0058] it follows that
p vD ( t D ) = ∫ 0 t D p hD ( τ ) G ( t D τ ) τ where ( 13 ) G = L - 1 ⌊ G _ vsD G _ hsD ⌋ ( 14 )
[0059] The function G(t) depends only on the geometry and the rock/fluid properties of the formation. It has diagnostic value for flow regime identification which is necessary to choose the correct inverse model for parameter estimation as set forth in previously incorporated U.S. Pat. No. 5,247,830 to Goode. The above analysis shows that a source of error in model identification and in the estimation of horizontal and vertical mobilities can be removed by equalizing the storage volumes at the monitor probes.
[0060] According to Goode, for system identification, one would normally deconvolve equation (13) to numerically calculate G and compare with known system behaviors. Inversion of equation (13) is numerically stable only if the vertical probe response “lags” that of the horizontal probe. When k v is larger than k h (e.g., in a formation with vertical microfractures) this is not necessarily the case and a modification of the G function to
G ^ = L - 1 [ G _ vsD G _ hsD + G _ vsD ] ( 15 )
[0061] would ensure that the numerator never leads the denominator signal.
[0062] In order to demonstrate the effectiveness of the modification, it is not necessary to model the details of the wellbore geometry and the formation. It is sufficient to consider response functions which are very similar to the proposed tool. This is achieved through the following approximations.
[0063] Regarding the self-response function such as Gss, Gvv, and Ghh, the presence of the wellbore is important since the radius of the probe r p is much smaller than the radius of the wellbore r w . Thus, the probe acts as though it is a source or sink in a flat plate. See, Wilkinson, D. and Hammond, P.: “A Perturbation Method for Mixed Boundary-Value Problems in Pressure Transient Testing”, Trans. Porous Media , (1990) 5, p. 609-636, and Ramakrishnan, T. S. et al.: “A Laboratory Investigation of Permeability in Hemispherical Flow with Application to Formation Testers”, SPE Form. Eval . (1995) 10, p. 99-108. However, this boundary value problem is of mixed-nature and cannot be exactly solved. For time scales larger than that required for pressure diffusion to propagate a few probe radii, the infinite time result may be used with the assumption of the transient being a point sink. This is equivalent to using an “effective probe radius”=(2/π)r p . Solving the diffusion equation with a point sink on a flat plate, and observing the pressure at (2/π)r p yields:
G _ ss , G _ vv , G _ hh = μ 4 kr p exp ⌊ - φμ cs k r p ⌋ ( 16 )
[0064] In contrast, since the vertical probe is far away form the sink, and l>>r w , as an observation probe, the presence of wellbore is secondary. Thus, for the response function {overscore (G)} vs an observation point may be considered in free space. Based on this, the following result is obtained:
G _ vs = μ 4 π kl exp ⌊ - φμ cs k l ⌋ ( 17 )
[0065] It may be seen from Goode, P. A. and Thambynayagam, R. K. M.: “Permeability Determination with a Multiprobe Formation Tester”, SPE Formation Eval. 7, pp. 297-303 (1992) that this is a good approximation because the wellbore shape factor approaches 1 for the vertical probe (i.e., the vertical probe is a point observation in free space).
[0066] In dimensionless form, the above equations reduce to:
G _ ssD , G _ vvD , G _ hhD = 1 4 exp ⌊ - r p l s D ⌋ and ( 18 ) G vsD = 1 4 π exp [ - s D ] ( 19 )
[0067] The approximation set forth above for the vertical probe is not as accurate when applied to the horizontal probe. If it is assumed that the probe is at a distance d in free space, then, instead of equation (17) for the vertical probe, the following is obtained for the horizontal probe:
G _ hs = μ 4 π kd exp ⌊ - φμ cs k d ⌋ ( 20 )
[0068] Here, the effective distance d may be approximated by the characteristic diffusion length πr w , and as a result, equation (20) reduces to
G _ hs = ≈ μ 4 π k ( π r w exp ⌊ - φμ cs k π r w ⌋ ( 21 )
[0069] This approximation differs from the true steady state value (s→0) by only about twenty percent. See, Goode, P. A. and Thambynayagam, R. K. M.; Permeability Determination with a Multiprobe Formation Tester,” SPE Formation Eval . (1992) 7, p. 297-303. Therefore, this approximation is expected to have the correct qualitative and nearly the same quantitative behavior as the correct response. In dimensionless form the following is obtained
G _ hsD = 1 4 π exp [ - ɛ δ s D ] ( 22 )
[0070] Application of equation (11) now yields
p _ vD p _ hD = exp [ - ( 1 - ɛ δ ) s D ] ( 1 + k h s D 4 exp [ - ɛ s D ] ) ( 1 + k v s D 4 exp [ - ɛ s D ] ) ( 23 )
[0071] Equation (23) allows an examination of the effect of having different storage volumes on the deconvolutional process utilized in the previously incorporated U.S. Pat. No. 5,247,830 to Goode. In particular, FIG. 3 shows the pressure-pressure response function (G vhD vs. time) for a homogeneous medium for observation probes having no storage (κ h =0 and κ v =0), for observation probes of the prior art where the horizontal probe storage volume is approximately 100 cc and the vertical probe storage volume is approximately 90 cc (corresponding to κ h =0.18 and κ v =0.17), and for observation probes having storage volumes such that κ h =0.18 and κ v =0.09. For purposes of generating the plots of FIG. 3, the formation permeability was assumed to be 10 mD, length l=70 cm, and r p =0.556 cm. As seen from FIG. 3, in a homogeneous formation, the deviation from the no-storage volume reference curve is minimal for the tool of the prior art. The deviation is somewhat larger where κ h =0.18 and κ v =0.09. In this case, because of the smaller storage volume in the vertical probe, there is a tendency for the vertical probe to lead the horizontal probe in comparison to the true response. Clearly, this can lead to a misinterpretation that the formation is anisotropic. Thus, according to the invention, it is desirable that the storage volumes at the observation probes be equal to each other (thereby reducing the right hand fraction term of equation (23) to one).
[0072] The impact of storage compensation in a heterogeneous medium is substantially larger than the impact in a homogeneous medium. This may be illustrated by first assuming a background homogeneous medium and by assuming that in the vicinity of the horizontal and vertical probes the formation permeabilities are k 1 and k 2 respectively. Thus, the self-response functions are determined by k 1 and k 2 . But G vs and G hs are based on the homogeneous permeability. As a result, equation (23) becomes
p _ vD p _ hD = exp [ - ( 1 - ɛ δ ) s D ] ( 1 + κ h s D k 4 k 1 exp [ - ɛ k s D k 1 ] ) ( 1 + κ v s D k 4 k 2 exp [ - ɛ k s D k 2 ] ) ( 24 )
[0073] It is evident that the right-hand fraction term of equation (24) cannot be reduced to one simply by choosing κ h =κ v . In fact, no universal solution is possible since it is impossible to adjust κ h and κ v to such that the storage effect is cancelled perfectly at all times. However, a practical solution is achieved by recognizing that the function G vv and G hh reach steady state much faster than G vh (due to the fact that r p /l<<1). As a result, a near-cancellation is achieved by choosing κ h and κ v to be proportional to k 1 and k 2 respectively. Mathematically, this is expressed by:
p _ vD p _ hD = exp [ - ( 1 - ɛ δ ) s D ] ( 1 + κ h s D k 4 k 1 exp [ - ɛ k s D k 1 ] ) ( 1 + κ v s D k 4 k 2 exp [ - ɛ k s D k 2 ] ) ≈ exp [ - ( 1 - ɛ δ ) s D ] ( 1 + κ h s D k 4 k 1 ) ( 1 + κ v s D k 4 k 2 ) ( 25 )
[0074] Equation (25) allows an examination of the effect of using different storage volumes on the deconvolution process with respect to heterogeneous formations. Using the same example used with respect to FIG. 3 (i.e., l=70 cm, and r p =0.556 cm), it is assumed that the background permeability is 10 mD and the permeability at the horizontal probe is 100 mD, while the permeability at the vertical probe is 1 mD. In particular, FIG. 4 shows the pressure-pressure response function (G vhD vs. time) for the heterogeneous medium. A reference response plot is set for observation probes having no storage (κ h =0 and κ v =0). A second plot for observation probes of the prior art where the horizontal probe storage volume is approximately 100 cc and the vertical probe storage volume is approximately 90 cc (corresponding to κ h =0.18 and κ v =0.17) is seen to be significantly displaced from the reference plot. However, adjusting the horizontal probe storage volume to one hundred times that of the vertical probe storage (based on the local permeability ratio) so that κ h =17.0 and κ v =0.17 is seen in FIG. 4 to essentially eliminate the displacement. Even partial compensation significantly improves the character of the response as can be seen from the plot where κ h =9.0.
[0075] There have been described and illustrated herein several embodiments of apparatus and methods for investigating properties of an earth formation traversed by a borehole. While particular embodiments of the invention have been described, it is not intended that the invention be limited thereto, as it is intended that the invention be as broad in scope as the art will allow and that the specification be read likewise. Thus, while a downhole tool having three probes was described, it will be appreciated that other numbers of probes could be utilized. Also, while a tool which permits probe fluid storage volume to be increased by a factor of about one hundred was described, it will be appreciated that the increase in probe fluid storage volume could be significantly smaller or significantly larger depending upon the accuracy of measurements desired and the formations likely to be encountered. Further, while it is preferred that the horizontally and vertically displaced probes have identical flow line characteristics, it will be appreciated that such an arrangement is only preferred, as given the flexibility associated with the branch flow lines, it will typically be possible to arrange the probes so that the flow line storage volumes are equal for homogeneous formations or portions thereof. It will therefore be appreciated by those skilled in the art that yet other modifications could be made to the provided invention without deviating from its spirit and scope as claimed. | The effects of storage on the interpretation of data obtained at observation probes of a borehole tool are eliminated by controlling the storage volumes relative to the observation probes. For a homogeneous medium, the effect of storage on the interpretation of data is eliminated by causing the flow line volumes connected to each observation probe to be equal to each other. For a heterogeneous medium, the effect of storage on the interpretation of data is eliminated by causing the flow line volumes to vary in proportion to the relative permeabilities of the strata of the heterogeneous medium adjacent the probes. The borehole tool is provided with mechanisms for conducting flow line volume adjustment. | 4 |
This invention relates to a method and apparatus for three dimensional inspection and, more particularly, a method and apparatus for three dimensional inspection of electrical component leads using a single axial camera and a single image.
BACKGROUND OF THE INVENTION
Prior art three dimensional inspection systems have involved multiple access mirrors and multiple cameras or a single camera and multiple images. These systems have been used to inspect printed circuit boards, integrated circuits and other small parts. The prior art requires a multiple number of images to accomplish the three dimensional inspections. Traditional prior art methods utilize a triangulation method that requires multiple images. Multiple images increase the cost of prior art solutions as well as the complexity and the time needed for inspection.
Prior art solutions do not include a method or apparatus for providing three dimensional inspections of a part having leads from a single image. Using a single image for three dimensional systems provides a speed and cost benefit. It is therefore a motivation of the invention to provide a three dimensional scanning system for a part having leads where the scanning system requires only one image of the part being taken.
Other scanning systems are disclosed in U.S. Pat. No. 5,173,796, issued Dec. 22, 1992 to Palm et al., entitled "THREE DIMENSIONAL SCANNING SYSTEM" and U.S. Pat. No. 5,276,546, issued Jan. 4, 1994 to Palm et al., entitled "THREE DIMENSIONAL SCANNING SYSTEM" the disclosures of which are incorporated herein, in their entirety, by the foregoing references thereto.
SUMMARY OF THE INVENTION
The invention provides a method and apparatus for three dimensional inspection of objects having electronic leads. An inspection system includes a transparent reticle for receiving a part for inspection on a central portion of the reticle. Optical elements are located around the central portion of the reticle to provide side views of the part to a single axial camera located below the reticle. The camera receives an image including a bottom view and side views. The reticle further provides a common reference point. A processor locates the position of a part feature in three dimensions using the relationship of the part feature to the common reference point. The processor calibrates the inspection system by imaging a precisely defined object such as a reticle mask to provide a set of dimensional data that is invariate over the system parameters. The calibration method provides a set of state equations. The need for a focusing element is eliminated through the choice of optics and the relative placement of the overhead mirrors or prisms with respect to the object to be inspected. The difference in optical path lengths between the bottom view and the overhead views are less than the depth of focus. Because only a single image is needed to provide the three dimensional analysis, the inspection system provides a cost effective, repeatable and high speed analysis.
The invention also provides a method for three dimensional inspection of electronic leads from a single image. The method starts by providing a transparent reticle having a top surface. The method then places a part having electronic leads for inspection on a central portion of the top surface of the transparent reticle. The method then provides fixed optical elements for providing a side perspective of the part. The method then provides a camera located beneath the transparent reticle to receive an image of the part and the additional perspective provided by the fixed optical elements wherein the camera provides image data. The method then processes the image data with a computer to provide a three dimensional analysis of the part.
The invention also provides a method to calibrate the computer using a reticle mask. In one embodiment the invention calibrates the computer by calibration of the bottom view by the following steps. The invention first locates the calibration dots on the reticle mask visible directly from the bottom view. The method then determines the location and size of each dot. The method then stores the location and size of each dot in memory. The method then determines the state values for the bottom calibration by comparing the location and size of each dot with the known values and then stores the state values in memory.
The invention further provides for calibration of the computer by calibration of a side view by the following steps. First the method of the invention locates the calibration dots visible in each of the fixed optical elements. The method then locates a reference edge. The method then calculates a distance from the reference edge to each dot in the side view image and the bottom view image. The method then determines state values for the fixed optical elements from known values and stores the state values in memory.
The invention also provides three dimensional inspection of an object having electronic leads from a single image. The method first waits for an inspection signal. Then the method acquires an image of the object including a bottom view and a side view. The method then processes the image to find a rotation, x placement and y placement of the object. Then the method locates the electronic leads of the object in the bottom view. The method then locates the electronic leads of the object in the side view and determines a reference point for each lead. The method then converts pixel values to world values. The method then converts word values to part values. The method then converts part values to measurement values, wherein the measurement values are determined by comparing the calculated part values to predetermined part values. Finally the method provides a part result based on the measurement values and predetermined tolerance values.
In one embodiment the part result comprises a result selected from the list consisting of: a pass result, a fail result and a rework result.
In another embodiment the predetermined tolerance values further comprise pass tolerance values and fail tolerance values.
In one embodiment the part result comprises a pass result if the measurement values are less than or equal to the pass tolerance values, a fail result if the measurement values exceed the fail tolerance values and a rework result otherwise.
In one embodiment the part may be removed after the camera acquires the image and a new part placed on the transparent reticle while the part result is calculated.
BRIEF DESCRIPTION OF THE DRAWINGS
To illustrate this invention, a preferred embodiment will be described herein with reference to the accompanying drawings.
FIG. 1A shows the apparatus of the invention for part inspection and calibration.
FIG. 1B shows an example image acquired by the system.
FIG. 1C shows a method for three dimensional inspection of electronic leads from a single image.
FIGS. 2A and 2B show a flow diagram of the three dimensional inspection loop of the invention.
FIG. 3A shows one method of the invention used to locate an object in three dimensions.
FIG. 3B shows an alternate method of the invention used to locate an object in three dimensions.
FIG. 4 shows one embodiment of a calibration dot pattern as viewed by a camera with four side optical elements.
FIG. 5 shows a method of the invention for determination of D S and D B .
FIG. 6 shows a flow chart of a method of the invention used for system calibration.
FIG. 7 shows a method for calibration of the optical elements.
FIG. 8 shows a flow chart of a method of the invention for determining three dimensional location.
FIGS. 9A, 9B, 9C and 9D show alternate embodiments of the part holder and optical elements of the invention.
FIGS. 10A, 10B, 10C and 10D show one embodiment of the subpixel lead dimension measurement method.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
In one embodiment of the invention, the method and apparatus disclosed herein is a method and apparatus for three dimensional inspection of objects having electronic leads.
FIG. 1A shows the apparatus of the invention for three dimensional inspection. The apparatus includes a camera 10 with a lens 12 and a reticle 20. The reticle 20 includes a central region 22 for receiving a part 30 having a lead 50 for imaging by the camera. The camera 10 is located below the central region 22 of the reticle 20 to receive an image of the part 30. The reticle 20 includes optical elements 40 to provide additional perspectives of the part 30. The optical elements 40 are attached to the reticle and are located around the central region 22 to provide multiple side views of the part 30 to the camera 10. In one embodiment of the invention, the optical elements 40 may comprise prisms. In an alternate embodiment of the invention, the optical elements 40 may comprise mirrors.
The camera 10 is located to receive the image of part 30 and the additional perspectives provided by the optical elements 40. The camera 10 includes a frame grabber board 18 to capture the image. The optics of the camera 10 have a depth of focus encompassing the optical paths of the bottom view from the reticle 20 and the side views provided from the optical elements 40. The camera 10 provides an image data output to a processor 14 to perform a three dimensional inspection as described in conjunction with FIGS. 2A and 2B. The processor 14 may store the image in a memory 16.
FIG. 1B shows an example image acquired by the system shown in FIG. 1A. The image 60 obtained by the camera 10 includes a bottom view 70 obtained by the view through the reticle 20. The bottom view 70 shows an image of the part 32 and images of the leads 52, 54, 56, 58. The image 60 further includes four side images 80, 82, 84, 86 obtained by the view through reticle 20 and reflected off the optical elements 40. The side images 80, 82, 84, 86 show a respective side image of the part 32 and the corresponding leads 53, 55, 57, 59. For example, lead 53 in side view 82 corresponds to lead 52 in bottom view 70, lead 55 in side view 84 corresponds to lead 54 in bottom view 70, and so on. As will be appreciated by those skilled in the art, the invention will work with any number of side images. For example, one image may be used for inspecting a single row of leads. Two images may be used for two rows of leads.
Refer now to FIG. 1C which shows a method for three dimensional inspection of electronic leads from a single image. The method starts by providing a transparent reticle having a top surface in step 1010. The method then places a part having electronic leads for inspection on a central portion of the top surface of the transparent reticle in step 1020. The method then provides fixed optical elements for providing a side perspective of the part in step 1030. The method then provides a camera located beneath the transparent reticle to receive an image of the part and the additional perspective provided by the fixed optical elements wherein the camera provides image data in step 1040. The method then processes the image data with a computer to provide a three dimensional analysis of the part in step 1050.
FIGS. 2A and 2B show a flow diagram of the three dimensional inspection loop of the invention. The process begins in step 110 by waiting for an inspection signal. When the signal changes state, the system initiates the inspection. The processor sends a command to a frame grabber board 18 to acquire an image of a part having leads from the camera in step 110. In step 120, the camera 10 captures an image comprising pixel values and the processor stores the image in memory. The image comprises information from both a bottom view of the part and a number of side views as shown in FIG. 1B.
In step 130, the inspection system sends a signal to a part handler shown in FIGS. 9B, 9C and 9D that the part may be moved off the inspection reticle and that the next part may be put into place. The handler may proceed with part placement while the inspection system processes the stored image data.
The inspection system processes the pixel values of the stored image in step 140 to find a rotation, X placement, and Y placement of the part relative to a center point found during calibration of the inspection system using the reticle mask shown in FIG. 4. The processor determines these placement values finding points on four sides of the body of the part. In step 150, the processor employs a part definition file that contains measurement values for an ideal part. By using the measurement values from the part definition file and the placement values determined in step 140, the processor calculates an expected position for each lead of the part for the bottom view portion of the image. The processor employs a search procedure on the image data to locate the position of the lead closest to the expected position in the bottom view. The processor then determines the lead's X and Y position in pixel values by finding edges on three sides of each lead with a sub-pixel image processing method as shown in FIGS. 10A-10D.
The processor proceeds in step 160 to calculate an expected position of each lead in the side view of the image using the known position of the side view as determined during a calibration procedure as described in FIG. 6, and the position of the lead found in the bottom view. The processor employs a sub-pixel procedure to determine the Z position of the lead in pixel values as described in greater detail in conjunction with FIG. 3A.
After the processor locates the leads, the inspection loop flows to step 170 to determine a reference edge for each lead. The processor determines a closest reference edge for each lead found in the side view. In one embodiment, the juncture of the optical elements with the reticle may serve as a reference edge. In an alternate embodiment, a reference edge may be inscribed on the transparent reticle. In another alternate embodiment, a virtual line of pixels may define the reference edge. The processor converts pixel values to world locations for each lead in step 180 by using the pixel values and parameters determined during calibration. The world locations represent physical locations of the leads in relation to the reference edge. The processor measures D S and D B dimensions and computes the Z dimension for each lead as further described in FIGS. 3A and 3B.
The processor then converts the world values to part values using the calculated part rotation, X placement, and Y placement in step 190 to define coordinates for the ideal part. The part values represent physical dimensions of the leads, such as lead length and lead width.
In step 200, these part values are compared to the ideal part values defined in the part file to calculate the deviation of each lead in three dimensions from the ideal location. In one example embodiment of the invention, the deviation values may include: tip offset, skew, bent lead, width and coplanarity. The processor compares these deviation values to predetermined thresholds with respect to the ideal part as defined in the part file in step 210 to provide an electronic lead inspection result. In one embodiment, the predetermined tolerance values include pass tolerance values and fail tolerance values from industry standards. If the measurement values are less than or equal to the pass tolerance values, the processor assigns a pass result for the part. If the measurement values exceed the fail tolerance values, the processor assigns a fail result for the part. If the measurement values are greater than the pass tolerance, but less than or equal to the fail tolerance, the processor designates the part to be reworked. The processor reports the inspection result for the part in step 220, completing part inspection. The process then returns to step 110 to await the next inspection signal.
FIG. 3A shows one method of the invention used to provide a three dimensional location of an object. Using parameters determined from the calibration procedure as shown in FIG. 6 and a single image, the processor computes a three dimensional location. The processor locates a reference line on the plane of the reticle 20 formed by the juncture of the optical element 40 with the plane of the reticle 20. Ray 300 shows the optical path from reference edge 302 to the camera 10. Rays 300, 310 and 320 are parallel with an axis of the camera 10. The processor measures a distance D S as the distance between the reference edge 302 and the reflected image of the object 330 of the reflective face 312 of the optical element 40 as shown by optical path 310. In one example embodiment, the angle of the reflective face 312 and the reticle 20 is 42°. One skilled in the art will realize that any angle may be used that will provide a view of the leads to the camera 10. The processor determines the distance D B as the distance between the reference edge 302 and the image of the object 330 as indicated by the optical path 320. Using the angle θ 340 defined by optical path 310 and a plane parallel to the reticle plane intersecting object 330, the processor determines the distance Z 350 of the object 330 above the reticle plane. FIG. 7 shows an example calculation of θ during a calibration of the system. The processor calculates the Z dimension using the equation:
Z=D.sub.S tan(45°-θ/2)-(D.sub.B -D.sub.S)tanθ
where:
D S =distance from the reference edge to the side view image of the object;
D B =distance from the reference edge to the bottom view image of the object;
θ=angle formed by the ray emanating from the object reflected by the optical element and received by the camera and the plane intersecting the object parallel to the reticle plane; and
Z=distance along the Z axis from the reticle plane to the object.
FIG. 3B shows an alternate method of the invention used to locate an object in three dimensions. In this method, the processor 14 begins by locating a reference line 360 inscribed on the reticle 20. The processor determines an angle θ 340 that is dependent upon the angle of the face 312 of the optical element 40 to the plane of the reticle 20. The angle θ 340 is determined by using two points 332 and 334. The processor determines a distance between points 332 and 334 by measuring the distance between two rays 333 and 335 that are parallel to the axis of the camera and extending downward from points 332 and 334. The processor then examines the side view for the corresponding rays 370 and 372 received by the camera from the optical element 40. The distance between these two rays 370 and 372 in the side view is measured as Δ Z. θ is determined using the following equation:
θ=ARCTAN ##EQU1## The process then determines an offset R where R is a measure of a distance from the intersection 382 of the face 312 of the optical element and the plane of the reticle 20 and the edge of the reference line 360. The offset R is determined according to the following equation: ##EQU2## where: d.sub.S =distance from a reference edge to the side view image of the object, which is the distance from rays 380 and 370;
d B =distance from a reference edge to the bottom view image of the object, which is the distance between rays 380 and 333;
θ=angle formed by the ray emanating from the object reflected by the fixed optical element and received by the camera and the plane intersecting the object parallel to the reticle plane; and
R=offset of reference line 360 and the intersection 382 between a reflective face of the optical element 40 and the transparent reticle 20.
The processor then determines the height Z of an object above the upper surface of the reticle 20, using the following equation:
Z=(d.sub.S +R)tan(45°-θ/2)-(d.sub.B -d.sub.S)tan θ
where Z equals the distance along the Z axis from the reticle plane to the object.
In one embodiment of the invention, the system is calibrated by placing a pattern of calibration dots of known spacing and size on the reticle plane. FIG. 4 shows one embodiment of a calibration dot pattern as viewed by the camera 10 with four side optical elements, fewer or more side optical elements may also be used. The camera receives an image including a bottom view and four side views from the optical elements located on the reticle plane. The calibration dots appear as direct images 410 and reflected images 420. FIG. 5 shows the relationship between the direct image 410, the reflected image 420 and the reference edge 302 and the values of D S and D B .
FIG. 6 shows a method of the invention used to calibrate the system using the reticle mask 400. The method begins at step 600 by finding the calibration dots. The processor finds a location and size of each dot visible directly from the bottom view and stores these results in memory. By comparing these results to known values stored in memory, the processor calculates the missing state values for the bottom calibration in steps 610 and 620. For example, in step 610 the processor determines camera distortion and roll angle and in step 620 the processor measures pixel width and height. These state values include pixel width and pixel height, pixel aspect ratio, optics distortion, and camera orientation with respect to the dot pattern. The processor then stores these results in memory. These results provide conversion factors for use during analysis to convert pixel values to world values.
The process flows to step 630 where the processor finds calibration dots visible in side views and reference edges. From these values, the processor determines the side view angles of the optical elements 40 in step 640 as shown in FIG. 7. The processor begins by finding the missing state values for each side mirror calibration from the data. These include the position of the mirror to the reticle plane. The state values are stored in memory.
FIG. 7 shows how the system determines angle θ 710 for the optical element 720 using D S and D B . The system locates a reference edge 730 and uses a reflected image 740 of the object 750 to determine a distance D S 760. D B is determined by the distance from the reference edge 730 and the object 750. The angle calculation for angle θ 710 may be determined by the following calculation: ##EQU3## where: D S =distance from a reference edge to the side view image of the object, which is the distance from rays 380 and 370;
D B =distance from a reference edge to the bottom view image of the object, which is the distance between rays 380 and 333; and
θ=angle formed by the ray emanating from the object reflected by the fixed optical element and received by the camera and the plane intersecting the object parallel to the reticle plane.
Once angle θ is known, the inspection system may use these known values to determine the three dimensional location of an object in space.
FIG. 8 shows one embodiment of a method of the inspection system of the invention to determine a three dimensional position of an object in space. The method begins in step 800 by finding an object from the bottom view. Using a search method, the processor determines coordinates for the object. In one embodiment, the processor may employ a subpixel method as shown below in FIGS. 10A-10D to find a repeatable position. The method then proceeds to step 810 to find the object in a side view. The processor determines a subpixel location for the object in the same manner as for the bottom view. The processor finds a reference edge to a subpixel location in step 820, and then computes the observed values for D S and D B in step 830. From these known values, the processor may determine the x, y and z positions of the object in step 840.
FIGS. 9A, 9B, 9C and 9D show alternate embodiments of the part holder and optical elements of the invention. In FIG. 9A, a pedestal 910 is attached to the central portion of the reticle 920. A part 900 may be received on the pedestal 910 for analysis. In FIG. 9B, a vacuum holder 950 is used to suspend a part 900 above the top surface of the reticle 920. The vacuum holder 950 suspends the part 900 substantially parallel to the face of the reticle 920. FIG. 9C shows a vacuum holder 950 suspending a part 900 above a reticle 920 where a central portion 922 of the reticle has been cut out. The central portion 922 of the reticle 920 has been cut out so that an inward face 942 of a prism 940 is substantially in line with the cut out portion of the reticle 920. FIG. 9D shows a configuration similar to that shown in FIG. 9C, except that a mirror 952 is used in place of the prism 940.
Refer now to FIGS. 10A-10D which show one embodiment of the subpixel lead dimension measurement method. The processor begins with known parameters determined from the bottom view to find an ideal location center for a lead 50 having a lead tip 51. Depending on the size of a part and other parameters such as lighting conditions, the ideal location center of the lead tip 51 may vary. The processor defines a region of interest, 11×19 pixels for example, around the ideal location center, shown in FIG. 10A as the coordinates nX, nY. For example the camera is a CCD camera that contains 1024×1024 pixels with a pixel representing approximately 1.6 thousandths of an inch of the lead. Other optical systems and camera types may be used without deviating from the spirit and scope of the invention. The size of the region of interest is chosen such that only one lead is contained in the region so that no other adjacent lead is contained in that region of interest. Using nW, an expected width in pixels, and nL, an expected length available of the lead 50 up to the body of the part, an expected lead dimensions are found as shown in FIG. 10A. Within the region of interest, a processor finds a lead tip 51 by moving from the outside edge opposite the lead tip 51 toward the lead tip 51 one pixel at a time. The processor determines the pixel having the maximum gradient to be the edge of the lead tip dT. The gradient for each pixel is found by subtracting a gray scale value of the pixel from the gray scale value of the next pixel. To reduce the possible effects of noise, the processor may proceed by averaging groups of three or more pixels, as an example, rather than using individual pixels. When the lead tip 51 is found, the processor determines the two lead tip edges positions, dS 1 and dS 2 by moving five pixels, for example, into the lead along an axis parallel to the lead as defined by the ideal part. Then the method moves toward each of the side edges along a line perpendicular to the lead until a maximum gradient is found along the line. The pixel with the maximum gradient dS 1 and dS 2 are defined as the side positions.
The processor then performs a subpixel operation as shown in FIG. 10B to find a more accurate seed position for a second subpixel operation. The processor defines a small 3×5 box around each position dT, dS 1 and dS 2 . The subpixel operation begins on dT by averaging the three pixels in each column moving left to right and finding a more repeatable seed position dT. Likewise, more accurate seed positions dS 1 and dS 2 are found for the side locations moving from the non-lead edge into the lead while averaging the pixels in each row.
Once these new seed pixels have been determined, the processor determines tip position using the new seed point dTip and defining a large subpixel box of size 2nW×2nW where the tip point is centered left to right on dT, and centered top to bottom on (dS 1 and dS 2 )/2 as shown in FIG. 10C. Once again, the processor moves from left to right from a non-lead edge into the lead while averaging the pixels in each column to find dTip as the tip position. By using a larger box having more pixels, a more repeatable result is obtained.
Likewise, as shown in FIG. 10D, the side positions are found using the seed positions dS 1 and dS 2 with a subpixel box of dimensions nL×nW. For one box the seed position is dS 1 and (dTip+nL/3). For the second box the seed position is dS 2 and (dTip+nL/3). The processor moves towards the lead averaging the pixels in each row, and using the subpixel process shown below, determines a subpixel location of the lead edges as dSide 1 and dSide 2 . The width of the lead is then computed as dSide 1 -dSide 2 .
One example of subpixel edge detection implemented in the C language is shown below.
______________________________________void IML.sub.-- FindHorzEdge ( int nXseed,int nYseed, int nWidth,int nLength, double * dEdge)int nXstart = nXseed - (nLength - 1) /2;int nYstart = nYseed - (nWidth - 1) /2;int nXstop = nXstart + nLength;int nYstop = nYstart + nWidth;int nArray [MAX.sub.-- LENGTH];double d1, d2, d3;double dL '2 nLength;double dM1 = 0.0;double dM2 = 0.0;double dM3 = 0.0;double dM3 = 0.0;double dM11;for (int x=nXstart;x<nXstop;x++){d1 = 0.0;nArray ]x-nXstart] = 0;for (int xYstart;y<nYstop;y++){ nArray ]n-nXstart] += GET.sub.-- PIXEL (x,y);}d1 = nArray [x-nXstart];d2 = d1 + d1;d3 = d2 + d1;dM1 += d1;dM2 += d2;dM3 += d3;}dM1 /= dL;dM2 /= dL;dM3 /= dL;dM11 = dM1 + dM1;double dS1 = dM3 - dM1 * (3.0 *dM2-2.0*dM11);double dS2 = (dM2 - dM11) * sprt(fabs (dM2-dM11));if (dS2 == 0.0) dS2 - 1.0;double dS3 = dS1 / dS2;double dP = 0.5-dS3/(2.0*sqrt(4.0 + dS3 * dS3));double dE = dP*dL + 0.5;if (nArray [0] > nArray[nLength - 1])*dEdge = (double)nXseed - (double) (nLength+1)/2.0+ dE;else*dEdge = (double)nXseed + (double) (nLength+1)/2.0 -dE;______________________________________
The invention has been described herein in considerable detail in order to comply with the Patent Statutes and to provide those skilled in the art with the information needed to apply the novel principles and to construct and use such specialized components as are required. However, it is to be understood that the invention can be carried out by specifically different equipment and devices, and that various modifications, both as to the equipment details and operating procedures, can be accomplished without departing from the scope of the invention itself. | A part inspection and calibration method for the inspection of printed circuit boards and integrated circuits includes a camera to image a precision pattern mask deposited on a transparent reticle. Small parts are placed on or above the transparent reticle to be inspected. An overhead mirror or prism reflects a side view of the part under inspection to the camera. The scene of the part is triangulated and the dimensions of the system can thus be calibrated. A precise reticle mask with dot patterns gives an additional set of information needed for calibration. By imagining more than one dot pattern the missing state values can be resolved using an iterative trigonometric solution. The system optics are designed to focus images for all perspectives without the need for an additional focusing element. | 6 |
The invention relates to plastisol compositions, in particular those based on vinyl homo- or co-polymers and containing optical brighteners, their production and use.
BACKGROUND OF THE INVENTION
Plastisols are used widely in auto body construction. The main applications are sealers between panels, bonding of sheets in body and paint shops, and adhesives. They are also used for protection of external areas, such as for undercoating and rocker panel coating.
For this purpose, plastisols based on PVC polymers or PVC copolymers, e.g., as described in DE 31 11 815, are most often used. Such plastisols consist of fine polymer particles dispersed in a nonvolatile plasticizer. At room temperatures, the solid particles are not soluble in the liquid phase, at higher temperatures (the gel temperature), the polymer particles dissolve in the plasticizer. On cooling, the homogeneous solution solidifies to an elastic or rigid film. Normally the plastisols contain additives such as fillers, rheological additives, stabilizers, pigments, solvents, water-absorbing substances, adhesion promoters, etc. The adhesion promoters facilitate adhesion to the surfaces of the respective substrates. Examples of such substrate surfaces are oily steel, galvanized or tinplated steel, electro-coated sheets, aluminum, etc.
Suitable adhesion promoters for sealants or coatings include polyaminoamides, polyamines, epoxy resins, reaction products of polyamines and epoxy resins, blocked isocyanates, organofunctional silanes, mixtures of urotropine and resorcinol, and combinations thereof.
In automotive construction, plastisols or other sealants and coating compounds can be applied to the oily substrates and subsequently degreased, phosphatized, and provided with an electro-dip coating which is baked at temperatures above 150° C. Usually the compounds are applied to surfaces already primed cataphoretically; the jelling or fusing of the plastisols occurs with the baking of the subsequently applied base coats or top coats.
It is often noticed that white, light, or pastel colored finish coats of the vehicle become discolored (yellowish or brownish) at those points where the finish paints are applied on top of the sealing compounds or underbody coatings. Where the finish paints are applied directly on the electrocoat, they yellow much less. Such undesirable discolorations occur regardless of whether the sealing compound was jelled before overpainting or whether the unjelled sealing compound was provided with the finish coat by the wet-on-wet process and baked only thereafter. The yellowish discoloration appears after a period of time, sometimes after only weeks or months. High moisture and elevated temperature accelerate the formation of the discolorations.
The observed discolorations are due, inter alia, to amines which migrate to the surface of the finish coats in small amounts and become transformed by oxidation into colored substances at the surface. These amines may originate from the electrophoretic coating or from the additives. The plasticizers in the sealants assist in the migration of these discoloring substances to the surface. The coats applied over the sealants absorb the plasticizers, leading to flexibilization of the paint and facilitating the diffusion of the dissolved substances. Many of the lacquer systems used today are acid-curing; that is, their crosslinking takes place under the influence of acid catalysts. Sealants and coatings preferably contain chalks or other basic fillers which partially neutralize these acid catalysts. The reduced concentration of the catalysts over the sealants leads to coatings which are less crosslinked. Thus the low crosslinking density also encourages the diffusion of the discoloring substances from the underlying plasticizer-containing materials to the surface.
It has been proposed to bind the unwanted amines by addition of acid substances to the sealant. In DE-PS 38 21 926, acid ion exchangers in powder form are added to the sealant. In DE-OS 38 43 994, the potentially color-giving amines are bound by reaction with tannins which are added to the plastisol. When acid substances are added, however, a part of the adhesion promoters may be absorbed; thus, the adhesion promoters are no longer available for interactions with the surfaces; for example, for the reaction with the electrocoated sheets or with the galvanized steel surfaces.
Finely divided acid ion exchangers are disadvantageous not only for reasons of cost, but also because the fine dust of such powders is extremely irritating to the respiratory tract and may lead to allergic reactions.
SUMMARY OF THE INVENTION
It is the purpose of the present invention to provide improved yellowing-resistant, overpaintable sealing compounds or coatings for vehicle construction, and to reduce the quantity of acid ion exchangers in powder form or to replace them in whole or part with a safe adjuvant pleasant to handle.
The solution to the problems resides in particular sealants or coatings which contain soluble optical brighteners. These migrate from the sealant into the overlying lacquer. There they compensate for the yellow color of the coloring substances, which also migrate from the underlying sealant to the surface. Further, a synergistic combination of acid ion exchangers with the optical brighteners has been found particularly useful.
Optical brighteners, as used herein, are substances which absorb radiation in the ultraviolet part of the spectrum and emit it in the visible longer-wave blue range. The absorbed ultraviolet light is reflected as a faintly bluish fluorescence, that is, as the color complementary to yellow. By this optical effect, the migrating brighteners compensate for the yellowing, in particular that caused by the oxidation products of amines at the lacquer surface.
DETAILED DESCRIPTION OF THE INVENTION
The plastisol composition according to the invention consists of a composition of homo- or copolymers of vinyl chloride, plasticizers, adhesion promoters, fillers, and various other optional additives. The composition contains 0.001% to 0.25%, preferably 0.05% to 0.075%, of optical brighteners and, preferably, strongly acid ion exchangers. (All parts and percentages in the specification and claims are by weight unless otherwise indicated.) The polymers are homopolymers of vinyl chloride, and copolymers of vinyl chloride with vinyl acetate, acrylic acid esters, or methacrylic acid esters wherein the alcohols have up to 8 carbon atoms, preferably 1 to 4 carbon atoms. Mixtures of the homopolymers with copolymers are also useful.
The plastisol compositions according to the invention desirably contain 20% to 60% plasticizers, preferably esters of aliphatic and/or aromatic acids with mono- or bifunctional alcohols which have 1 to 22 carbon atoms. The plastisol may additionally contain secondary plasticizers.
The adhesion promoters are preferably chosen from polyaminoamides, polyamines, epoxy resins, blocked isocyanates, organofunctional silanes, and mixtures of urotropine and resorcinol, as well as combinations thereof. The mineral or organic fillers or pigments are the usual ones, known to the prior art; also, the strongly acid ion exchangers have been described before, e.g. in DE-OL 3, 821, 926.
As optical brighteners, most preferable are derivatives of 4,4'-diaminostilbene,4,4'-distyryl-biphenyl,methyl umbelliferone, cumarine, dihydroquinolinone, 1,3-diarylpyrazoline, naphthalic acid imide, systems of benzoxazol, benzisoxazol, and benzimidazol which are linked by CH═CH bonds, and pyrene derivatives substituted by heterocycles, all well known in the art. The concentration of the optical brighteners is preferably in the range of 10 to 2500 ppm, especially 50 to 750 ppm, based on the total composition.
In the process for the production of the plastisol composition according to the invention, the optical brighteners can be added to the plastisol at any stage of the production process or even immediately prior to use. To ensure optimum distribution, the optical brighteners can be mixed into the composition as a solution or dispersion in plasticizers or solvents or diluted with fillers. Thus, for example, the dissolution of the optical brightener in the plasticizer occurs in production or before storage, preferably at room temperature or else while jelling at elevated temperature.
The production of plastisols, and the equipment used therefor, is state of the art and is described for example in Krekelen, Wick; Kunststoff Handbuch (Plastics Manual) (1963), Volume 2, Part 1, page 21 ff (W. A. Colomb Verlag, Stuttgart); or Becker, Braun; Kunststoff Handbuch (1968) Volume 2, Parts 1 and 2, (Hanser Verlag, Munich, Vienna).
In a special embodiment of the invention, strongly acid ion exchangers are employed as a 10% to 30% paste with the plasticizers, the proportion of ion exchanger in the total plastisol composition being 0.5% to 3%. Preferably the optical brighteners and the strongly acid ion exchangers are employed as a blend of the ingredients.
The plastisols according to the invention contain, for example, the following components in the quantities stated, a) to e) totaling 100 parts:
a) 10 to 60 parts of a homopolymer of vinyl chloride, a copolymer of vinyl chloride with vinyl acetate, acrylic acid esters, methacrylic acid esters, other copolymerizable monomers, or mixtures of such polymers produced by emulsion, microsuspension, suspension, solution, or mass polymerization;
b) 20 to 60 parts of a plasticizer based on esters of aliphatic or aromatic mono- or polycarboxylic acids with mono- or bifunctional alcohols, which optionally contains secondary plasticizers on based on chloroparaffins, hydrocarbons, fatty acid esters, sulfonic acid esters, phosphoric acid esters, and the like;
c) 1 to 5 parts of adhesion promoters;
d) 5 to 60 parts of mineral or organic fillers or pigments;
e) 0 to 5 parts of strongly acid ion exchangers in powder form;
f) 10 to 2500 ppm, based on the total plastisol, of optical brighteners; and
g) optionally, further additives such as stabilizers, rheological additives, solvents, etc.
The application of plastisols in automotive construction by extrusion or spraying is known to those active in the field. The plastisols can be overpainted before or after passage through the jelling oven, the lacquer application being possible in multiple layers, for example filler/primer, base coat, top coat, and/or clear coat. The composition and application of these paint systems are also familiar to the person of ordinary skill.
The yellowing tendency of a white or light colored lacquer surface applied over plastisol can be accelerated in the test laboratory, in that the test sheets carrying the overpainted plastisol are stored in the dark at 80° C. in an atmosphere having elevated moisture. Yellowing of a plastisol overpainted with a white color (without the yellowing stabilization according to the invention) can be observed instrumentally after one week, to the eye the color change becomes visible after two weeks. If after 8 weeks storage at 80° C. no difference is visible to the eye, it can be assumed that it is yellowing resistant.
A color or a color change can be determined with the aid of a remission spectrometer. By this method the color impression is characterized in the L,a,b, system (DIN 6174, CIE-LAB 1976). The "b" value indicates the position on the yellow/blue axis and will therefore serve as a measure of the yellow values. Yellow value differences of 0.05 can be determined instrumentally.
In the following, yellowing is indicated as the differences of the "b" values between aged and unaged specimens:
Δb=yellow value after aging-yellow value of the freshly baked lacquer
The examples were produced with paste-forming emulsion PVC powder, all additives in powder form had a grain size of less than 80μ. Before application, the plastisols were stored for at least 24 hours. They were applied in layer thicknesses of 0.25 to 2.5 mm on the surface of cataphoretically electro-coated panels which had previously bee baked for 30 minutes at 180° C.
If the plastisol was jelled before overpainting, this was done for 30 minutes at 165° C. If the lacquers were applied before the jelling, that is, in the wet-on-wet process, the jelling of the plastisol was carried out simultaneously with the baking of the lacquer at 135° C. for 30 minutes. But the positive effect of the additions according to the invention was not dependent on whether baking was carried out before or after overpainting.
In the tests, the overpainting took place with an acid-curing, solvent-containing, white cover lacquer based on acrylic and alkyd resins crosslinked with melamine in a layer thickness of 40-50μ.
______________________________________ EXAMPLES:Test number *00 01 02 03 04______________________________________1. PVC homopolymer -- 8 8 8 82. PVC copolymer -- 5 5 5 53. Plasticizer (DINP) -- 28 28 28 284. Polyaminoamide -- 2 2 2 25. Ground chalk -- 39 39 39 396. Precipitated chalk, surface- -- 13 13 13 13 treated7. Titanium dioxide -- 2 2 2 28. Calcium oxide, pulverized -- 3 3 3 39. Strongly acid ion exchanger -- -- -- -- -- in powder form, 20% in DINP Subtotal, parts by weight -- 100 100 100 10010. Optical brighteners in ppmUVITEX OB (CIBA- -- -- 300 600 1000 GEIGY AG)LEUCOPUR EGM -- -- -- -- -- (SANDOZ AG)Results: Δb after agingFreshly baked, room temp. 0.0 1.0 0.0 -0.8 -1.5After 2 weeks at 80° C. 0.9 1.8 1.0 0.1 -0.3After 4 weeks at 80° C. 1.6 2.4 1.6 0.9 0.4After 8 weeks at 80° C. 2.6 3.0 2.2 1.4 1.1______________________________________ Remarks: 2. with 5% vinyl acetate 3. DINP = Diisononyl phthalate 4. Reaction product of dimerized linseed oil fatty acid with an excess of diethylene triamine, amine number 290, 50% solution in plasticizer 11. Strongly acid cation exchanger in the H form, 4.4 mVal/g, max. grain size 40 mμ 20% dispersion in plasticizer *Blank: freshly baked lacquer on cataphoresis sheet
EXAMPLES:Test number 05 06 07 08______________________________________1. PVC homopolymer 8 8 8 82. PVC copolymer 5 5 5 53. Plasticizer (DINP) 26 27 27 284. Polyaminoamide 2 2 2 25. Ground chalk 38 38 39 396. Precipitated chalk, 13 13 13 13 surface-treated7. Titanium dioxide 2 2 2 28. Calcium oxide, pulverized 3 3 3 39. Strongly acid ion exchanger 3 2 1 -- Subtotal, parts by weight 100 100 100 10010. Optical brighteners in ppmUVITEX OB (CIBA-GEIGY -- -- -- -- AG)LEUCOPUR EGM (SANDOZ -- 150 300 300 AG)Results: Δb after agingFreshly baked, room temp. 0.35 -1.0 -0.45 -0.75After 2 weeks at 80° C. 1.35 0.8 0.25 0.9After 4 weeks at 80° C. 1.6 1.2 0.95 1.55After 8 weeks at 80° C. 2.3 1.95 1.65 2.10______________________________________ Remarks: 2. with 5% vinyl acetate 4. Reaction product of dimerized linseed oil fatty acid with an excess of diethylene triamine, amine number 290, 50% solution in plasticizer 11. Strongly acid cation exchanger in the H form, 4.4 mVal/g, max. grain size 40 mμ 20% dispersion in plasticizer | Yellowing-resistant, overpaintable plastisol compositions based on vinyl chloride homo- or copolymers which contain optical brighteners and, preferably, strongly acid ion exchangers. They are especially suitable for overpaintable sealers, coatings, and adhesives, and find particular application in automobile body construction. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
This is a non-provisional application claiming priority under 35 USC §119 (e) to U.S. Provisional Patent Application No. 61/249,828 filed on Oct. 8, 2009.
TECHNICAL FIELD
The present disclosure generally relates to construction vehicles and, more particularly, relates to pipelayers.
BACKGROUND
Pipelayers are specialized vehicles used for installing large, heavy lengths of conduit into or above ground. Such conduits may be used, for example, to carry oil and gas from remote well locations over vast distances to a receiving station or refinery. In so doing, transportation costs for shipping, trucking or otherwise moving the oil and gas can be avoided. In addition to petroleum pipelines, pipelayers can also be used to install piping for other materials, or for installing of drain tile, culverts or other irrigation and drainage structure.
However, the installation of such pipelines is often very challenging. The locations of such oil and gas wells are commonly some of the most remote areas on earth, and the terrain over which the pipeline must traverse is often some of the most rugged. The climate of the installations can have very high or very low temperatures. The land may have significant elevational changes, and be subject to mudslides, severe weather, deep forestation and the like. In order to install the pipe, the pipelayer must be able to operate in all of the above-climate conditions, navigate over such terrain, and still be able to lift loads often in excess of 200,000 pounds.
Not only must pipelayers be able to handle such tasks, but given that the pipes are installed in long segments welded or otherwise secured together, they must be installed with great precision. The ends of the pipe being welded together must butt up against each other within a very tight tolerance. In addition, the pipes are often installed in connected fashion. This can result in a very long length of conduit (sometimes exceeding a mile) which must be laid into the ground in coordinated fashion. A series of pipelayers in such a situation will therefore be called upon to work in concert to lay the pipe.
When installing pipelines, if a natural or pre-made easement does not exist, a path through the terrain is first cleared through the forest, mountain pass or other geographical challenge at hand. A trench is then dug to the desired size, which is typically many feet deep and many feet wide. A right-of-way is also provided to one or both sides of the trench to allow for passage of trucks to transport the pipe into the location, and for passage of pipelayers to install the pipe. This right-of-way is ideally flat and sufficiently wide to easily accommodate the pipelayer but given the constraints imposed by the area topography and space availabilities of the local region or country, this may not always be the case. Pipelayers therefore often need to carry not only very heavy loads, but do so without being on level, stable ground.
Current pipelayers typically work on a track-type undercarriage and operate with a side-boom that can be extended at a variable angle to the chassis of the pipelayer. A cable is trained from a winch or other power source through a series of pulleys and terminates in a grapple hook or other suitable terminus. The grapple hook or other suitable terminus can then be secured to the pipe in such a way that when the winch recoils, the pipe is lifted. The boom arm is then extended and the pipelayer itself is navigated to a desired location for accurate installation of the pipe.
While effective, it can be seen that the weight of the pipe is positioned in cantilevered fashion away from the chassis, engine and undercarriage of the pipelayer. As the chassis, engine and undercarriage comprise the majority of the weight of a pipelayer, depending on the weight of the pipe being lifted and the length of the boom arm, the pipelayer can be subject to potential tipping and instability. Conversely, if the pipelayer is to be maintained in a stable position, the ability of the pipelayer to access the desired installation location can be significantly limited.
To offset these concerns, current pipelayers typically include a counterweight. The counterweight may comprise a series of heavy plates secured to a hinged structure such that through the use of a hydraulic cylinder or the like, the counterweight can be swung away from the chassis of the pipelayer on the side of the pipelayer opposite to the boom and thus counterbalance the weight of the load being lifted.
However, the counterweight systems of currently available pipelayers are operated entirely at the discretion of the operator and thus are arbitrarily applied. The operator of the pipelayer is able to extend the counterweight as he or she sees fit without regard to optimizing lifting capacity or stability of the pipelayer. Often, the counterweight is simply extended and left in that position during operation of the pipelayer. The lifting capacity and possible boom angle are therefore largely limited by such a fixed system.
Current demands being placed on pipelayer design, moreover, are requiring higher lifting capacities and boom lengths/angles. The pipelayer could in theory simply be made larger and heavier to satisfy these needs, but realistically the general footprint of the pipelayer is limited by cost, maneuverability, and transportation considerations. As stated above, pipelayers need to be operated in very remote and difficult locations. Once built, they need to be sent by rail and/or truck for use, and thus the size of those rails and trucks limit the upper end in terms of dimensions of overall pipelayer design. Even if they could be shipped to the location, they also have to be nimble enough to perform the job. Moreover, over-sizing the undercarriage and boom of the pipelayer will also increase manufacturing costs in terms of materials, and operating costs in terms of fuel.
SUMMARY OF THE DISCLOSURE
In accordance with one aspect of the disclosure, a pipelayer is therefore disclosed which comprises an undercarriage, a boom movable relative to the undercarriage, and a counterweight movable relative to the undercarriage ranging between fully deployed and fully retracted positions, the counterweight being movable to the fully deployed position only when the boom has extended a predetermined distance from the undercarriage.
In accordance with another aspect of the disclosure, a method of operating a pipelayer is disclosed, which comprises extending a boom away from an undercarriage, measuring the distance the boom is extended away from the undercarriage, and deploying the counterweight only when the measured distance is greater than a predetermined length.
In accordance with a further aspect of the disclosure, a heavy lift assembly for a pipelayer is disclosed which comprises a position sensor adapted to measure a parameter indicative of the distance a boom is extended away from an undercarriage of the pipelayer, a processor receiving the measured parameter signal indicative of boom extension distance from the position sensor, and an operator interface connected to the processor and provided with an input device through which an operator can engage the heavy lift assembly, wherein the input device is actuable only when the boom has extended away from the undercarriage by a predetermined distance.
In accordance with a still further aspect of the disclosure, in a pipelayer having an undercarriage, chassis and boom weight of A and a machine maximum lifting capacity of B, a heavy lift attachment is disclosed which is adapted to increase the machine maximum lifting capacity to a value greater than B within a heavy lift operating range while maintaining the machine weight as A.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an isometric view of pipelayer constructed in accordance with the teachings of this disclosure;
FIG. 2 is a front view of a pipelayer relative to a trench in which pipe is being laid, and with a boom of the pipelayer extended to a distance providing the pipelayer with maximum lifting capacity;
FIG. 3 is a front view of the pipelayer similar to FIG. 2 , but showing the pipelayer boom extended to a normal operating distance and causing the pipelayer to start to tilt;
FIG. 4 is a front view of the pipelayer similar to FIG. 3 , but showing a heavy lift attachment of the pipelayer deployed to counterbalance the load being lifted
FIG. 5 is a flowchart depicting a sample sequence of steps which may be practiced according to the method of the present disclosure;
FIG. 6 is a schematic representation of the present disclosure;
FIG. 7 is a chart depicting the lift curve of a conventional pipelayer; and
FIG. 8 is a chart similar to FIG. 7 , but showing the improved lift curve of a pipelayer constructed in accordance with the teachings of this disclosure.
DETAILED DESCRIPTION
Referring now to the drawings, and with specific reference to FIG. 1 , a pipelayer constructed in accordance with the present disclosure is generally referred to by reference numeral 100 . While the following detailed description and drawings are made with reference to a pipelayer, it is important to note that the teachings of this disclosure can be employed on other earth moving or construction machines including, but not limited to, loaders, back-hoes, lift-trucks, cherry-pickers, forklifts, excavators, or any other movable vehicle where a load is being lifted at a distance from the main body of the vehicle.
The pipelayer 100 may include an undercarriage 102 comprised of first and second drive tracks 104 , 106 supporting a chassis 108 . A power source, typically a diesel engine, 110 is supported by the chassis 108 . An operator seat 112 and control console 114 may also be supported by the chassis 108 from which the operator can control one or both tracks 104 and 106 to drive the pipelayer 100 forward, backward and turn. Each of the tracks 104 , 106 may be composed of a series of interlinked track shoes 116 in an oval track or high drive configuration. As shown, the tracks 104 , 106 may be trained around first and second idlers 118 , 120 supported by a track roller frame 119 , a sprocket 121 , as well as a series of other rollers 122 in a high-drive configuration.
Extending relative to the undercarriage is a boom 124 . The boom 124 may include first and second legs 126 , 128 independently hinged to the undercarriage 102 at a base 130 , and which terminate at a joined tip 132 . The boom 124 may be up any length desired, with up to twenty-eight or more feet long being suitable. A lifting cable(s) 134 extends from a winch 136 through a series of sheaves 138 at the boom tip 132 and terminates in a grapple hook 140 , vacuum lift (not shown) or are other suitable arrangement for wrapping around or otherwise securing to a pipe 142 ( FIGS. 2-4 ) to be lifted.
In operation, FIGS. 2 and 3 show that the pipelayer 100 is typically navigated by tracks 104 , 106 to be adjacent a trench 144 pre-dug into ground 145 . More precisely, the pipelayer 100 should be positioned away from the trench 144 according to applicable regulations. Once in such a position, the boom 124 may be extended away from the undercarriage 102 to facilitate lifting the pipe 142 and laying same into the trench 144 . For the purposes of this disclosure, the distance that the boom 124 is extended away from the undercarriage 102 , specifically the distance the tip 132 is extended away from the roller 122 , will be referred to as overhang 146 .
However, as shown in FIG. 2 , the pipelayer 100 has its greatest lifting capacity when the boom 124 is extended away from the undercarriage 102 by an overhang 146 of zero to four feet. This distance gives the pipelayer its shortest tipping point, and thus the counterweight its maximum mechanical advantage. Current pipelayers are provided with myriad different lifting capacities, with 40,000; 90,000; 140,000 and 200,000 pound lifting capacities being examples. However, with the direction of the industry gaining momentum to put larger, heavier pipe in the ground, machines with even larger lifting capacities are desired. Regardless of the maximum lifting capacity of the given pipelayer, it is to be understood that the entire pipelayer 100 , including the undercarriage 102 , boom 124 , and engine 110 , as dictated by current ISO (International Organization for Standardization) standards need to be designed and engineered to handle that load. This is true even though that maximum lifting capacity is not often called for, the importance of which will be discussed in further detail herein.
Referring now to FIG. 3 , it will be seen that the boom 124 has been extended to a much greater overhang 146 . In fact, in such a position the weight of the pipe 142 , length of the boom 124 and the overhang 146 may create a moment great enough to overcome the weight of the pipelayer undercarriage 102 , engine 104 and associated machinery, and thereby start to cause the pipelayer 100 to tilt. As a result of this and other factors, in the position of FIG. 3 , the lifting capacity and stability of the pipelayer 100 are significantly diminished. However, given the diameter of the pipe 142 and the relative dimensions of the trench 144 and pipelayer 100 , the operator has no choice but to extend the boom 124 to an overhang 146 at which the lifting capacity and stability of the pipelayer 100 are less than maximum. In other words, as the pipe 142 may itself have a diameter of, for example, three or four feet, and the pipelayer 100 is required to be a minimum of the depth of the trench 144 away from the trench 144 , the overhang 146 of the boom 124 in normal operation is may be well past the point of maximum lifting capacity.
In order to offset the moment created in FIG. 3 , a counterweight 148 can be extended in a direction laterally opposite to the boom 124 as shown best in FIG. 4 . The counterweight 148 may be comprised of a series of heavy plates 150 (see FIG. 1 ) secured to a counterweight frame 152 . The counterweight frame 152 may be hingedly attached to the undercarriage 102 and/or chassis 108 and be movable between the retracted position of FIGS. 2 and 3 , and the deployed position of FIG. 4 , or anywhere in between by way of a hydraulic cylinder 154 or the like. In so doing the center of gravity of the pipelayer 100 is moved laterally away from the trench 144 , thus balancing the pipelayer 100 .
However, while this approach is effective, it has significant practical limitations. In theory, if the lifting capacity of the pipelayer 100 is to be increased, the overall size of the undercarriage 102 , length and strength of the boom 124 , horsepower of the engine 110 , power of the hydraulic system 154 and winch 136 can all be increased to supply the lifting capacity needed. In practice however, this could easily result in a pipelayer which is either too big to manufacture cost-effectively, too big to ship on existing rail systems and roadways, too bulky to maneuver on the challenging terrain mentioned above, or too expensive to operate in terms of fuel consumption.
The present disclosure therefore sets forth an apparatus and method by which the lifting capacity of the pipelayer 100 is increased without increasing the size or cost of the undercarriage 102 , boom 124 , engine 110 or the like. The present disclosure does so by, among other things, providing additional counterweight 148 , but only allowing deployment of the counterweight 148 after the boom 124 has been extended a predetermined distance. More specifically, the pipelayer 100 monitors the position of the boom 124 and enables deployment of the counterweight 148 in a smart, closed-loop fashion. A heavy-lift attachment (HLA) 156 may be used to do so as either part of a newly constructed pipelayer 100 or as a retrofit to existing pipelayers. As used herein, HLA is defined as a collection of components which can be added to a pipelayer 100 to increase the lifting capacity of the pipelayer across a predetermined overhang range without increasing the size of the undercarriage 102 , chassis 108 , boom 124 , or engine 110 .
As shown in FIG. 6 , the HLA 156 may include a position sensor 158 which measures a parameter indicative of the overhang distance 146 . The sensor 158 may be provided in any number of forms including, but not limited to, an encoder provided on a rotating shaft of the boom or winch, a rotary sensor, a magnetic sensor, a proximity switch or the like. One of ordinary skill in the art will understand the various types of sensors which can be used to monitor the angular position of the boom 124 or overhang distance 146 and generate a signal indicative of same.
As shown in FIG. 6 , the HLA 156 may also include a processor 160 electronically communicating with the position sensor 158 , and an enable/disable/automatic switch 162 also in communication with the processor 160 . The enable/disable/automatic switch 162 may be integrated into an existing operator interface 164 on the control console 114 such as with a control screen or the like, or may be provided as a stand-alone switch added to the control console 114 . The HLA 156 may also include software 166 electronically stored in a memory 168 also in electronic communication with the processor 160 . The operator may also be given the opportunity to have the processor 160 automatically control the HLA 156 .
In operation, the pipelayer 100 may work as set forth in the flowchart of FIG. 5 . As shown, the operator would navigate the pipelayer 100 to be adjacent the trench 144 with the pipe 142 secured to cable 134 as shown by a step 170 . The boom 124 would then be extended (step 172 ) away from the undercarriage 102 to an overhang distance 146 at which the radial center of the pipe 142 is directly over the centerline of the trench 144 . The winch 136 would then be operated to lower the pipe 142 into the trench 144 (step not shown in FIG. 5 ).
As the boom 124 is being extended, the position sensor may continually monitor the overhang distance 146 and decide as in step 174 if the overhang distance 146 is greater than the predetermined distance at which the pipelayer 100 enters a heavy-lift operating range 176 (see FIG. 8 ). As indicated above, this range is typically from six to twenty feet of overhang 146 , but may be anywhere from four to twenty-eight feet (or more if the boom 124 is longer than twenty-eight feet). Ensuring the boom 124 is extended far enough so that the pipelayer 100 is in the heavy-lift operating range 176 is important because if the boom 124 is closer to the undercarriage 102 , extension of the counterweight 148 at that time could potentially increase the maximum lifting capacity of the pipelayer 100 beyond its overall rating and thereby require the undercarriage 102 , chassis 108 , boom 124 , and all associated machinery to be increased in size and strength to handle that increased load. As indicated above, as it would be desirable to use a conventionally sized undercarriage and other supporting structure, disabling the HLA 156 when the boom 124 is not in the heavy-lift operating range 176 satisfies both needs.
Referring again to FIG. 5 , if the overhang distance 146 is in the heavy-lift operating range 176 , the processor 160 will send a signal to the enable/disable/automatic switch 162 or other operator interface 164 informing the operator that heavy-lift capability is available as shown in step 178 . If the overhang distance 146 is not in the heavy-lift operating range 176 , the enable/disable/automatic switch 162 is not enabled as shown by step 180 . Alternatively, the processor 160 may automatically keep the HLA 156 on or off.
Once heavy-lift capability is available, the operator can be provided with the option of engaging same as shown by step 182 . If so, the processor 160 causes the hydraulic cylinder 154 to extend the counterweight 148 as shown in a step 184 . The counterweight 148 may be fully deployed or be positioned to a distance to most effectively offset the moment created by the extended boom 124 and load supported by the extended boom 124 . In addition to, or as an alternative to, adjusting the relative deployment position of the counterweight 148 , the counterweight 148 can be hinged or separately provided to only deploy the weight needed to counteract the aforesaid moment. For example, if the counterweight 148 is provided in a series of plates 150 or other masses, less than all the counterweight 148 can be deployed.
Once deployed, the pipelayer 100 may continually monitor (as shown in a step 186 ) the overhang distance 146 to determine if it the boom 124 has retracted to a point where the pipelayer 100 is no longer in the heavy-lift operating range 176 . If so, the processor 160 may cause the counterweight 148 to automatically retract as shown in a step 188 .
By providing such a system, the pipelayer 100 of the present disclosure is able to greatly increase its maximum lifting capacity across a large portion of its operating range. This is best shown in a comparison of FIGS. 7 and 8 . FIG. 7 depicts a load curve for a prior art pipelayer listing the maximum lifting capacity on the vertical axis, and the overhang distance on the horizontal axis. As can be seen the pipelayer has its maximum lifting capacity (200,000 lbs. in the depicted embodiment) at an overhang distance of four feet. As the overhang distance increases it drops precipitously until reaching its minimum lifting capacity (25,000 lbs. in the depicted embodiment) at an overhang distance of twenty-eight feet.
However, as dramatically shown in FIG. 8 , the maximum lifting capacity of the pipelayer 100 , using the same size undercarriage 102 and engine 110 as the prior art example, may be increased by as much as 15% percent or more at all overhang distances 146 supported by the HLA system. In fact, the maximum lifting capacity at four feet of overhang 146 has been increased to roughly 230,000 pounds. Moreover, as it desirable to employ conventionally sized undercarriages 102 and other support structure, the pipelayer 100 of the present disclosure disables the HLA 154 until the overhang 146 has entered the heavy-lift operating range 176 . The heavy lift operating range 176 differs depending on the size of the pipelayer 100 , but is typically at a distance at which the lifting capacity of the pipelayer 100 , even with the HLA deployed is still at or below the maximum lifting capacity of the pipelayer 100 , thus enabling the load to be lifted without over-sizing or re-engineering the undercarriage 102 and other supporting structure of the pipelayer 100 . FIG. 8 shows that the heavy-lift operating range 176 extending from eight feet to twenty-eight feet, but as indicated above, depending on design characteristics of the given pipelayer, the heavy-lift operating range 176 may be six to twenty feet, or anywhere from four feet to the entire length of the boom (twenty-eight feet in the depicted embodiment).
Couching the two curves of FIGS. 7 and 8 in machine production terms, two exemplary models of pipelayers manufactured by the present assignee have maximum lifting capacities of roughly 200,000 pounds and 230,000 pounds, respectively. Those pipelayers have overall machine weights of roughly 117,000 pounds, 151,000 pounds, respectively. By utilizing the teachings of the present disclosure, a pipelayer having roughly the size and weight of the smaller machine can now be produced having the ability to perform the same work as the larger machine in the working range. The foregoing data is of course only one example, and other sized machines and savings are possible within the scope of this disclosure. Nonetheless, from this example it can be seen that compared to conventional pipelayers having an undercarriage, chassis and boom weight of A, and a maximum lifting capacity of B, the present disclosure allows a pipelayer to be manufactured with an a maximum lifting capacity across the heavy lift operating range that is greater than B and at least as high as 1.15B, while still maintaining the weight as A. Moreover, not only can new pipelayers be built in this fashion, but by utilizing the HLA, existing pipelayers can be retrofit to have this added power as well.
While the maximum lifting capacity B of the pipelayer 100 is increased by the teachings of this disclosure, it is important to understand that the present disclosure disables the HLA 154 at cut-off 190 as shown in FIG. 8 . In other words, even though the HLA could in theory be used to extend the maximum lifting capacity of the pipelayer 100 across the entire overhang range of 0-28 feet in the depicted curve, the HLA is only engageable across the heavy lift operating range 176 . As shown, this results in a transition to a new curve which begins at cut-off 190 and extends to the maximum overhang point 192 of FIG. 8 . The portion of the curve depicted in FIG. 8 for overhangs of four to eight feet is only provided to show the potential lifting capacity if the HLA were not disabled at the cut-off 190 . If the HLA were not disabled once the overhang 146 dropped below the cut-off 190 , the operator might try to lift a load which was beyond the maximum lifting capacity for which the undercarriage 102 is designed and result in structural damage to the pipelayer. By limiting the use of the HLA 154 to the heavy lift operating range 176 , and disabling the HLA once the overhang 146 is less than the cut-off 190 , the operator is able to lift a greater load across the relatively wide range of overhangs defined by the heavy lift operating range 176 , without damaging the pipelayer 100 or requiring the pipelayer 100 to be manufactured with a larger undercarriage 102 to handle that load.
INDUSTRIAL APPLICABILITY
From the foregoing, it can be seen that the technology disclosed herein has industrial applicability in a variety of settings such as, but not limited to, increasing the lifting capacity of pipelayers without over-sizing or increasing the size of the undercarriage, engine, boom or other structures of the pipelayer. The pipelayer does so by providing additional counterweight, monitoring the position of the boom overhang, comparing that to the maximum load curve stored in memory, and only when the overhang distance increases to a point at which the resulting lifting capacity of the pipelayer is at or below the overall maximum lifting capacity, does the pipelayer allow a heavy lift attachment to deploy the counterweight. Deployment of the counterweight offsets the moment created by the extended boom and attached load of the pipe, thereby balancing the pipelayer while at the same time increasing its lifting capacity across a majority of its operating range.
While the foregoing has been made with primary reference to a pipelayer, it is to be understood that its teachings can be employed to increase the operating range of any number of similar vehicles including, but not limited to, loaders, excavators, lift trucks, cherry pickers, back-hoes, fork-lifts, or any other movable vehicle where a load is being lifted at a distance from the main body of the vehicle and thereby creating a moment tending to tip the vehicle. | A pipelayer providing higher lifting capacities without adding weight or size to an undercarriage or boom of the pipelayer is disclosed. The pipelayer is designed and sized to have a maximum lifting capacity when the boom is extended from the undercarriage a predetermined, relatively short distance. However, in use the boom often needs to extend further away from the undercarriage, and in so doing the lifting capacity of the pipelayer decreases. The present disclosure provides additional lifting capacity in that extended range by selectively deploying a counterweight away from the undercarriage once the boom is extended past the predetermined distance. In so doing, not only is the lifting capacity of the pipelayer increased, but the size and weight of the undercarriage and boom are not increased. This enables standard sized undercarriages and other supporting structure to be used, thereby aiding in maneuverability and shipping of the pipelayers, while at the same time reducing manufacturing and usage costs. | 1 |
BACKGROUND OF THE INVENTION
This invention relates to task or work chairs of the type typically associated with office work stations, and specifically for use in the performance of certain tasks such as keyboard entry of data into computers, typing and the like.
In the past, various attempts have been made to provide office chairs with several degrees of adjustability built into the chair to maximize comfort, minimize fatigue, and so on. For example, it is well known to utilize a pneumatic piston/cylinder arrangement to raise or lower the chair seat to the desired vertical position. In addition, it is known to provide vertical adjustability for a seat back mounted on a substantially vertical or L-shaped post. Typically, it is the case that the seat back mounting post is slidably mounted for horizontal movement toward or away from a seat mounting plate which is connected to the piston for vertical reciprocation. In this way, the spatial relationship of the chair back to the chair seat may be changed as desired. It is also a characteristic of this type of chair that the substantially vertical or L-shaped seat back post be constructed of a relatively thin and relatively narrow, e.g., 1.5 to 2.0 inches, strip of metal, such as steel, which will permit the seat back to recline or flex backwardly under pressure by the user. Alternatively, the seat back post may be pivotally mounted to the seat mounting plate for spring-biased reclining action.
In chairs of the above mentioned type, the pressure required to recline the seat back increases significantly as the seat back approaches the limit of its movement. As a result, rather than being in a relaxed orientation, the user is actually working hardest as the seat back reaches the limit of its reclining action.
Another problem frequently experienced with prior art chair designs has to do with the fact that to make seat adjustments, it is necessary to stand up, adjust the chair, and then sit down to see if the correct adjustment has been made. If it has not, then the process must be repeated.
Conventional chairs also in most cases lack the capability for adjusting the pitch of the seat with respect to the chair back.
It is the primary object of this invention to overcome the problems experienced with prior art office-type chairs by providing an office, or task, chair which facilitates mental activity, minimizes fatigue, conforms to all body types and sizes, and which incorporates simple manual controls, all but one of which can easily be reached while the user is sitting in the chair.
In accordance with a preferred embodiment of this invention, an office-type chair is provided in which:
(a) seat pitch can be adjusted within a 10° range, so that, for example, the seat may be pitched downward for optimum computer keying tasks, or upward for other tasks;
(b) seat height with respect to the floor can be raised or lowered approximately 41/2 inches;
(c) seat depth, i.e., the distance between the seat and the seat back, may be adjusted up to two inches;
(d) the seat back pitch may be adjusted with respect to the seat, i.e., the back reclines up to 20°, for providing lumbar region support in all positions;
(e) the seat back may be raised or lowered up to 2 inches independently of the seat, to accommodate users of various size.
To carry out the various adjustments, a plurality of adjustment mechanisms are employed. Before describing these mechanisms in detail, however, it is important to understand the basic structure of the chair.
In one exemplary form of a chair, a pneumatic piston and cylinder extends between a five spoke pedestal base and a seat supporting brace. The brace is an integrally formed, combination horizontal seat support and generally vertical seat back support post, having a stylized L-shape.
It will be appreciated that actuation of the pneumatic piston will raise or lower both the seat and the seat back by reason of the unitary brace construction.
A lever is provided within reach of a user seated on the chair for actuating the piston/cylinder to effect upward or downward movement of the seat. This, of course, is advantageous in that the user is not required to adjust the seat in a trial and error-type operation.
The seat portion of the chair is slidably mounted on the support brace and pivotally movable with respect thereto so as to enable both horizontal sliding and pitch adjustment of the seat relative to the seat back.
A pair of concentrically arranged, inner and outer handwheels are located centrally and just behind the lower front edge of the seat for adjusting both the depth and the pitch of the seat. While the adjusting wheels are concentrically arranged, the adjustments themselves are independent of each other so that the seat is forwardly and rearwardly slidable at any adjusted pitch angle. Here again, the adjustment mechanism is within easy reach of a user seated on the chair.
The pitch adjustment is particularly useful because it allows the seat to be tilted, or canted, forwardly to a position which has been determined to be most desirable for carrying out certain office tasks, particularly keying data into a computer.
Pitch adjustment is effected by an adjustable screw, connected to the inner handwheel, which abuts a recessed dimple in a plate secured to the seat bottom. The rearward position of the seat is pivotally secured so that, upon rotation of the inner handwheel, the front of the seat is caused to pivot upwardly or downwardly, depending on the direction of rotation of the screw.
The outer handwheel of the concentric pair of handwheels acts to loosen or tighten the seat against the stationary brace to which it is slidably mounted.
A third handwheel is located on the rearward side of the seat back for purposes of adjusting the height of the seat back along the substantially vertical seat back support portion of the brace.
It is also a characteristic of the chair that the seat back and seat back support portion of the brace be reclinable with respect to the seat and seat support portion of the brace. This is accomplished as the result of carefully orchestrated removal of material from the brace in an area which connects the seat support portion to the seat back support portion. In a preferred embodiment, this connecting area is defined by a rearwardly looped, generally C-shaped integral hinge or flex connection. Material is removed from this area, preferably in the form of slots which extend throughout the C-shaped portion and, at least to some extent, into the vertical and horizontal portions of the brace. This structure permits the seat back to recline away from the seat within a range of 20° from its normal, generally vertical position. In addition, because of the careful tuning of the brace through this selective removal of material, the force required to move the seat back through the first 5° of its range of inclination remains generally constant. In other words, there are no increasing compressive forces exerted against the user as the seat back moves through the first 5° of its 20° range. It is this first 5° that is considered the normal operating range most often encountered during use of the chair. Reclining between 5° and 20° generally occurs only sporadically while stretching, etc.
The pneumatic piston and cylinder arrangement and the five spoke pedestal base, which typically includes associated casters, are of conventional design.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a task chair in accordance with an exemplary embodiment of this invention;
FIG. 2 is a front view of the chair illustrated in FIG. 1;
FIG. 3 is a side view of the chair illustrated in FIG. 1;
FIG. 4 is a rear view of the chair illustrated in FIG. 1;
FIG. 5 is a cross-sectional view of a seat back taken along the line 5--5 of FIG. 2;
FIG. 6 is a partial cross-sectional view of the rearward facing cover of the seat back illustrated in FIG. 5 and further in conjunction with a seat back support post;
FIG. 7 is a cross-sectional view of a seat back adjustment knob assembly;
FIG. 8 is a side view of a unitary brace for use with the chair in accordance with this invention, shown in association with a height adjusting cylinder and with a double handwheel adjustment assembly for adjusting a seat with respect to the brace;
FIG. 9 is a partial top view of the brace illustrated in FIG. 8, with the double handwheel removed;
FIG 10 is a front view of the brace illustrated in FIG. 8 and further showing a detail of how a seat is mounted to the brace in accordance with an exemplary embodiment of the invention;
FIG. 11 is a detailed cross-sectional view of a concentrically arranged double handwheel assembly for adjusting a seat in accordance with an exemplary embodiment of the invention;
FIG. 12 is a front view of a slide adjustment plate for use in mounting a seat to a seat support in accordance with an exemplary embodiment of the invention;
FIG. 13 is a sectional view of the slide adjustment plate taken along the line 13--13 in FIG. 12; and
FIG. 14 is a top plan view of the slide adjustment plate illustrated in FIG. 12.
DETAILED DESCRIPTION OF THE INVENTION
Referring to FIGS. 1 through 4, there is illustrated an adjustable task chair which will first be described in general terms. The chair 2 is provided with a seat 4, a seat back 6, arms pads 8 mounted on arm support members 10, a pedestal base 12 and casters 14. The seat is operatively connected to, and rotatable about, the pedestal base through a piston and gas cylinder assembly 16 which is partially covered by a cylindrical sleeve 18. The piston/cylinder assembly 16 serves to adjust the height of the seat and seat back with respect to the pedestal base (and floor) via an actuating lever 20.
The pedestal base with casters is of a conventional type well known in the art, as is the utilization of a piston/gas cylinder arrangement for adjusting the height of the seat. The particular details associated with these aspects of the chair need not be described further herein.
In accordance with this invention, a unitary, or integral, combination seat support and seat back support brace 22 has welded on the underside thereof a sheet metal box element 25 (see FIG. 8) which receives the sleeve 18 as well as the piston/cylinder height adjustment mechanism. The piston/cylinder mechanism is located at a position along the seat support portion 24 of the brace 22 so as to provide the most stable arrangement for all horizontally adjusted positions of the seat.
The seat is mounted for sliding as well as for pivotal movement with respect to the brace 22. This unique mounting arrangement, described in greater detail below, permits forward and backward adjustment of the seat along the brace 22 and, at the same time, permits independent pitch adjustment of the seat about a pivot point located toward the rear of the seat.
The seat back 6 is slidably mounted on the substantially upright seat back support portion 26, hereinafter referred to simply as the back support portion, of the brace 22 for vertical adjustment relative to the seat 4.
The seat back 6 is also permitted to tilt or recline with respect to the seat 4 by reason of the unique configuration of the brace 22, and particularly by reason of the slotted, curved hinge area 28 which interconnects the seat support portion 24 and the back support portion 26.
A detailed description of the chair construction and the adjustment mechanisms associated therewith follows.
THE UNITARY SEAT AND BACK BRACE
The brace 22, including integrally formed seat support portion 24 and back support portion 26 is shown in further detail in FIGS. 8 through 10.
The brace 22 is constructed of steel, preferably 1070 hot rolled steel approximately 0.187 inches in thickness, and heat treated to spring temper and a Rockwell C hardness of 44-48. The brace is preferably about 3.50 inches wide, in contrast to prior art back support posts which are typically 1.50 to 2.0 inches wide. The additional width of the brace 22 provides substantial support for the seat back 6 but, at the same time, allows the back support portion to tilt rearwardly about 20° from its normal at rest position, which is about 5° rearward of vertical, by reason of the configuration of the curved hinge or connection area 28.
The curved hinge or connection area 28 defines essentially a 2.0 inch radiused portion which extends rearwardly, i.e., concavely, away from the substantially upright back support portion 26 before merging with the horizontal seat support portion 24. Extending throughout the entirety of the connection portion, and extending slightly into both the back and seat portions, respectively, are a plurality of apertures in the form of elongated slots 30. The slots, preferably three in number, are approximately 0.50 inches in width and approximately 8.0 inches in length. As a result, the back support portion 26 is permitted to flex or pivot rearwardly through an approximately 20° range from its normal position. Significantly, the carefully orchestrated removal of material from the brace by reason of the specific configuration of the slots, enables rearward flexing in the first 5° of the 20° range to occur upon exertion of a substantially constant amount of force or effort.
In other words, this chair is unlike prior art chairs where increasing effort is required a the chair back moves through its tilting range. The substantially constant amount of effort or force required to move the seat back through the normally utilized 5° range of rearward flexing is one of the essential features of the chair according to this invention.
It has also been found that the curved and slotted configuration of the connection or hinge area 28 allows the seat back portion to twist about its longitudinal axis so as to accommodate and absorb rotational forces exerted thereon from time to time by the user of the chair.
The brace 22 is further characterized by a slot 32 adjacent a curved upper end of the back support portion 26 which permits vertical adjustment of the seat back 6 as described in further detail below.
The horizontal, seat support portion 24 includes a downwardly angled connector portion 34 which merges with a horizontal offset portion 36. This configuration facilitates the mounting of the seat 4 to the brace in a manner to be hereinafter described.
Immediately forward of the connector portion 34, there is a hole 38, located centrally of the box 25, which is reamed to accept a tapered portion of the piston/cylinder assembly 16.
The forward end of the seat support portion 24 of the brace 22 is formed with an open-ended slot 40 which enables the seat 4 to slide horizontally forward and backward with respect to the brace 22, and seat back 6, in a manner described in detail below.
SEAT CONSTRUCTION AND ADJUSTABLE MOUNTING
The seat 4 is constructed of a suitable base material, such as 3/4 inch plywood, and covered on its upper side with conventional padding, such as 3.2 lb. density high resiliency urethane foam, approximately two inches in thickness, and covered with suitable upholstery material. The underside of the seat is protected by a thermoplastic cover 42, as shown in FIGS. 1 through 4 and 11.
The underside of the seat 4 is further provided with a pair of slide adjustment angle brackets, one of which is shown in FIGS. 12 through 14. The bracket 44 is provided with an upper, horizontal mounting flange 46 provided with a plurality of holes 48 by which the brackets may be fixedly attached to the underside of the seat, rearwardly of the seat center, by screws or other suitable fasteners. A vertically downwardly extending wall 50 is formed with a horizontally oriented, elongated slot 52, approximately 2.50 inches in length. A pair of brackets 44 are mounted on the underside of the seat so as to be located on either side of the brace 22, in lateral alignment with upstanding ears or flanges 52, 54 provided on the sheet metal box 25, as partially shown in FIG. 10. Aligned apertures 56, 58 formed in flanges 52, 54, respectively, receive a slide adjustment rod 60 which extends laterally outwardly beyond the flanges. The rod is secured within the apertures, preferably by tack welding.
The seat is mounted such that the ends of rod 60 are received in slots 52 of brackets 44. By this arrangement, horizontal adjustment of the seat 4 toward or away from the seat back is facilitated. At the same time, the slide adjustment rod serves as a pivot axis about which the seat may be tilted to adjust the pitch thereof.
In the center forward section of the underside of seat 4, there is mounted a seat pitch/depth knob assembly 64 which, in conjunction with brackets 44, serves as a third mounting point for the seat 4 to the brace 22. As best seen in FIG. 11, the assembly 64 comprises a retaining plate 66 fastened by screws 68 to the plywood base of the seat 4. The plate is pierced at 70 to receive a reduced neck portion 72 of a pitch adjustment stud 74. The plastic cover 42 on the underside of seat 4 is dimpled at 76 so as to receive and capture a relatively enlarged head 78 of the stud 74. A threaded shank portion 80 of the stud 74 extends downwardly away from the seat and terminates in a pitch adjustment knob 82 molded about the stud end 84.
A pitch adjustment sleeve 86 is provided with an annular groove or slot 88 by which the sleeve is mounted for sliding movement within the slot 40 provided in the brace 22. The sleeve 86 is further provided with a threaded bore 90 for threadably receiving the pitch adjustment stud 74. By this arrangement, it will be appreciated that by turning the pitch adjustment knob 82, the forward end of the seat 4 is caused to be raised or lowered about the slide adjustment rod 60. A pitch adjustment of about 5° on either side of horizontal is permitted with the disclosed configuration.
At the same time, it will be appreciated that because rod 60 is slidably received within slots 52 of brackets 44, and because sleeve 86 is slidably received within slot 40 of brace 22, the seat 4 may be moved forward or backward, regardless of the pitch angle, within a range of two inches, as indicated by dimension A in FIG. 8. In other words, the horizontal forward and rearward sliding movement of the seat is independent of the pitch angle adjustment.
The sleeve 86 is also provided with an exterior threaded portion 92 which receives an annular seat slide adjustment knob 94 which is formed with an annular bearing surface 96 designed to engage the underside of brace 22. It will be appreciated that by loosening knob 94, the seat 4 may be adjusted horizontally through its approximately two inch range of movement. Tightening of the knob locks the seat in the desired position. As is clearly illustrated in FIG. 11, knobs 82 and 94 of the assembly 64 are concentrically arranged, one within the other, so as to provide dual, independent adjustment at one convenient location on the underside of the seat 4. The location of the dual seat pitch/depth knob assembly 64 is designed to permit easy adjustment of the chair seat by the user while in the seated position.
SEAT BACK CONSTRUCTION AND ADJUSTABLE MOUNTING
With reference now to FIGS. 5 and 6, it may be seen that the seat back 6 is also constructed so as to include a plywood base 97, preferably about 3/8 inch thick and padded with a 2.7 lb. density urethane foam 98. The padding is covered with upholstery material (not shown), preferably identical to that used on the seat 4. The rearward facing surface of the back 6 is covered with a thermoplastic cover 100, similar to the lower seat cover 42, which is approximately 0.080 inches thick and held in place by any suitable fastening means preferably located laterally outwardly of the cover center, as at 101. The fastening means may comprise, for example, one or more pressure sensitive adhesive pads at each location 101.
In the central region of the cover 100, there is an integrally formed or molded recess 102 which is configured to receive a molded insert 104 which cooperates with recess 102 to form a slot by which the seat back 6 is slidably mounted on the substantially vertical seat back support portion 26 of the brace 22. A seat back height adjustment knob 106, as best seen in FIG. 7, is molded about a threaded stud 108 which passes through the insert 104, slot 32 in the back support 26, and is threadably received in a T-nut 110 secured within the plywood base 96.
A relatively thick neoprene washer 112, with a relatively thin nylon washer 114 adhered to one face thereof, is located within the insert 104 between the knob 106 and the back support portion 26. With knob 106 rotated to a loosened position, the seat back 6 may be slidably raised or lowered on the back support portion 26 of brace 22 to the desired position, within a range of about two inches, as limited by slot 32. Subsequent tightening of the knob 106 compresses the neoprene washer 112 to create a friction lock between the seat back 6 and back support portion 26.
From the foregoing description, it will be appreciated that the task or work chair according to the present invention affords the user thereof with a high degree of flexibility and adjustability not heretofore found in chairs of this type.
While the invention has been described in what is presently regarded as its most practical embodiment, it will be appreciated by those of ordinary skill in the art that various changes and modifications may be made therein without departing from the spirit and scope of the claims which follow. | An office, or task, chair comprising an integrally formed brace comprising a combination seat support and back support connected to a chair base by a piston/cylinder height adjustment mechanism. A seat is mounted on the seat support for forward and backward sliding adjustment and for pitch adjustment. A seat back is mounted for sliding adjustment on the back support portion of the brace. The seat support and seat back support portions of the brace are connected by an integrally formed hinge or flex area which permits the seat back support to incline and twist with respect to the seat support portion. Adjustments of the seat with respect to the seat support are carried out in association with dual, concentric handwheels reachable by a user from a seated position. Adjustment of the seat back is done in association with another handwheel located on the rear face of the seat back. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to pulse code modulation telephone switching systems generally and more particularly, to an arrangement for flexibly intermixing digital trunks, connected to the system via a T1 carrier span, having either "Ground Start" or E&M Signalling.
2. Description of the Prior Art
Private automatic branch telephone exchanges (PABX's) function as centralized switching systems. They provide connection between a number of locally connected subscriber telephone lines with associated telephone apparatus and one or more trunk circuits connecting the private automatic branch exchange to one or more distant central offices.
Until very recent times private automatic branch exchanges (PABX's) have provided switching between lines and trunks on a space divided basis. That is, switches of either an electro-mechanical or electronic configuration have provided selective paths through the switching system to interconnect lines to each other or to trunk circuits serving the PABX. In such systems, the signals transmitted through the PABX were generally of an analog nature. In the situation where a line or a trunk circuit utilizing digital techniques such as pulse code modulation was employed, interface providing analog to digital and digital to analog conversion circuitry was a necessity.
More recently a new generation of PABX systems employing time division switching have been provided. Some such systems as the "Dimension" PABX manufactured by Western Electric Company have provided time division switching of analog signals. Other more recent developments in PABX systems have provided time division switching of pulse code modulated signals. Systems of this type have been manufactured by GTE Automatic Electric Company and designated GTD 120, GTD 1000 and GTD 4600. In such systems as the GTD series, analog to digital, digital to analog interfaces have been provided between the lines and trunks and the time division switching system.
To effect greater economies in transmission equipment more extensive use has been made in recent years of digital transmission equipment. Of particular wide acceptance has been the so called T1 type carrier systems which employ pulse code modulation (PCM) to provide a number of multiplexed signal paths over a single transmission facility such arrangements are currently in use primarily between telephone central offices. To date little utilization of such economies has taken place in transmission facilities between central offices and private automatic branch exchanges. The state of the art and time division switching systems employing pulse code modulated signals as the transmission format is exemplified by such systems as the aforementioned GTD 120 the operation of which is described in U.S. Pat. No. 4,007,338 issued to D. W. McLaughlin on Feb. 8, 1977. The use of two one-way lines for signalling in the D2 or D3 PCM type format is discussed in the article "Second Generation Toll Quality PCM Carrier Terminal" by L. Dean Crawford in the April, 1972 issue of the Automatic Electric Technical Journal. A channel bank unit of the type employed and as described above is manufactured by GTE Lenkurt Incorporated and designated the 9002A channel bank.
Accordingly, it is the primary object of this invention to provide facilities in a private branch exchange for trunk circuits connected via a T1 span line and employing pulse code modulation without the introduction of channel bank equipment and to be able to extract and insert the supervisory information necessary for the control of the trunks from and into the T1 span format.
SUMMARY OF THE INVENTION
The data incoming on the span is bipolar and requires a span interface circuit (SIL) to interface to the physical span and convert the incoming bipolar stream of pulses to an unipolar stream of pulses. It does this and provides the signal DINX which is "Data IN". It also creates a data strobe to allow a safe time to monitor the DINX bits called SINX which is "Strobe IN". The DINX signal can then be strobed with the SINX signal and the PCM code to obtain the A and B signalling bits and the S bit.
The frame detector circuit (FDC) monitors these together to find the S bit. Once it is known which bit is the S bit all other bits are known. The frame detector then provides the information to the line compensator circuit (LCM) to enable the correct storage of the PCM bits for 24 channels, and information to the trunk information store (T1S) to enable the correct storage of the A and B bits for 24 channels. The line compensator circuit (LCM) then stores two frames of PCM data in a buffer using the signal (DINX) and the indication of "load data in" (LDI) from the frame detector circuit. The T1 Buffer (T1B) can then request the LCM to forward the signal "send channel zero" (SCO) and the PCM codes will be provided. Note that the GTD-120 system operates from its own clock while the span is not only some fixed phase delay from it but, also that the delay can vary due to thermal as well as other effects. The line compensator LCM then must synchronize to the span data (DINX) using the LDI signal indication from the FDC and, also synchronize in outputting data (PCM Code) to the T1B. Thus, it can compensate for span variations, jitter or thermal drift. This compensation is achieved by the use of two frames of buffering.
The T1B has a one frame buffer. It contains 24 channels of PCM coded data in eight-bit words which are sequentially written corresponding to the span channel's data. However, the reading is random in that the order of extraction depends on the random channel assignment in the GTD-120 network. This read address is derived by monitoring the output of the network channel memory (CH) looking for trunk identities. This address used in conjunction with the sensing of the absence of GTD-120 analog trunk circuits, indicates when digital trunk PCM is required to be extracted from the incoming T1 buffer and sent to the GTD-120 Information Memory (I).
The loading of this PCM code during network time slots will result in the outputting of PCM code due to the "time switching" operation of the network. This PCM code will be sent to the outgoing T1 buffer to be stored. It will again be a function of the trunk identity and absence of the associated analog trunk. The PCM code is stored in the outgoing T1 buffer to be later serially read out; to be sent to the span interface SIL and combined with the outgoing A&B bits (OSB) and S bit. All of which will be combined in the span interface circuit SIL; first to a serial data stream out (DOTX) and finally converted to bipolar. The distant channel bank will sync to the S bit and extract the PCM and signalling data bits.
The frame detector circuit FDC sends information to the T1 supervisory circuit T1S to extract the incoming A and B signalling bits from the DINX data stream. This is via the signal LDI, which indicates the beginning of a frame (clear to the counter) and the digit check signal "DCK" which occurs every channel and clocks the incoming channel counter to generate a write address. The load incoming supervisory Bit A (LISA) and B (LISB) signals are used to write the associated DINX A or B bit into the A or B buffer, respectively.
The reading of this data is dependent on the CPU trunk scan program. This program will asynchronously request a trunk status by outputting the trunk address. This address will be converted to an address of zero through 23 by the T1 supervisory circuit T1S and the corresponding A and B bits will be extracted and converted to the analog trunk data format by the logic and data there located for the CPU to read. When the CPU decides to seize or pulse a trunk, it will again output the analog trunk identity which is converted to an address from zero through 23, and two data bits in the supervisory circuit T1S. The T1 supervisory circuit T1S wil write these into the respective digital trunk A and B outgoing supervisory buffers. These operations only occur if the T1 supervisory circuit T1S has sensed the absence of the analog trunks. The outgoing A and B bits are available to be sent sequentially to the T1 supervisory circuit SIL. The outgoing span data is run from the T1 buffer circuit T1B counter which in turn is a slave to the GTD-120 network time slot counter. The outgoing S bit is created by the T1B 12 frame counter being decoded to generate the correct pattern. The T1B counter provides the channel counter, frame 6 and frame 12 indications to allow for correct PCM bits and A&B supervisory bits to be combined in the span interface circuit SIL to give proper D2 or D3 format. This combined data will then be sent to the distant end office.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic block diagram of the trunk interface of an electronic pulse code modulated switching exchange embodying the principles of the present invention.
FIGS. 2, 3 and 4 when arranged with FIG. 2 at the top and FIGS. 3 and 4 below it is another schematic block diagram as FIG. 1 but in greater detail.
FIG. 5 is a schematic abstract from the trunk supervisory circuit showing the logic for analyzing and coding the trunk types.
FIGS. 6-10 are pulse and timing charts illustrating various clock and timing pulses of the system.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The invention is shown in general terms in FIG. 1. Basically the invention can connect a line in the PABX to some distant subscriber or even two distant subscribers. The second case will be described to better illustrate the disclosure. This case is a trunk to trunk connection as far as the GTD-120 system is concerned. The first situation consists of a line to trunk connection.
Description (FIGS. 2, 3 and 4) the detailed block diagram in these figures shows the basic GTD-120 system to the right and the Distant office channel bank to the lower left. In the upper left of FIG. 2 is the T1 supervisory circuit T1S. To the right is the line compensation module LCM, the frame detector circuit FDC and finally the span interface circuit SIL on the lower center of FIG. 3. The T1 buffer T1B is on the right side of FIG. 3.
This block diagram is also arranged to show a trunk to trunk call through the GTD-120 system using the T1 option and Distant office channel bank. The distant office will use channel unit 1 to be a foreign exchange (FX) channel unit and channel unit 13 to be an E&M type channel unit. This defines the span channels to be used in this connection. Thus the GTD-120 system must allow channel 1 and channel 13 of the span to be time switched in the GTD-120 system to allow for the interchange of PCM codes for a conversation to exist between subscribers using the FX and E&M channel units. The GTD-120 system will recognize channel 1 of the span as digital trunk location 0 or analog trunk #5 which corresponds to identity 132. The GTD-120 system will recognize channel 13 of the span as digital trunk location 12 or analog trunk #17 which corresponds to identity 144. The digital trunk locations number zero through 23 in the T1 associated circuits. The analog trunk's number 128 through 155 of which 132 through 155 correspond to digital locations 0 through 23 in the T1 associated circuits and channels 1 through 24 on the T1 span.
It is also a requirement that the first twelve digital trunks be assigned channels in group 1 of the GTD-120 network because of the physical location of the associated analog trunks (i.e. Identities 132-143). Likewise, the second twelve digital trunks must be assigned channels in group 3 of the GTD-120 network because of the physical location of the associated analog trunks (i.e. Identities 144-155).
The distant end office will provide voice coded samples of both distant subscribers over the span in fixed channels. These channels correspond to the associated distant channel units. The supervisory status of each circuit (i.e. idle seizure, ringing, etc.) will also be included in these channels according to the standard D2 or D3 formatting. This standard formatting is first divided into frames and channels. A frame is considered as 24 eight bit channels and one framing bit for a total of 193 bits per frame.
The supervisory frames are further defined as supervisory "Channel A" which occurs on the 6th frame and supervisory "Channel B" which occurs on the 12th frame. The data value during "Channel A" will be different than that of "Channel B" if the decode is for a "Foreign Exchange" (FX) ground start channel compared to an E&M supervisory channel.
FOREIGN EXCHANGE (FX) GROUND START SIGNALLING the foreign Exchange ground start channel signalling, when receiving data from the far end during supervisory "Channel A" time will receive "TIP GROUND" present or absent data. When receiving data from the far end during Supervisory "Channel B" time it contains "RINGING" present or absent information.
Transmitting data to the far end from the GTD-120 during supervisory "Channel A" time (F6-1) is the "LOOP" closed or open information. During supervisory "Channel B" time (F12-1) "RING GROUND" or "RING OPEN" data is transmitted. The difference between the D2 and D3 formats is that during Receive "Channel A" and Transmit "Channel B" the data bits are inverted. (See Table A).
TABLE A______________________________________(SIGNALLING FORMAT) D3 D2 CH-A CH-B CHA CHB (F6-1) (F12-1) (F6-1) (F12-1)TRANSMIT (OSB) (OSB) (OSB) (OSB)______________________________________Ring Open -- 1 -- 0Ring ground -- 0 -- 1Loop Open 0 -- 0 --Loop Closed 1 -- 1 --RECEIVE CH-A CH-B CH-A CH-BTip Open 1 -- 0 --Tip grd 0 -- 1 --No ring -- 1 -- 1Ringing -- 0 -- 0______________________________________ NOTE: Receive data in the Table A reflects the true value of the span, the data stored in Receive Memories A & B are the inverse of these values. Transmit data reflects the data value at the output sequence buffer (OSB) and is the true value of the span.
E & M SIGNALLING
The supervisory signalling of the E & M channel differs from the FX ground start channel in that Channel A Channel B both carry the same value. The data represents an "ON-HOOK" or "OFF-HOOK" condition at either end. The Receive Memory A & B both store the same value during their respective channel times, the data is read at Receive "Memory A" only. (See Table B).
TABLE B______________________________________(SIGNALLING FORMAT) D2 D3RECEIVE CH-A CH-B CH-A CH-B______________________________________On-Hook 0 0 0 0Off-Hook 1 1 1 1______________________________________ CH-A CH-B CH-A CH-B (F6-1) (F12-1) (F6-1) (F12-1)TRANSMIT (OSB) (OSB) (OSB) (OSB)______________________________________On-Hook 0 0 0 0Off-Hook 1 1 1 1______________________________________ NOTE: Receive data in Table B reflects the true value of the span, the data stored in Receive Memories A & B are the inverse of these values. Transmit data reflects the data value at the output sequence buffer (OSB) and is the true value of the span.
In both Tables A & B the Transmit Memories contain a value of "0 " when a function is being performed such as "TIP Grounded", "Loop closed" or "Off-hook".
Network Operations (FIG. 2)
Assuming that the FX trunk, is channel Unit 1 and thus T1 span channel 1 as well as digital trunk location 0 of the T1 circuits, is assigned channel 2 of Group 1 in the GTD-120 network or Time Slot 9(00010-01). Assuming also, that the E&M trunk, which is channel Unit 13 and thus T1 span channel 13 as well as digital trunk location 12 of the T1 circuits, is assigned channel 1 of Group 3 in the GTD-120 network or Time Slot 7 (00001-11). This is defined by the placement of Identity 132 in time slot location 9 of the network memory CH and identity 144 in time slot location 7 of the network memory CH, respectively. This operation will allow the T1B to detect the digital trunk identity via the bus CHE. The "Time switching" or PCM interchange is accomplished by placing time slot 9 into the time slot 7 location of the CA memory and time slot 7 into the time slot 9 location of the CA memory. The trunk to trunk connection has been established. This example also allows for Pad 1 (-2 db) on time slot 7 PCM or what the E&M trunk hears and Pad 0 (0 db) on time slot 9 PCM or what the FX trunk hears. This use of the pads is not important to the discussion since it only controls the levels of transmission.
The above stated connection will result in a trunk to trunk connection existing until the network memories are cleared by the CPU. This will occur when the CPU has sensed the trunk release via the interface T1S. It should be pointed out that the Distant end office channel bank, SIL, LCM and FDC are continually transmitting T1 span data regardless of the network connection. The T1 S and T1 B incoming T1 buffers are also loaded every frame and the outgoing T1 buffers outputted to the span every frame. The T1S incoming T1 buffer locations will be read as the trunk scan program accesses digital trunks and the T1S outgoing T1 buffer will be loaded when the CPU wants to control a digital trunk (for seizure, pulsing, etc.). The T1S incoming T1 buffer is only read and T1S outgoing T1 buffer is only written while the associated digital trunk identity for the respective memory location exists in the channel memory CH.
The following sequence of events will occur for the previously stated connection:
During every frame the distant office channel bank codes all 24 channels to correspond to the respective channel units. The signalling bits are stuffed into the least significant bit during frame 6 (A bit) and frame 12 (B bit). The meaning of these signalling bits varies with channel unit type and D2 or D3 format. Both ends of the span must use the same signalling format for each channel. In this case, channel 1 will be FX signalling and channel 13 will be E&M. Non-equipped channel units will still result in data being sent over the span since the channel bank common equipment operates the same every channel. The S bit is also provided every frame and will allow the frame detector (FDC) to synchronize to the incoming T1 span data stream and recognize frame 6 and 12.
A stream of 193 bits per frame is sent to the span interface (SIL) via the T1 span line. The span will be made up of N repeaters depending upon the physical length. The span must terminate on an office terminating shelf (which includes a final repeater) before entering the SIL.
The SIL converts the span line bipolar data to unipolar data (DINX) and derives a strobe signal SINX.
The frame detector (FDC) uses SINX to strobe DINX and monitors the serial data stream for the S bit. This is recognized by the toggling bit pattern every other frame. This is known as the terminal framing pattern (TF), once the S bit is located the signalling framing pattern (SF) is available to show the signalling frames. This is accomplished by monitoring the SF pattern for transitions. While "in frame" the FDC forwards the load data in (LDI) signal to the LCM to synchronize its write address counter. This is done by clearing it when the S bit occurs and clocking it from SINX. The digit check (DCK) signal is forwarded to the T1S along with LDI. Since DCK occurs every channel to indicate bit 2 for alarm checking by bit 2 suppression at the distant end, it is used by the T1S to clock its incoming T1 channel counter. The LD1 signal synchonizes the counter to the S bit. The load incoming supervision bit A (LISA) and load incoming supervision bit B (LISB) occur during the supervision bit of every channel for frame 6 and 12, respectively. These then allow the T1S to know which DINX bits are A and B bits, respectively, and since the Incoming T1 channel counter is synchronized as well as DINX to the S bit via LDI control, the incoming T1 buffer can store the received A and B span signals.
The line compensator (LCM) stores the incoming T1 span data (DINX) into its two frame buffer. This is done using the write address counter which is synchronized to the S bit via the LDI signal and increments one count for every SINX pulse. The memory actually stores two bits in 96 locations for the first frame and also a parity bit. The second frame stores another array of two bits for 96 locations giving a total of 192 locations. This two frame buffer allows for writing in one frame buffer while reading from the second. The read address counter is controlled by the T1B signal send channel zero (SC0) and increments from an eight phase clock which cycles every 648 nanoseconds or 193 times every frame. This allows the read function to be synchronized to the network clock. It should be noted that the read and write addresses of the LCM will shift with respect to each other due to span jitter and temperature variations but, the line compensator is able to compensate using the two frame buffer and its read/write control logic. The method used to achieve this is not important and will not be discussed here. The output to the T1B must be in eight bit parallel data format occurring every channel so, a four bit shift register two bits wide is used to store each channel data and once shifted in completely it is transferred to a PCM buffer at the end of the channel (i.e. after the fourth shift).
The T1B now, using the LCM PCM Buffer output loads its incoming T1 buffer. Location zero will then contain the first word received from the span and is the PCM code generated from the FX channel unit in the distant office channel bank. Likewise, location 12 contains the E&M channel units PCM code which was channel 13 of the span. The incoming T1 buffer of the T1B will always contain the span PCM code for every channel regardless of network connections. If all channels are idle, the buffer will contain idle channel PCM code.
The identity of the E&M trunk (144) will be read out of the network CH memory two channels early according to the address of early counter. This will be converted to a zero to 23 binary address, stored in a binary buffer and finally put into a five bit shift register which is 5 bits wide. This is done via the CHE bus of the basic GTD120 by the T1B and results in this case of 144 being converted to 12. The shift register shifts twice each channel or only during group 1 or 3 time slots since this is the only position which a digital trunk identity may reside in the channel memory CH. After four shifts or two channels the D output of the shift register will show the previously loaded 12. The PCM code of the E&M channel unit will now be outputted onto the network PCM IN BUS and stored in time slot location seven.
The CA address of time slot 7 contains time slot 9 and will result in the FX PCM code stored last frame (this is described in a following paragraph) being first stored in the speaker A latch and finally outputted on the PCM OUT BUS. Note that the network P memory has pad value of 1 which corresponds to the -2 db pad. Thus, the outputted PCM will be reduced 2 db by the network PROM table lookup. Also, note that the hold bit in the CB memory overrides the comparison logic of the network forcing the selection of speaker A and that the force conference signal (FCONF-0) is inactive. This time switching operation take one time slot or one quarter of a channel in the GTD-120 system.
The T1B shift register has again shifted and the shift register E output contains the 12. This allows the PCM OUT BUS data to be stored in location 12 of the outgoing T1 buffer. It should be noted that no writing will occur once the identity 144 is removed from memory CH and whatever was last written into location 12 will remain until identity 144 again appears somewhere in the CH memory (of course only in Group 3 time slots).
Two time slots latter the identity of the FX trunk (132) was read from the CH memory and converted to zero by the T1B. It then follows the converted identity of the E&M trunk (12), in the shift register since only every other time slot causes a load and shift. While the 12 is at position E the 0 is at position D which allows the PCM code of the FX channel unit to be outputted to the network PCM IN BUS and stored in time slot location nine. There is a delay between the two bus outputs since they are controlled by the group 1 and 3 network PCM out strobes. Thus, the group 2 strobe will allow PCM to be loaded in time slot 8. Also, the normal analog to digital converter output during digital trunk time slots is disabled by routing these signal via the T1B which blocks the pulse whenever it outputs PCM to the bus.
The CA address of time slot 9 contains time slot 7 and results in the E&M PCM code just stored during time slot 7 being sent out on the PCM OUT BUS. Again, the speaker A buffer is steered out excluding the conference but, now Pad 0 is enabled so no conversion occurs. The two PCM codes have been "time switched" since the code of time slot 7 has been sent to time slot 9 and that of time slot 9 has been sent to 7. This occurring every frame allows conversation to be exchanged between the E&M and FX channel units.
The T1B shift register again shifts and register E output contains the 0. This allows the PCM OUT BUS data to be stored in location 0 of the outgoing T1 buffer. It is apparent that this operation will cease occurring every frame once identity 132 is removed from the CH memory. It is also apparent that if identity 132 were to be written into time slot 5 instead of 9 that the PCM for the FX channel unit will still be stored in location 0 of the T1 buffer due to the connection logic. That is, it is not location dependent on the CH memory assignment, but it is time dependent since in the case of a time slot 5 assignment the time switching process will occur four time slots or one channel earlier for the FX channel unit. Its identity would in this case preceed that of the E&M channel unit in the T1B shift register.
The reading of the outgoing T1 buffer of the T1B is controlled by a time slot counter which is slaved to the network time slot counter. This counter also drives the eight phase clock which the LCM & SIL require as well as a 12 frame counter. The 12 frame counter generates the frame 6 and frame 12 indications to the T1S to request the A and B outgoing signalling bits, respectively. It also generates the outgoing S bit pattern for the distant office channel bank synchronization to the T1 span data stream it receives. The T1S also is given a channel pulse (C1) to run its outgoing T1channel counter and a frame resent (RESET-0) signal to synchronize it. The result of all these things is that the outgoing span will be synchronized to the T1B counters, and thus to the GTD-120 network clock. The output of the outgoing T1 PCM buffer is sequentially sent in eight bit parallel to the SIL and load with the signal load voice sample (LVS).
The CPU reads the T1S Incoming T1A/B buffer by providing the digital trunk identity which the T1S converts to 0 through 23. The writing of the outgoing T1A/B buffer uses the same conversion since the CPU can only read or write. Then, the FX trunk will be presented by the CPU as 132 and converted to 0 while the E&M trunk will be presented as 144 and converted to 12. The outgoing T1 A/B Buffer always contains the last data written to that trunk location by the CPU. The CPU read and write operations are controlled by the GTD-120 software program.
The outgoing T1A Buffer is read during frame 6 sequentially according to the outgoing T1 channel counter of the T1S. Likewise, the B buffer is read during frame 12. The common output of A or B data is presented to the SIL as the outgoing supervisory bit signal (OSB).
The SIL receives the PCM code and S bit from the T1B and the OSB signal from the T1S along with the LVS signal. It also receives the eight phase clock outputs and using LVS as a synchronization signal counts the eight phase clock in a counter. The SIL combinational logic converts the data to the proper span format and then uses the counter to convert to serial. The serial unipolar data stream DOTX is then converted to bipolar. The bipolar stream is then sent to the distant office channel bank via the T1 span line. The SIL combinational logic senses the S bit by noting that its counter counts on extra count between LVS signals. It stuffs the A bits (OSB) into the least significant bit of every channel during frame 6 and the B bits (OSB) into the lease significant bit of every channel during frame 12.
The channel bank receive common senses the S bit and extracts the A&B bits of every channel. It has a channel counter running off its clock drive to distribute the A and B bits to the correct channel unit and converts the PCM codes to PAM. The PAM is then converted to analog by the respective channel unit.
RECEIVING AND DECODING OF DATA ON CHANNEL A & B (FIG. 5)
The status of the T1 supervisory circuit Receive Memory A & B data for all 24 channels is continuously being updated every 125 micro-seconds by the incoming data from the span. The GTD-120 Central Processor scans sense points -LLDR4 thru -LLDR7 by addressing the Receives Memories via a 5 bit address and by enabling the tri-state buffers (223, 224, 225 and 226) via the CPV read strobe.
The data read from the Receive Memories A (201) & B (202) is conditioned to the proper format expected by the processor complex by gates 206-210 and 215 and 216. The steering logic is controlled by the eight bit data selector multiplexor 228 for reading data out of the Receive Memories A & B (201 and 202). The last 3 bits of the 5 bit CPV channel read address are used to decode the eight bit data selector input lead from the manual program board 205. Each input lead from the program board decodes the supervisory status for four consecutive channel addresses. This grouping is for convenience only since should it be required each individual trunk address could be coded.
The signalling format is pre-set for all 24 channels and is decoded as of the "D2" type if no shorting pin is inserted between pins 1 and 9 of the program board.
Gates 206, 207 and 208 provide the data steering based on the format, if the format is "D2" gate 207 inverts the receive Memory A (201) data to the input of gate 215.
Gates 209, 210 and 211 are conditioned by the eight bit data selector to read Receive Memory B (202) data if it decodes an "FX-IN" mode. If the mode is E & M signalling, steering gate 210 steers the inverted data from Receive Memory A (201).
Gate 215 Ands the ground detected signal from Receive Memory A (201) with the "FX-IN" command to the tri-state sense point -LLDR7 via gate 223 to be read by the Central Processor.
The Central Processor will read and is interested in data bits "-LLDR4" thru "-LLDR7" for trunk circuits that are of the FX loop or ground start type. If the mode of incoming supervision is of the E & M type gates 215 and 216 inhibit data sense points "-LLDR7" and "-LLDR5", respectively. Sense point "-LLDR4" is unused in either FX loop or ground start or E & M T1 interface, this leaves "-LLDR6" as the incoming supervision sense point.
Conditioning and Transmitting of Data to the Far End Office
The Central Processor writes the data instructions into Transmit Memories A & B (203, 204). The data is read out of the Transmit Memories A & B (203 and 204) during the decoded Channel address from the read cycle of the T1 span. Again, the last 3 bits of the 5 bit T1 read channel address are used to decode gate 229 which in turn reads the status for the group of four channel identities from the Program board.
Gate 229 decodes the mode of supervision to be transmitted to the far end office. Gates 212, 213 and 214 provide data steering based on the signalling format, in the event of a D2 format the data read from Transmit Memory B (204) is inverted to the input of Gate 212.
Gates 220, 221 and 222 provide data steering depending on the signalling type. If the signalling is FX loop or ground start they pass data read from Transmit Memory B 204. If the decode is for E & M supervision, data from Transmit Memory B (204) is blocked at gate 221 and data from Transmit Memory A (203) is forwarded to the multiplexor steering gate 217.
Gate 217 multiplexes data from Transmit Memory A during "F6-1" time or "Channel A" data from either Transmit Memory B (204) or "Memory A" (203) during "F12-1" time or "Channel B".
Output sequence buffer 227 facilitates the interface to the span interface card.
Gate 216 provide the logic to simulate a current flow signal to sense point "-LLDR5", the current flow signal is a function of being in the FX loop or ground start signalling mode and having transmitted a loop closure signal to the far end and having received a "ground detected" signal from the far end office. These two conditions plus the transmitting of a loop closure signal to the far end office are the requirements to simulate current flow. During the Central Processor read cycle both the Receive and Transmit memories are enabled, since the span data to determine current flow are in Receive Memory A and in Transmit Memory A.
While a preferred embodiment of the apparatus and method provided by the present invention has been described, various modifications may be made without departing from the invention as defined in the appended claims. | Digital Carrier Trunks connected via a supervisory decoding and multiplexing logic to an electronic digital PABX. The circuit is arranged to receive or transmit the supervisory signal in either the "Ground Start", E&M modes or a combination of both in either the D2 or D3 signalling format over a T1 carrier span without converting to the analog signal form. | 7 |
BACKGROUND
[0001] 1. Technical Field
[0002] The present invention relates to a method for preparing a carbon dioxide absorbent based on natural biomass, and a carbon dioxide absorbent based on natural biomass that is prepared by the method. More particularly, the present invention relates to a method for preparing a carbon dioxide absorbent that utilizes alkali metal or alkaline earth metal components, such as Ca, Ma and K, inherent to a natural plant biomass material, thus enabling the preparation of a highly efficient carbon dioxide absorbent at low cost.
[0003] 2. Description of the Related Art
[0004] Carbon dioxide is a major cause of global warming and its concentration in the atmosphere has been sharply increasing since the Industrial Revolution. The carbon dioxide issue is considered a global problem through the Rio Declaration on Environment and Development and the Kyoto Protocol, and solutions to solve this problem have been actively studied.
[0005] Carbon dioxide sources are usually flue gases released from the burning of fossil fuels, synthetic gases produced during coal gasification, and synthetic gases produced during natural gas processing. Many methods for removing carbon dioxide are known, for example, wet chemical absorption, adsorption, membrane separation and low temperature distillation. However, these methods incur high costs and are thus difficult to commercialize.
[0006] According to a known method for removing carbon dioxide from a gas stream using a dry sorbent, an active component present in the solid sorbent is allowed to chemically react with carbon dioxide to produce a carbonate or bicarbonate. The sorbent can be regenerated and reused after heating in a regeneration reactor. The dry sorbent should meet the following requirements: 1) inexpensive materials, 2) easy regeneration, 3) applicability to low energy absorption processes, and 4) the ability to remove carbon dioxide present at a very low concentration. Other requirements for the dry sorbent are environmental friendliness, good absorptivity for carbon dioxide, and high reaction rate. Further, the dry sorbent should be made of a physically or chemically durable material.
[0007] U.S. Pat. No. 6,387,337 issued to the United States Department of Energy (DOE) suggests a method for preparing a dry sorbent using an alkali metal or alkaline earth metal compound deposited on a support. Further, Korean Patent No. 620546 discloses the preparation of a dry sorbent that uses an alkali metal or alkaline earth metal compound as an active component to increase the removal efficiency of carbon dioxide. According to this patent, the dry sorbent is prepared by dispersing a sorbent composition essentially composed of an active component, a support and an inorganic binder in water to prepare a slurry, molding the slurry in a spray dryer to prepare a granular absorbent, and calcining the absorbent. However, the above patents are based on the ability of alkali metals and alkaline earth metals to absorb carbon dioxide and are associated with artificial addition of the corresponding components for the dry carbon dioxide absorbents. No study has been, to our knowledge, reported on a technology for removing carbon dioxide utilizing alkali metals and alkaline earth metals inherent to natural biomass materials.
[0008] Thus, the present inventors have continued to investigate a method for preparing a high performance carbon dioxide absorbent in an environmentally friendly and economical manner without artificial addition of alkali metals and alkaline earth metals. As a result, the present inventors have succeeded in developing a method for preparing a high performance carbon dioxide absorbent that utilizes natural alkali and alkaline earth metals inherent to a natural biomass material, contributing to cost reduction.
BRIEF SUMMARY
[0009] It is an object of the present invention to provide a method for preparing a high performance carbon dioxide absorbent from natural plant biomass in an environmentally friendly and economical manner. It is another object of the present invention to provide a carbon dioxide absorbent based on natural biomass that is prepared by the method.
[0010] One aspect of the present invention provides a method for preparing a carbon dioxide absorbent based on natural biomass, the method including (S1) carbonizing a plant biomass material containing alkali metals or alkaline earth metals, and (S2) pulverizing the carbonized biomass material.
[0011] Now, a detailed description will be given concerning the respective steps of the method for preparing a carbon dioxide absorbent based on natural biomass according to the present invention.
[0012] First, a plant biomass material containing alkali metals or alkaline earth metals is carbonized (step S1). This carbonization enables the removal of low boiling point impurities, such as wax and pectin, from the plant biomass material and can increase the physical strength of a final carbon dioxide absorbent while improving the surface area and porosity of the carbon dioxide absorbent.
[0013] The plant biomass material used in the present invention is naturally occurring one and the kind thereof is not fundamentally limited. For example, any natural plant biomass material that contains an alkali metal selected from the group consisting of lithium, sodium and potassium or an alkaline earth metal, such as calcium or magnesium, may be used in the present invention. Plant cellulose containing large amounts of alkaline earth metal components, such as calcium (Ca) and magnesium (Mg), is particularly preferred. Any natural plant cellulose material may be used as the plant biomass material in the present invention. For example, the plant biomass material may be selected from the group consisting of, but not necessarily limited to, henequen fibers, kenaf, abaca, bamboo, hemp, flax, jute, pineapple, ramie, sisal hemp, rice straw, barley straw, wheat straw, rice husk, and mixtures thereof.
[0014] According to one embodiment of the present invention, the carbonization may be performed by raising the temperature of the plant biomass material from 500 to 1,800° C. under a nitrogen/hydrogen atmosphere in a closed state for 0.2 to 2 hours. In the present invention, as the carbonization temperature increases, the surface area of the carbonized biomass material and the ratio of the metal content of the sample to the carbon content thereof can be increased. In this step, the carbonization temperature is preferably in the range of 500 to 1,800° C., particularly preferably 900 to 1,100° C. If the carbonization is performed at a temperature not higher than 1,000° C., large amounts of tar components, such as wax and pectin, may be produced. There is thus a need to prevent a vent port from being contaminated by the impurities. To this end, a filter is installed and the impurities are periodically washed out. Alternatively, a catalytic combustion device may be introduced to remove the impurities. The nitrogen/hydrogen atmosphere in a closed state may be created by any suitable method known in the art, for example, by supplying nitrogen and hydrogen in a volume ratio of 1:1 to a quartz tube maintained in a closed state, but the present invention is not necessarily limited thereto.
[0015] According to a further embodiment of the present invention, step S1 may further include impregnating the plant biomass material with liquid nitrogen and cutting the frozen plant biomass material into 1 to 2 mm long pieces before carbonization to further enhance the effects of the subsequent carbonization.
[0016] Next, the carbonized biomass material is pulverized to prepare a carbon dioxide absorbent (step S2). This pulverization can increase the surface area of the carbonized biomass material, leading to an improvement in the performance of the carbon dioxide absorbent.
[0017] The carbon dioxide absorbent prepared in step S2 preferably has a thickness of 0.5 mm or less and a length of 1 mm or less, but is not necessarily limited to this size. The size of the carbon dioxide absorbent may be varied depending on where the absorbent is used. The method may further involve pulverizing the carbon dioxide absorbent into a finely divided powder. The fine powder may be allowed to react with an inorganic binder, such as cement, clay or ceramic, followed by molding into beads.
[0018] Another aspect of the present invention provides a carbon dioxide absorbent based on natural biomass that is prepared by carbonizing a plant biomass material containing alkali metals or alkaline earth metals and pulverizing the carbonized plant biomass material.
[0019] The carbon dioxide absorbent of the present invention can be effectively used for dry carbon dioxide absorption processes necessary to recover carbon dioxide contained in flue gases, which arise from the conversion of fossil fuels in industrial facilities, such as thermal power stations, before release into the atmosphere.
[0020] The carbon dioxide absorbent of the present invention utilizes, as active components, alkali and alkaline earth metal components in the form of highly dispersed nanoparticles that are inherently present in a natural plant biomass material. The present invention is distinguished from a conventional technology in which alkali and alkaline earth metal components as active components are dispersed on the surface of a support, such as zeolite, alumina or Celite, to absorb carbon dioxide. The present invention has the advantages that the processing cost is drastically reduced, the performance of the absorbent is improved, and the metal components, which have been discarded after use, can entirely be recovered by burning carbon components.
[0021] In addition, the alkali metal or alkaline earth metal components as active components of the carbon dioxide absorbent of the present invention are in a highly dispersed state in the natural biomass material. Therefore, there is no need for a process for maintaining a highly dispersed state of the active components upon addition, which is essential to prepare conventional carbon dioxide absorbents, contributing to a drastic reduction in processing cost.
BRIEF DESCRIPTION OF DRAWINGS
[0022] FIG. 1 shows the quantities of carbon dioxide adsorbed to carbon dioxide absorbents prepared in Examples 1 and 1-1 and Zeolite Y as a conventional carbon dioxide absorbent, which were measured in accordance with Test Example 2.
[0023] FIG. 2 shows the quantities of carbon dioxide desorbed from carbon dioxide absorbents prepared in Examples 1 and 1-1 and Zeolite Y as a conventional carbon dioxide absorbent, which were measured in accordance with Test Example 2.
[0024] FIG. 3 shows the rates of adsorption of carbon dioxide on carbon dioxide absorbents prepared in Examples 1 and 1-1 and Zeolite Y as a conventional carbon dioxide absorbent.
[0025] FIG. 4 shows the rates of desorption of carbon dioxide from carbon dioxide absorbents prepared in Examples 1 and 1-1 and Zeolite Y as a conventional carbon dioxide absorbent.
DETAILED DESCRIPTION
[0026] The present invention will be illustrated in more detail with reference to some examples. However, it should be understood that the following examples are provided for illustration only, and that various modifications, variations, and alterations can be made without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be limited only by the accompanying claims and equivalents thereof.
Example 1
Preparation of Carbon Dioxide Absorbents Using Natural Henequen Fibers
[0027] For ease of carbonization, natural henequen fibers were split into fiber strands having a thickness of tens to hundreds of micrometers, impregnated with liquid nitrogen, and cut into 1-2 mm long fiber pieces. After the henequen fiber samples were placed in quartz tubes, nitrogen and hydrogen in a volume ratio of 1:1 were supplied to the quartz tubes for 30 min to remove impurities from the quartz tubes. The quartz tubes in the nitrogen/hydrogen atmosphere were heated at a rate of 10° C./min to respective temperatures of 500° C., 700° C., 900° C. and 1100° C. and maintained for 1 hr at the temperatures to carbonize the henequen fibers. Thereafter, the carbonized henequen fibers were pulverized into powders using a mortar and pestle to prepare carbon dioxide absorbents.
Example 1-1
Preparation of Carbon Dioxide Absorbents Using Natural Bamboo Samples
[0028] For ease of carbonization, pristine bamboo samples were cut in the lengthwise direction into 1-2 cm thick sticks and chopped into 1-2 cm long pieces. The bamboo pieces were cut into powders of several nm to several mm using a chopper. After the bamboo powders were placed in quartz tubes, nitrogen was supplied for 30 min to the quartz tubes to remove impurities from the quartz tube. Subsequently, the quartz tubes were heated at a rate of 10° C./min to respective temperatures of 500° C., 700° C., 900° C., 1,100° C., 1,300° C. and 1,800° C. while supplying nitrogen and hydrogen in a volume ratio of 1:1 to the quartz tubes, and maintained for 1 hr at the temperatures to carbonize the bamboo fibers. Thereafter, the carbonized bamboo samples were pulverized into powders using a mortar and pestle to prepare carbon dioxide absorbents.
Test Example 1
Measurements of BET Surface Areas, Pore Volumes and Pore Sizes of the Henequen Carbonization Products (Example 1)
[0029] The BET surface areas, pore volumes and average pore diameters of Zeolite X and Zeolite Y as conventional carbon dioxide absorbents and the carbon dioxide absorbents (the henequen fibers after carbonization) prepared in Example 1 were measured using an accelerated surface area and porosimetry analyzer (ASAP2010, Micromeritics). The results are shown in Table 1. For the BET surface area measurements, the carbon dioxide absorbents were pretreated at 150° C. (heating rate=10° C./min) for 800 min and depressurized to 100 μmHg at an evacuation rate of 5.0 mmHg/s. The BET surface areas were measured at pressures of 0 to 800 mmHg and room temperature (25° C.).
[0000]
TABLE 1
Mesopores
Micropores
BET
(BJH des. data)
(H-K data)
Henequen
surface
Pore
Average
Maximum
Average
carbonization
area
volume
diameter
volume
diameter
temp. (° C.)
(m 2 /g)
(cm 3 /g)
(Å)
(cm 3 /g)
(Å)
Before
6
—
—
—
—
carbonization
(pristine)
Henequen 500
16
0.02
70
0.00
13
Henequen 700
74
0.04
41
0.03
7
Henequen 900
578
0.18
52
0.23
6
Henequen 1100
991
0.38
50
0.36
7
Zeolite X
573
0.13
18
0.30
5
Zeolite Y
524
0.21
26
0.33
6
[0030] As can be seen from the results in Table 1, the BET surface areas and the mesopore and micropore volumes of the absorbents were increased with increasing carbonization temperature. The pore diameters of the absorbents were decreased with increasing temperature. The henequen fiber carbonized at a temperature of 1,100° C. was found to have the largest BET surface area, the largest pore volumes and the smallest pore diameters.
Test Example 1-1: Measurements of BET Surface Areas, Pore Volumes and Pore Sizes of the Bamboo Carbonization Products (Example 1-1)
[0031] The BET surface areas, pore volumes and average pore diameters of Zeolite X and Zeolite Y as conventional carbon dioxide absorbents and the carbon dioxide absorbents (the bamboo samples after carbonization) prepared in Example 1-1 were measured using an accelerated surface area and porosimetry analyzer (ASAP2010, Micromeritics). The results are shown in Table 2. For the BET surface area measurements, the carbon dioxide absorbents were pretreated at 150° C. (heating rate=10° C./min) for 800 min and depressurized to 100 nmHg at an evacuation rate of 5.0 mmHg/s. The BET surface areas were measured at pressures of 0 to 800 mmHg and room temperature (25° C.).
[0000]
TABLE 2
Mesopores
Bamboo
(BJH des. data)
carbonization
BET surface area
Pore
Average
temp. (° C.)
(m 2 /g)
volume (cm 3 /g)
diameter (Å)
Before
10
—
—
carbonization
(pristine)
Bamboo 700
66
0.00
57
Bamboo 900
51
0.01
36
Bamboo 1100
13
0.00
6
Bamboo 1300
17
0.01
5
Bamboo 1500
7
0.01
6
Bamboo 1800
8
0.01
6
Zeolite X
573
0.13
18
Zeolite Y
524
0.21
26
[0032] As can be seen from the results in Table 2, the surface areas of the bamboo samples after carbonization at a temperature of 700° C. or more tended to increase compared to those before carbonization. Specifically, the bamboo sample carbonized at 700° C. had a surface area of 66 m 2 /g. However, the BET surface areas of the bamboo samples showed a tendency to decrease with increasing carbonization temperature, unlike the henequen samples. On the other hand, the bamboo samples had few or no mesopores and did not appear to be greatly affected by the thermal treatment temperature. The mesopore diameters of the bamboo samples showed a tendency to considerably decrease with increasing thermal treatment temperature, which is similar to the tendency of the BET surface areas. As a consequence, the bamboo product carbonized at a temperature of about 700° C. had the largest BET surface area.
Test Example 2: Measurements of Carbon Dioxide Adsorption (Physical and Chemical Adsorption)
[0033] The characteristics of “Henequen 900” and “Henequen 1100” prepared by carbonization of henequen at 900° C. and 1,100° C., respectively, “Bamboo 700”, “Bamboo 900” and “Bamboo 1100” prepared by carbonization of bamboo at 700° C., 900° C. and 1,100° C. respectively, and commercial Zeolite Y as carbon dioxide absorbents were compared.
[0034] The carbon dioxide adsorption/desorption performance and rates of the carbon dioxide absorbents were measured using an accelerated surface area and porosimetry analyzer ASAP2010 (Micromeritics) in the pressure range of 0 to 800 mmHg at room temperature. The results are shown in FIGS. 1 to 4 . As shown in FIG. 1 , Henequen 900 adsorbed the largest quantity of carbon dioxide (2.41 mmol), and Henequen 1100 adsorbed the second largest quantity of carbon dioxide (2.05 mmol). The bamboo samples adsorbed smaller quantities of carbon dioxide than Henequen 900 but adsorbed a quantity of carbon dioxide comparable to Henequen 1100 despite their considerably smaller BET surfaces than the henequen samples. Specifically, Bamboo 700 and Bamboo 900 adsorbed 1.9 mmol and 1.88 mmol of carbon dioxide, respectively, less than the henequen samples. On the other hand, Zeolite Y adsorbed a relatively small quantity of carbon dioxide (1.67 mmol) compared to Henequen 900, Henequen 1100, Bamboo 700 and Bamboo 900. The desorption curves of FIG. 2 showed a similar tendency to the absorption curves of FIG. 1 . From these results, it can be inferred that the CO 2 adsorptivity of Henequen 900 was highest and that of Bamboo 700 and Bamboo 900 follows in this order.
[0035] The adsorption and desorption rates of the absorbents were compared based on the results shown in FIGS. 1 and 2 , and the results are shown in FIGS. 3 and 4 , respectively. In these figures, Henequen 900 was found to have higher adsorption and desorption rates than the conventional zeolite samples, demonstrating that Henequen 900 is very useful in actual applications.
[0036] In conclusion, Henequen 900 has better ability to adsorb carbon dioxide and higher CO 2 adsorption and desorption rates than the conventional zeolite samples. This fact proves the usefulness of Henequen 900 in actual applications. Although the bamboo carbonization samples (particularly, Bamboo 700) showed slightly inferior characteristics in terms of the total adsorptivity and adsorption/desorption rate, their application would be very desirable because their biomass resources are available in Korea and can be prepared in an economical and simple manner.
Test Example 3: Measurement of Carbon Dioxide Adsorption (Chemical Adsorption)
[0037] The quantities of CO 2 chemically adsorbed to the carbon dioxide absorbents of Examples 1 and 1-1 were calculated using a Micromeritics Autochem 2910 analyzer. First, the carbon dioxide absorbents (Henequen 900 and Zeolite Y) in the form of powders were heated to 200° C. in an argon atmosphere to remove moisture, and chemical adsorption tests were conducted in a pulsed mode at room temperature (25° C.). As a result of the chemical adsorption testing, Henequen 900 adsorbed 5.2 ml/g CO 2 and Bamboo 700 adsorbed 4.5 ml/g CO 2 , whereas substantial chemical adsorption did not occur in Zeolite Y. From these results, the increased quantities of CO 2 chemically adsorbed to the henequen or bamboo samples are thought to be due to the presence of the alkali and alkaline earth metal components inherent to the samples. No chemical adsorption in Zeolite Y is explained by the absence of active sites where carbon dioxide is chemically adsorbed on the surface of Zeolite Y.
[0038] The results of Test Examples 2 and 3 confirm better performance of the carbon dioxide absorbents based on natural biomass prepared in accordance with the method of the present invention.
Test Example 4: ED-XRF Analysis
[0039] Energy dispersive x-ray fluorescence (ED-XRF) analysis was conducted to analyze the components of the henequen carbonization products and the bamboo carbonization products used as the carbon dioxide absorbents prepared in Examples 1 and 1-1. The results are shown in Table 3. The henequen products were obtained by carbonization at temperatures of 500° C., 700° C., 900° C., 1,100° C., 1,300° C., 1,500° C., and 1,800° C., and the bamboo products was obtained by carbonization at temperatures of 700° C., 900° C., 1,100° C., 1,300° C., 1,500° C., and 1,800° C.
[0000]
TABLE 3
K (wt %)
Ca (wt %)
Si (wt %)
P (wt %)
Henequen 500
4.98
93.57
—
—
Henequen 700
3.68
95.46
—
—
Henequen 900
2.79
95.53
—
—
Henequen 1100
2.82
95.59
—
—
Henequen 1300
2.94
95.97
—
—
Henequen 1500
2.62
94.58
—
—
Henequen 1800
1.25
96.86
—
—
Bamboo 700
75.55
16.17
0.00
2.11
Bamboo 900
74.43
15.09
5.21
2.15
Bamboo 1100
75.26
16.54
4.49
1.81
Bamboo 1300
72.53
19.31
5.32
1.92
Bamboo 1500
63.65
25.88
5.63
3.53
Bamboo 1800
16.20
42.44
32.61
8.24
[0040] The ED-XRF analytical results shown in Table 3 are the relative proportions of the metal components in the samples and the numbers indicated by wt % are not absolute values but relative proportions. As shown in Table 3, the henequen and bamboo samples were found to include alkali and alkaline earth metals, such as K and Ca. In addition, the Ca contents of the henequen samples were much higher than the K contents thereof, whereas the K contents of the bamboo samples were high relative to the Ca contents thereof. The absolute metal contents were confirmed by a suitable technique, such as inductively coupled plasma optical emission spectrometry (ICP-OES). | A method for preparing a carbon dioxide absorbent based on natural biomass, and a carbon dioxide absorbent based on natural biomass that is prepared by the method. The method utilizes alkali metal or alkaline earth metal components, such as Ca, Ma and K, inherent to a natural plant biomass material. The method can provide a carbon dioxide absorbent with improved performance in an environmentally friendly manner at greatly reduced cost. | 8 |
BACKGROUND OF THE INVENTION
[0001] 1. Technical Field
[0002] The present invention relates generally to the laundering of textiles. More particularly, the invention relates to the insurance of an acceptable level of cleanliness of the textiles. Specifically, the invention relates to the testing of the water solution in which the textiles are cleaned for the presence of adenosine triphosphate (ATP).
[0003] 2. Background Information
[0004] In the field of industrial laundering, there is a need to ensure that textiles which are laundered meet certain standards of cleanliness. Of particular concern is the amount of bacteria on the laundered textiles although the amount of other contaminants is also important. Testing for the presence of adenosine triphosphate (ATP) is a useful indicator of various contaminants including bacteria because ATP delivers energy to all living organisms and is found in organisms both living and dead.
[0005] One of the current primary test methods involves the direct testing of textiles which have been laundered and dried. In particular, test procedures have been developed which utilize a swab rubbed directly on textiles in order to obtain a test sample of ATP therefrom. A luminometer is then used to quickly analyze the concentration or amount of ATP on the swab. A test kit using such a swab is described in greater detail in U.S. Pat. No. 6,180,395 granted to Skiffington et al., which is incorporated herein by reference. This test method provides rapid results and thus is a great advantage over the relatively slow process of bacterial colony growth, which usually takes about two days and is obviously not suitable for the purposes of testing laundered textiles.
[0006] While such swabbing methods are very convenient, they nonetheless have some drawbacks. One disadvantage is that the testing occurs after the textiles have been dried. Thus, if a given piece or batch of textiles must be re-washed due to an unacceptable ATP level which remained after laundering, that piece or batch of textiles will have already undergone the costly and time consuming step of drying. In addition, the swab testing of a given textile may produce different results depending on where the textile is swabbed. More particularly, a given textile may have been heavily soiled in one area and lightly soiled in another area so that even after laundering, the area which was heavily soiled may retain a greater degree of contamination. In addition, in order to obtain a suitable sample size which is likely to be representative of a large batch of textiles, a fairly large number of textiles must be individually tested in the present swabbing method to minimize concerns related to random sampling. Thus, there is a need in the art to provide a test for sanitation of textiles at an earlier stage of the laundering process while minimizing the number of tests performed.
BRIEF SUMMARY OF THE INVENTION
[0007] The present invention provides a method comprising the steps of cleaning textiles with a water solution whereby the water solution becomes used; and testing the used water solution for the presence of adenosine triphosphate (ATP).
[0008] The present invention also provides a method comprising the steps of cleaning textiles with a water solution whereby the water solution becomes used; and testing the used water solution to determine a level of contaminants therein in no more than 15 minutes.
[0009] The present invention further provides a method comprising the steps of cleaning textiles with a water solution in a cleaning vessel whereby the water solution becomes used; and testing the used water solution to determine a level of contaminants therein while the textiles remain in the cleaning vessel.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0010] FIG. 1 is a diagrammatic view of a washing machine and a testing device for testing the water solution drained from within the washing machine.
[0011] FIG. 2 is a diagrammatic view of the testing device.
[0012] FIG. 3 is similar to FIG. 1 and shows additional water solution being extracted from the drained textiles and the testing of the extracted water solution.
DETAILED DESCRIPTION OF THE INVENTION
[0013] A first method of the present invention is described with reference to FIGS. 1-2 ; and a second method is described with reference to FIG. 3 . Generally, the methods of the present invention are used to ensure the sanitation or cleanliness of laundered textiles.
[0014] FIG. 1 shows a cleaning device in the form of a washing machine or washer 10 having a cleaning vessel in the form of a rotatable drum 12 which defines a washer compartment therein in which laundry or textiles 14 may be placed for washing in a water solution 16 which may contain various detergents and chemicals suitable to promote the cleaning of textiles 14 . Textiles 14 may be made up of various textiles such as aprons, butcher coats, sheets, towels, surgical garments, napkins, various other types of uniforms, linens, and so forth. A container or catch vessel 18 is disposed below washer 10 to catch the soiled or dirty water solution 16 which is drained (arrow A) from washer 10 subsequent to the washing or laundering of textiles 14 . Vessel 18 is initially free of adenosine triphosphate (ATP) prior to catching the soiled water solution 16 , commonly known as sour drain.
[0015] Washing textiles 14 in washer 10 is not the only method or device for cleaning textiles 14 , and the process shown in the figures is meant to represent the cleaning of textiles by any method using a water solution. For example, dry cleaning utilizes a water solution having dry cleaning chemicals therein to achieve the cleaning process. The present test method may be used to test the used water solution from the dry cleaning process as well. In addition, newly manufactured textiles are typically cleaned by dipping them in a cleaning solution at the manufacturing textile mill. At least the final solution used in this cleaning process involves a water solution which may also be tested by the present method.
[0016] An ATP tester 20 is used to test the drained solution 16 . In the exemplary embodiment, tester 20 includes a luminometer 22 , a sample cylinder 24 and a swab 26 which is removably insertable into cylinder 24 and held by handle 27 . Depending on the specific test, the cylinder and/or swab may be inserted into the luminometer 22 , or, for instance, a portion of cylinder 24 may be inserted into luminometer 22 . One such tester is described in the afore mentioned U.S. Pat. No. 6,180,395, which as previously mentioned is incorporated herein by reference. Such testing devices are sold by Charm Sciences, Inc. of Malden Mass. under the names Pocketswab® Plus, Watergiene® and Allergiene®. Another portable swab-type device used in an ATP bioluminescent test is sold under the name Lightning® by Idexx Laboratories, Inc. of Westbrook, Me.
[0017] These swab-type devices typically have a pre-moistened swab for gathering a test sample which is mixed within a tube such as cylinder 24 with a buffer solution and luciferin-luciferase test reagents which provides for bioluminescence which is read by the luminometer in relative light units (RLU). The Pocketswab® device utilizes a buffer to facilitate the rapid release of ATP from any organic source including micro-organisms and a neutralizer buffer for optimizing the luciferin-luciferase reaction.
[0018] Various other ATP tests are also available. Other bioluminescent ATP tests include one which is described in “The Handbook of ATP-Hygiene Monitoring” by Bio-Orbit Oy of Turku, Finland; and one known as the Charm ABC Swab Test sold by the above referenced Charm Sciences, Inc.
[0019] As further shown in FIG. 1 , swab 26 is dipped in or otherwise wetted by the drained water solution 16 , reinserted into cylinder 24 and mixed with the appropriate buffer solution and luciferin-luciferase reagents in order to provide the bioluminescence which is then measured by luminometer 22 . FIG. 2 shows that luminometer 22 has a display 28 on which is displayed a specific read out or result 30 of the ATP detected from swab 26 , measured in RLU's. Once the sample is placed in luminometer 22 , it takes only about five seconds to obtain result 30 . A predetermined acceptable level of ATP is typically stored within luminometer 22 and compared with result 30 so that luminometer 22 may also display a pass or fail indication.
[0020] If the ATP level is below the acceptable predetermined value, textiles 14 are then removed from washer 10 and dried in a dryer typically heated by a gas or electric heat source. This may be followed by various finishing steps, such as ironing, pressing, steaming such as through a steam tunnel, and the hanging of textiles such as garments on hangers and enclosure of the textiles within bags, boxes or the like. Preferably, no additional sanitizing steps are required after removing the textiles from the washer, as detailed further below.
[0021] However, if the ATP level is greater than the acceptable value, textiles 14 will be re-washed or otherwise additionally cleaned and retested in the same manner until the test result is within an acceptable range. Typically, textiles 14 go through multiple cleaning or washing cycles which include washing, draining, rinsing and possibly extraction by centrifuge or the spinning of drum 12 at relatively high speeds. Based on previous testing and general knowledge within the field, personnel within the field of laundering may already know that for a given type of textiles, it will take a certain number of washes and rinses in order to approach the degree of sanitation desired. Thus, a given load of textiles may be washed and rinsed more than once and often many times before the drain water solution is tested for ATP. Because the various types of tests used in the present invention are relatively quick, generally taking no more than five or ten minutes and potentially even less, the testing of the drained water solution will normally be done while the textiles remain in the washer. Preferably, the testing period takes no more than 15 minutes.
[0022] Referring to FIG. 3 , the second method of testing is described. The second method is very similar to the first method except that the water solution which is tested is that which is extracted from textiles 14 after the standard drain of solution 16 by gravity and/or pumping thereof. More particularly, drum 12 goes through a spinning cycle, or is rotated at relatively high speeds in order to extract additional water solution 16 from textiles 14 via a centrifuge effect or centrifugal force. Rotation of drum 12 is shown at arrows B and the extracted solution is indicated at arrow C. The extracted solution 16 is then drained into vessel 18 and tested in the same manner as described above.
[0000]
TABLE 1
Comparison of Test Locations
Test Location
Dry Soiled Textile
Test Vessel
Washer Drain
ATP (RLU)
173,387
835,793
5,444,266
Hach Test Kit
<100
100,000
1,000,000
(CFU)
Table 1 Notes:
1. The “dry soiled textile” test was performed prior to being washed; the “test vessel” test was of soiled water solution extracted from a textile which was placed in a water solution in a vessel and stirred or slightly agitated; and the “washer drain” test was a test of soiled water solution drained from the washer in which the textile was washed, the latter being indicative of a high degree of agitation.
2. All ATP results from a swab method with readings from a NovaLum ® luminometer.
3. Hach Test Kit readings were taken after 48 hours of bacterial growth and reported as colony-forming units (CFU). In particular, the tests were done with a Hach Paddle Tester, Total Aerobic Bacteria/Disinfection Control Test Kit sold by the Hach Company of Loveland, CO.
[0023] Table 1 primarily shows that the test of the dry soiled textile is generally inaccurate and thus may be misleading. As will be appreciated, even when the test of the dry textile is performed with a pre-moistened swab, the testing of the textile directly, especially when dry, is essentially a surface test which will not indicate the level of ATP or various contaminants further entrapped within the fibers of the cloth. The “test vessel” test shows that even a small degree of agitation of the dirty textile in a water solution allows various contaminants to be released or extracted therefrom to a notably greater degree than possible from the swabbing of the dry soiled textile. The soiled washer drain solution shows a far greater amount of ATP which is in keeping with the ability of the high-agitation washer to strip all sorts of contaminants from the fabric via mechanical action, solubility in water and/or the entrainment of the contaminants in the water solution.
[0024] The results from the Hach test kit provide a similar comparison. In addition, the test results from the Hach test kit indicate that the dry soiled textile may actually be within an acceptable range of sanitation which would be expected only subsequent to the textile being washed. The results from Table 1 thus emphasize the need for a test which better establishes a more accurate reading of the ATP level in the textiles.
[0000]
TABLE 2
ATP Test Results of Various Textile Types
Max.
Sour
Wet
Capacity
Drain
Textile
(lbs. clean
Textile
No. of
Test
Test
Washer
dry cotton)
Type
Steps
(RLU)
(RLU)
#1
450
white
21
39624
0
industrial
#2
450
65/35
17
9510
—
shirts
#3
600
colored
15
40000
0
cotton
#4
600
65/35
13
18034
0
pants
Table 2 Notes:
1. The term “65/35” stands for 65% polyester and 35% cotton; typically, the white industrial textile type is of a 65/35 blend.
2. The number of steps typically includes a combination of washing, draining, rinsing and spinning in various orders depending on the textile type.
3. Tests performed via Pocketswab ® Plus method with readings provided by a NovaLum ® luminometer.
4. In the sour drain test, the swab was wetted with the soiled water solution drained from the washer after the final step indicated in the number of steps column.
5. In the wet textile test, the swab was rubbed on the wet textile which was still wet with the water solution of the wash after the final step of washing.
[0025] As Table 2 shows with reference to the Pocketswab® Plus test, even when the sour drain test gave an ATP reading of 40,000 RLU, the test of the wet textile gave an ATP reading of 0 RLU. This further emphasizes the difficulty of obtaining an accurate result concerning the level of contaminants via the direct swabbing of a textile.
[0026] If the textiles are sufficiently clean at the end of the washing or other cleaning process, there is no need, absent any re-contamination of textiles, for additional sanitizing steps thereafter. This is the most preferred condition of the textiles subsequent to washing or other cleaning in order to eliminate these additional sanitizing steps which may be relatively costly. Thus, it is preferred to maintain the textiles in a sanitary condition during the process of drying and all of the finishing steps and delivery to the customer or user of the textiles without additional sanitization.
[0027] Applicant's method of ATP testing thus provides a more accurate indicator of the level of ATP and associated bacteria of laundered textiles than do tests based on the direct swabbing of the textile. In addition, the textiles are tested for ATP at an earlier stage of the laundering process which can avoid the unnecessary repetition of various steps of the laundering process. Moreover, the present method may eliminate the need for sanitizing procedures subsequent to the washing or other cleaning process while maintaining a level of sanitation equal to or better than that of the prior art methods.
[0028] In the foregoing description, certain terms have been used for brevity, clearness, and understanding. No unnecessary limitations are to be implied therefrom beyond the requirement of the prior art because such terms are used for descriptive purposes and are intended to be broadly construed.
[0029] Moreover, the description and illustration of the invention is an example and the invention is not limited to the exact details shown or described. | A method of testing for sanitization of textiles comprises the steps of cleaning textiles in a water solution and testing the water solution for the presence of contaminants such as adenosine triphosphate (ATP), typically with a luminometer. Typically, the water solution will be drained from a cleaning vessel and tested. Another option is the testing of the water solution extracted after draining such as by a spin cycle. The method provides improved accuracy of test results as to the level of cleanliness. In addition, testing at this early step of the laundering process allows for additional cleaning if needed without having undertaken costly and time-consuming steps such as drying. Moreover, absent re-contamination of the textiles after the cleaning process, drying and finishing procedures may be accomplished without further sanitizing the textiles. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to connectors for tubing and, more particularly, to connectors for (a) attaching corrugated tubing to other structures without special modification of the tubing and (b) securing a covering of braided wire in position about the tubing.
2. Description of the Prior Art
Although various types of connectors for tubing are known, these known connectors have suffered from several drawbacks. One of the most important drawbacks relates to a need to modify the ends of tubing in order to connect the tubing to other structures. For example, in the case of well-known riser tubes used in residential plumbing systems, one end of a corrugated tube must be formed without corrugations. The uncorrugated, straight-walled end section is adapted to receive a nut and an annular ferrule. The end section with ferrule attached then can be inserted within the inner diameter of an existing fitting and the nut can be tightened about the tube so as to compress the ferrule within the fitting. Upon continued tightening of the nut, the ferrule or the tube, or both, will be deformed and a fluid-tight seal will be created. In many circumstances, however, a consumer installing such a tube may improperly tighten the nut if care is not taken, and the connector often will leak.
The other end of a typical riser tube includes an upset portion having an annular flange for attachment to existing plumbing fixtures. Although connection of such an upset end portion to a fitting is relatively easy, such a connection by definition requires that the tube be manufactured with an upset end portion. Consequently, the cost of producing the tube is higher than desired.
The requirement that both ends of a riser tube be specially configured necessarily limits the lengths of tubes which can be used by consumers. That is, because very few individuals doing plumbing work possess the equipment needed to modify the ends of a corrugated tube to permit it to be used with existing connectors, corrugated tubing having appropriately configured ends must be manufactured in discreet lengths so that consumers can select a length of tubing appropriate for the job at hand. Obviously, the expense of manufacturing and maintaining an inventory of otherwise identical tubing, differing only in length, presents a considerable difficulty to manufacturers and distributors. It also presents a difficulty to the consumer who must carefully choose the proper length of tubing when making a purchase.
Yet an additional problem with corrugated tubing relates to the performance of the tubing itself as regards vibration and internal pressures. In certain applications, corrugated tubing is provided with a covering of braided wire rigidly secured to connectors attached to the tubing at each end. Assuming that the braided wire is of proper length and is rigidly secured to the connectors, the wire will prevent tube elongation under high internal pressure. The wire also will dampen vibration in the tube and can provide some protection for the tube from such undesirable influences as abrasion and impact.
A problem with prior corrugated tubing employing braided wire has been the attachment between the wire and the connectors carried by the ends of the tubing. In the past, it has been necessary to weld the wire braid to the connectors. Welding is undesirable because it is timeconsuming, is difficult to carry out on a production basis, and it may adversely affect the strength characteristics of the tubing or the connectors. In addition, welding the wire to the connectors reduces the available materials from which the connectors, the tubing, or the wire can be chosen. Desirably, a connector for tubing would include provisions for securing a covering of braided wire or other material to the connector and/or the end of the tubing without the need for welding.
In view of the foregoing difficulties, it is an object of the present invention to provide a connector for corrugated tubing in which no special modification of the ends of the tubing are required to effect a fluid-tight seal.
It is yet another object of the invention to provide a connector for corrugated tubing whereby the tubing can be cut to length by the user of the tubing and the connector can be fitted to the end of the tubing at the job site.
It is yet another object of the invention to provide a connector for corrugated tubing by which a covering of braided wire or other material can be quickly secured in place about the tubing without the need to weld the covering to either the connector or the tubing.
SUMMARY OF THE INVENTION
In response to the foregoing concerns and in carrying out the objects of the invention, the present invention provides a new and improved connector for corrugated tubing in which modification of the ends of the tubing is not necessary to establish a fluid-tight connection and in which a covering of braided wire or other material can be properly secured in place about the tubing without the need for welding. The invention is particularly adaptable to annularly corrugated tubing and will be described in such an environment.
In order to use the connector according to the invention, a corrugated tubing is severed is one of the corrugation "valleys" by means of a hacksaw or other cutting device. The connector includes a retainer nut which is fitted over the end of the tubing, as well as a ferrule in the form of specially configured, semi-annular half-sections which are fitted about the end of the tubing. The half-sections engage the corrugations at the end of the tubing so that relative axial movement between the tubing and the half-sections is not possible. In one embodiment of the invention, an elastomeric sealing member, such as an O-ring, is fitted within the retainer nut and is pressed in place against the endmost corrugation of the tubing and the end of the assembled half-sections. Thereafter, the retainer nut can be connected to a pipe or other existing fitting. Continued tightening of the nut will cause the pipe or fitting to engage the sealing member and/or the endmost corrugation of the tubing. Yet additional tightening of the retainer nut will cause sufficient displacement of the sealing member or the corrugation, or both, to effect a fluid-tight seal. The ferrule prevents axial displacement of the retainer nut relative to the tubing and thereby permits the sealing member and/or the endmost corrugation of the tubing to be deformed. Ferrules of various configurations may be provided to accommodate various existing fittings or to take into account different tubing wall thicknesses, material compositions, or corrugation forms.
An alterative embodiment of the invention is provided for those instances where a covering of braided wire or other material is to be fitted about the tubing. The invention is particularly useful with a covering of wire and will be described hereafter in such an environment. A preferred version of the braided wire embodiment employs a retainer nut adapted to loosely surround the end of the tubing. The end of the wire covering is fitted intermediate the inner diameter of the retainer nut and the outer diameter of the tubing. A cylindrical bushing also is fitted between the inner diameter of the covering and the outer diameter of the tubing. A ferrule in the form of alternating washer-like half-sections is fitted about one or more of the endmost corrugations of the tubing. A compression nut is threaded within the inner diameter of the retainer nut and is engageable with the endmost washer. Upon continued tightening of the compression nut, the washers and spacers are brought into contact with each other and the endmost corrugations of the tubing are compressed axially. The compression nut presses into the flask of the endmost corrugation and forms a seal by deforming and displacing the wall of the tube end. Also, the wire covering is tightly radially compressed. Accordingly, the retainer nut and the bushing tightly hold the covering, and the retainer nut and the compression nut effectively are clamped to the end of the tubing. Different versions of the braided wire embodiment include a unitary ferrule and different retaining nut configurations for clamping the wire covering.
The net result of using the present invention is that corrugated tubing can be supplied to consumers, either industrial or domestic, in discreet or continuous lengths which can be easily sized to fit individual job requirements. It no longer is necessary for tubing manufacturers to provide discreet lengths of tubing having specially configured end portions. Moreover, the attachment of a braided wire covering can be carried out with the utmost simplicity, without welding, and without regard for the materials of which the covering and the tubing are comprised. With either embodiment of the invention, a substantial savings in tubing manufacturing expense and on-site assembly time is made possible. These advantages and a fuller understanding of the invention may be had by referring to the following description and claims, taken in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an elevational view, partly in section, of a corrugated tubing to which connectors according to the invention have been applied;
FIG. 2 is a perspective view of one end of the connector and tubing of FIG. 1, with portions of the connector being broken away and removed for clarity;
FIG. 3 is an enlarged elevational view of the end of the tubing of FIG. 1, with a portion of the connector broken away and removed for clarity, and showing a sealing member in a compressed, fluid-tight configuration;
FIG. 4 is an enlarged elevational view of the end of the tubing of FIG. 1, illustrating a different form of ferrule which may be used with the connector;
FIG. 5 is a view similar to FIG. 4 in which a sealing member is used, but a ferrule is not used;
FIG. 6 is a view similar to FIG. 5 showing the components of FIG. 5 in a compressed, fluid-tight configuration;
FIG. 7 is a view similar to FIG. 4 showing a ferrule which also acts as a sealing member;
FIG. 8 is a view similar to FIG. 7 showing the components of FIG. 7 in a compressed, fluid-tight configuration;
FIG. 9 is a view similar to FIG. 1, in which the tube is covered by braided wire and specially configured nuts and ferrules are used to seal the end of the tube and clamp the braided wire;
FIG. 10 is a view similar to FIG. 9, showing the components of FIG. 9 in a compressed, fluid-tight configuration;
FIG. 11 is an exploded, perspective view of the embodiment of FIGS. 9 and 10, with certain portions being broken away and removed for clarity;
FIG. 12 is an embodiment of the invention similar to that shown in FIGS. 9-11, in which a modified form of ferrule is used;
FIG. 13 is a view similar to FIG. 12 in which yet another form of ferrule is used;
FIG. 14 is a view of the embodiment of FIG. 13 showing the components in a compressed, fluid-tight configuration;
FIG. 15 is a view similar to FIG. 9 of an especially preferred embodiment of the invention adapted to secure a covering of braided wire in place about a corrugated tube;
FIG. 16 is a view of the embodiment of FIG. 15 showing the components in a compressed, fluid-tight configuration; and
FIG. 17 is an end view of the embodiment of the invention shown in FIGS. 15 and 16.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1, a tube 10 is shown connected at one end to a pipe 12 having a threaded end portion 14. The end portion 14 includes a generally flattened end surface 16. The tube 10 includes annular corrugations defined by alternating crests 20 and troughs, or valleys 22. In those instances where the tube is severed at a location intermediate adjacent crests 20, a facing, inclined flank 26 will be formed. The tubing 10 can be formed from a variety of materials, but most likely will be formed from copper, brass, or a plastics material.
A connector 30 according to the invention includes a retainer nut 32 adapted to be fitted about the end of the tube 10. The nut 32 shown in FIG. 1 is connected to the threaded end portion 14 of the pipe 12 in conventional fashion. The nut 32 includes a bore 36 having a relatively small inner diameter. The bore 36 is slightly larger than the outer diameter of the crests 20. The nut 32 also is counterbored as at 37 and the counterbored portion 37 includes a threaded portion 38. The threaded portion 38 is engageable with the threaded end portion 14. A shoulder 40 connects the bore 36 and the counterbored portion 37. The nut 32 also has a number of flats 42 on its outer surface to facilitate gripping by a wrench.
The connector 30 also includes a ferrule 50 in the form of half-sections 50a, 50b adapted to be placed about the endmost corrugations of the tube 10. Each of the half-sections 50a, 50b includes a body portion 54 adapted to mate with at least one corrugation of the tube 10, an end face 56, an elongate, relatively thin-walled extension 58, and an inwardly turned end portion 60. The outer diameter of the body portion 54 and the extension 58 are different, and a shoulder 62 is formed at approximately the mid-point of the ferrule 50. The connector 30 also includes a sealing member in the form of an O-ring 64. The O-ring 64 is comprised of an elastomeric substance so that it can be readily deformed in order to carry out a sealing function.
The connector 30 is assembled by first cutting a length of tubing 10 adequate for the job at hand. The tube 10 can be cut by any conventional technique such as through the use of a hacksaw, pipe cutter, and the like. The tube is severed in the root section of one of the valleys 22 so that a flank 26 is formed. Thereafter, the half-sections 50a, 50b defining the ferrule 50 are fitted together about the end of the tube 10 so that the body portion 54 is fitted between opposed crests 20. The nut 32 then is slipped over the tube 10 until the bore 36 engages the outer surface of the extension 58 and the shoulders 40, 62 are in contact with each other. The O-ring 64 then is placed inside the nut 32 and the threaded portion 38 is secured to the end portion 14. Upon sufficient tightening of the nut 32, the components of the connector 30 eventually will attain that configuration shown in FIG. 3. The O-ring 64 will be distorted radially outwardly and inwardly into fluid-tight engagement with the end surface 16, the flank 26, the end face 56, and the counterbored portion 37. The assembly will be held together tightly by the interaction of the shoulders 40, 62 and by engagement between the body portion 54 and one of the crests 20.
The embodiment of the invention shown in FIG. 4 is substantially similar to that shown in FIGS. 1-3, except that the sealing member 64 is replaced by an elastomeric ferrule 50' having an extra end section 66 extending forwardly of the flask 26 of the tube 10. The end section 66 engages the end surface 16 and, like the O-ring 64, is deformed upon tightening of the nut 32 so as to create a fluid-tight seal.
Referring to FIGS. 5 and 6, an alternative embodiment of the invention is shown. In this and subsequent embodiments of the invention, reference numerals from the earlier-described embodiments will be used where appropriate. In the embodiment of the invention shown in FIGS. 5 and 6, the tube 10 again is joined to the threaded end portion 14 by means of the nut 32. The ferrule 50 is not used, and the sealing member 64 performs both a sealing function and a mechanical connection function formerly performed by the ferrule 50. In this embodiment of the invention, the O-ring 64 is tightly stretched into place intermediate the last two crests 20. Upon tightening the nut 32, the O-ring 64 will be contacted by the shoulder 40 and distorted to that configuration shown in FIG. 6. If the O-ring has been properly sized, deformation adequate to provide a fluid-tight seal as well as reasonable mechanical strength will occur. The embodiment of FIGS. 5 and 6 is not as preferred as other embodiments of the invention, because the mechanical connection between the tube 10 and the pipe 12 is not as strong. Nevertheless, for certain applications, and certainly in emergency situations, an adequate connection can be made using this embodiment of the invention.
Yet another embodiment of the invention is illustrated in FIGS. 7 and 8. In this embodiment of the invention, a separate sealing member is not used, and a modified ferrule 70 provides both a sealing function and a mechanical connection function formerly performed by the ferrule 50. The ferrule 70, in undistorted configuration (FIG. 7), includes a cylindrical body portion 72 having a corrugated portion 74 and an enlarged-diameter, cylindrical end portion 76. The ferrule 70 is of unitary, metallic construction and is sized to be able to be tightly fitted about the crests 20 of the tube 10. The ferrule 70 is made of a material softer than the other components of the assembly so that it will be the first to be deformed. Upon tightening the nut 32 and after abutting the flank 26 with the end surface 16, the end surface 16 will contact the end portion 76. Continued displacement of the nut 32 and the pipe 12 relative to each other will result in the corrugated portion 74 becoming buckled. Referring now to FIG. 8, the buckled corrugated portion 74 will be tightly compressed between the shoulder 40 and the endmost crest 20. The end portion 76 will be tightly engaged by the end surface 16. Accordingly, the ferrule 70 will provide both mechanical and fluid-sealing capabilities.
Referring to FIGS. 9-11, an embodiment of the invention especially adapted for attaching a covering of braided wire about the tube 10 is shown. A connector 80 not only engages the end of the tube 10, but also securely clamps a braided wire covering 82 fixedly with respect to the tube 10 without the need for welding. The connector 80 includes a ferrule 84 in the form of half-sections 84a, 84b each having a body portion 86, corrugations 88 for engagement with the corrugations on the tube 10, a threaded outer diameter 90, an extension 92, a beveled slot 94 at that part of the body portion 86 adjacent the extension 92, and an inwardly turned end portion 96. A retainer nut 98 is fitted about the end of the tube 10 and includes, on its inner surface, a plurality of serrations 100. The nut 98 also includes a beveled rim 102 engageable with the beveled slot 94 of the ferrule 84. The nut 98 also includes a threaded portion 104 for engagement with the threaded outer surface 90 of the ferrule 84.
A compression nut 106 also is engageable with the ferrule 84 and the end of the tube 10. The compression nut 106 includes a cylindrical center section 108 having a projecting, relatively sharp end portion 110. The nut 106 also includes a wall 112 within which an annular groove 114 has been formed. A sealing member in the form of an O-ring 115 is contained in the groove 114. An annular slot 116 is disposed radially outwardly of the wall 112 and includes a threaded surface 118 for engagement with the threaded outer surface 90 of the ferrule 84. The nut 106 also includes a threaded inner surface 120 for connection to a pipe or other conventional fitting.
Assembly of the embodiment of FIGS. 9-11 is carried out as follows:
1. The tube 10 is cut to a desired length and the two-part ferrule 84a, 84b is fitted about the endmost corrugations of the tube 10.
2. The covering 82 is pushed over the tube 10, over the corrugated portion 88 of the ferrule 84, and into the slot 94 as far as it will go.
3. The retainer nut 98 is pushed over the covering 82 and is threaded tightly into engagement with the ferrule 84. The interacting wedging action of the slot 94 and the rim 102 causes the covering 82 to be tightly compressed against the outer surface of the extension 92 of the ferrule 84. The serrations 100 securely grip the outer surface of the covering 82.
4. The O-ring 115 is placed in the groove 114 and the compression nut 106 is threaded onto the ferrule 84. Continued tightening of the nut 106 results in contact between the projection 110 and the O-ring 115 with the flank 26. The endmost portion of the tube 10 and the O-ring 115 are deformed to that configuration shown in FIG. 10, whereupon a fluid-tight seal is created.
The embodiment of the invention illustrated in FIG. 12 is similar to that shown in FIGS. 9-11. The components of the invention shown in FIG. 12 are in a deformed, fully assembled configuration. A ferrule 122 includes a body portion 124 having a plurality of inwardly directed corrugations 126 engageable with the corrugations included as part of the tube 10. The outer surface 128 of the ferrule 122 is threaded. The ferrule 122 also includes an inclined end surface 130. The other end of the ferrule 122 includes a horizontally disposed portion 132, a vertically disposed portion 134, and a connecting portion 136 inclined at an angle to the horizontal.
A retaining nut 138 is threaded about the outer portion of the tube 10 and the ferrule 122. The nut 138 includes an inner diameter 140 larger than the diameter of the portion 132, and sufficient to contain the covering 82 therebetween. The nut 138 also includes a portion 142 inclined from the horizontal the same angle as the portion 136. The nut 138 also includes a threaded inner surface 144 engageable with the threads 128 and a shoulder 145 connecting the portion 142 and the surface 144. A compression nut 146 includes a body portion 148 having a forwardly projecting, rounded inner end surface 150. The nut 146 also includes an inclined surface 152 engageable with the inclined surface 130, as well as a threaded surface 154 engageable with the threaded surface 128.
Assembly and operation of the embodiment of FIG. 12 is similar to that of the already-described embodiment of FIGS. 9-11. The corrugations 126 firmly retain the ferrule 122 relative to the tube 10, and the covering 82 is firmly clamped in place relative to the tube 10 and the connector by being compressed between the confronting surfaces 132, 140 and 136, 142. The end portion 150 deforms the flank 26, and the surfaces 130, 152 tightly engage each other so as to provide a fluid-tight seal.
The embodiment of the invention illustrated in FIGS. 13 and 14 is similar to that shown in FIG. 12, and only the important differences will be described. A ferrule 160 is largely similar to the ferrule 122, except that a tapered slot 162 has been formed in the body portion 124, and the surface 136 has been eliminated. A beveled, elastomeric ring 164 is insertable in the slot 162. The nut 138 has been modified by extending the depth of the threaded surface 144 and the inclined portion 142 has been eliminated. As can be seen in FIG. 13, during initial assembly of this embodiment of the invention, the covering 82 is inserted into the slot 62 as far as it will go and the ring 164 is also placed in the slot 162 on the outer surface of the covering 82. Upon tightening of the components (FIG. 14), the ring 164 is deformed until it fills substantially all of the space in the slot 162 not occupied by the covering 82. The covering 82 thus is tightly wedged within the slot 162 and is securely retained relative to the tube 10.
An especially preferred embodiment of the invention is illustrated in FIGS. 15-17. This embodiment of the invention has sufficient strength characteristics that it can be used with corrugated tubing made of steel and proper tube deformation can be brought about to provide a fluid-tight seal. Although it is anticipated that the composition of the tube will be steel, the numeral 10 still is used to identify the tube insofar as its external dimensions remain unchanged. The connector of this embodiment includes a ferrule 170 comprised of alternating, washer-like half-section rings 172 and unitary spacers 174. Although four rings 172 and three spacers 174 are illustrated, the exact number of rings 172 and spacers 174 used with the invention can be varied. A retainer nut 176 includes an inner diameter 178 larger than the outer diameter of the tube 10 and sufficiently so that the covering 82 can be inserted intermediate the diameter 178 and the tube 10. A cylindrical bushing 180 having a flared end 181 also can be inserted intermediate the covering 82 and the outer diameter of the tube 10. The nut 176 further includes a cylindrical, straight-walled section 182 engageable with the outer diameter of the rings 172 and the spacers 174. A threaded inner surface 184 is a continuation of the straight-walled section 182. A shoulder 185 connects the inner diameter 178 and the straight-walled section 182.
A compression nut 186 also is provided. The compression nut 186 includes a body portion 188 from which an end portion 190 projects. The portion 190 is rounded at its end and preferably is heat treated to provide it with the requisite hardness to deform the steel tube 10. The nut 186 is threaded on its outer surface as indicated at 192 for engagement with the threaded portion 184 of the nut 176. The nut 186 also is threaded on its inner surface as indicated at 194 for engagement with a pipe or conventional fitting. The nut 186 includes a surface 196 positioned at right angles with respect to the end portion 190. A cylindrical stop ring 198 is positioned about the end portion 190 in engagement with the surface 196. The outer diameter of the ring 198 is less than the inner diameter of the threaded portion 184 so that interference between the ring 198 and the threaded portion 184 will not exist. The nut 186 additionally includes a pair of longitudinally extending openings 200 formed near its periphery at diametrically opposed locations. The openings 200 are adapted to receive a spanner wrench for imparting considerable torque to the nut 186.
Assembly of the embodiment of FIGS. 15-17 is carried out as follows:
1. The cover 82 is pushed over the tube 10.
2. The nut 176 is slipped over the cover 82.
3. The bushing 180 is placed over the tube 10 and underneath the cover 82.
4. Alternating half-section rings 172 and spacers 174 are fitted about the endmost corrugations of the tube 10.
5. The cover 82 is positioned such that it flares radially outwardly and is compressed between the shoulder 185 and the flared end 181 of the bushing 180.
6. The ring 198 is seated in position at the end of the nut 186 and the nut 186 is tightened within the nut 176. Contact between the rounded end portion 190 and the flank 26 eventually results. Afterwards, the end of the ring 198 contacts the forwardmost ring 172.
If enought torque is applied to the nut 186, the components eventually will attain that position shown in FIG. 16 where the rings 172 and the spacers 174 are tightly compressed against each other and the endmost corrugations of the tube 10 are compacted. A fluid-tight seal is created by engagement between the flank 26 and the end portion 190, and the covering 82 is firmly clamped in position by the inner diameter 178, the shoulder 185, and the flared end 181.
It will be appreciated from the foregoing description that a connector according to the invention can be used to connect corrugated tubing to pipes, fittings, or other tubing without any modification whatsoever being required of the tubing except for cutting it to proper length. Each embodiment of the invention can be assembled quickly and without special skill or special tools. For those applications where a covering of braided wire or other material is necessary or desirable, the covering can be quickly and securely attached to the connector without need to resort to the prior art practice of welding.
Although the invention has been described in its preferred embodiment with a certain degree of particularity, it will be appreciated that various changes and modifications may be made without departing from the true spirit and scope of the invention. It will be understood that the patent shall cover, by suitable expression in the appended claims, whatever features of patentable novelty exist in the invention disclosed. | A connector for connecting corrugated tubing to pipes or fittings permits the corrugated tubing to be used without any modification to its ends. The corrugated tubing need only be cut to length by severing at a "valley" of one of the corrugations. A ferrule in the form of semi-annular half-sections is fitted about the endmost corrugations of the severed tubing. Inwardly extending projections of the ferrule engage at least one of the valleys to prevent relative axial movement between the ferrule and the tubing. A retainer nut previously placed over the tubing is slipped over the ferrule to retain the ferrule in place. An outwardly extending portion of the ferrule engages an inner portion of the nut to prevent axial movement of the nut over the ferrule. An O-ring or other sealing member may be inserted within the retainer nut and positioned against the endmost corrugation of the tubing. Thereafter, the retainer nut can be threaded about an existing pipe or fitting and tightened in place until deformation of the end corrugation and/or the sealing member occurs. A fluid-tight seal results. Various embodiments of the invention are disclosed, including several especially adapted for securing a covering of braided wire about the tubing without the need for welding the covering to the connectors. In the braided wire embodiments of the invention, the covering is inserted intermediate a specially configured retainer nut and the outer corrugations of the tubing. The retainer nut clamps the covering in position relative to the retainer nut and the tubing. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is related in subject matter to co-pending application Ser. No. 069,209, filed Aug. 23, 1979, entitled "Apparatus For Pumping Fluid From A Well Through A Tubing String", and co-pending application Ser. No. 073,395, filed Sept. 7, 1979, entitled "Rodless Pump Comprising Reference Pressure Means" with each being assigned to the same assignee as this application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to rodless pumps and in particular to a rodless pump comprising a gas spring.
2. Description of the Prior Art
Presently, low pressure, non-flowing oil wells account for over 90% of the oil wells in the United States. There are various means available for pumping these non-flowing oil wells. The most common of these pump means is the sucker rod type subsurface pump. Other types of pumps include electrical and hydraulic actuated subsurface pumps. One problem which is common to each of these subsurface pumps is that they require a separate energy transmission path for supplying the actuating energy to the pump.
Although sucker rod type pumps are not the most energy efficient, they are probably the most reliable. However, sucker rod failures are still a major problem, as studies have shown that a sucker rod fails an average of once every two years. These failures result in significant repair and maintenance costs.
There have been several attempts to provide a rodless subsurface pump system which does not require a separate energy transmission path for activating the pump. This type of pump system typically includes a surface unit which is connected to the subsurface pump by a single fluid conduit. The surface unit activates the subsurface pump by applying pressure to the fluid in the conduit to compress a spring means in the pump and displace a slidable piston to draw fluid from the well into a pump chamber. When the surface unit releases the fluid pressure, the spring means of the subsurface pump will displace the piston and lift the fluid in the pump chamber into the fluid conduit. Such systems are disclosed in U.S. Pat. Nos. 2,058,455; 2,123,139; 2,126,880 and 2,508,609.
However, these pressure activated subsurface pump systems have some inherent problems. When fluid pressure is applied to the fluid conduit, the actual energy applied to the system is much greater than the energy supplied to the subsurface pump. Since thousands of feet typically separate the surface unit and the subsurface pump, considerable work is done compressing the fluid in the conduit, ballooning the conduit, and moving fluid to compress the subsurface pump spring. In these systems, considerably more energy is consumed in compression and ballooning than is used to lift fluid. Thus, these systems are energy inefficient.
There are also several problems associated with these subsurface pumps. Typically, it has been desirous to provide a subsurface pump having a relatively long stroke length such that more fluid could be produced for a given amount of energy input. However, early subsurface pumps utilized strong helical compression springs as a means for lifting the fluid into the fluid conduit. These springs severely limited the maximum stroke length which could be attained.
Other subsurface pumps, such as the one disclosed in U.S. Pat. No. 4,013,385, utilize an inert gas pressurized chamber which functions as the spring means. When pressure is applied to the fluid conduit, a piston will compress the gas within the chamber and, when the fluid pressure is relieved, the gas will expand to lift fluid into the conduit. However, in this type of subsurface pump, it is difficult to maintain an effective seal between the gas chamber and the associated fluid.
SUMMARY OF THE INVENTION
The present invention relates to a fluid pressure actuated, rodless pump for pumping fluid through a conduit, such as a tubing string in a well. A piston chamber is connected to the lower end of the tubing. The chamber has a fluid inlet and a check valved outlet to the tubing. A piston is slidably movable in the chamber and defines a pump cavity with the chamber between a check valve in the piston and the check valved outlet.
The piston is connected to a cylinder by a pull rod. The cylinder includes an elastomeric bladder separating a gas filled chamber from an upper fluid chamber which is separated from a lower fluid chamber by a wall. A fluid passageway is formed in the wall and a charge valve connects the fluid chambers with the tubing. The lower fluid chamber encloses a stationary piston. The gas filled and the upper and lower fluid chambers function to eliminate any significant compressional forces on the pull rod thereby permitting an increased stroke and pumping capacity.
The upper end of the tubing is connected to a means for cyclically applying pressure to the fluid in the tubing. The pressurized fluid forces the cylinder and the movable piston downwardly to draw fluid into the pump chamber. At the same time, fluid is forced from the lower to the upper fluid chamber to compress the gas in the gas filled chamber. Alternating with the cyclic pressure, the gas expands to force fluid from the upper to the lower chamber to move the cylinder and the piston upwardly and release fluid from the pump cavity to the tubing.
During the cycles of applied pressure, the charge valve functions to replace any fluid lost from the lower fluid chamber past the stationary piston when tubing pressure is at its maximum, the charge valve equalizes the pressure in the upper and lower fluid chambers with the fluid pressure in the tubing. The pressurized fluid in the upper fluid chamber also militates against the leakage of gas through the elastomeric bladder.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a rodless pump system according to the present invention shown during a down stroke.
FIG. 2 is a schematic diagram of the rodless pump of FIG. 1 shown at the bottom of its stroke.
FIG. 3 is a schematic diagram of the rodless pump of FIG. 1 shown during an up stroke.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 1, 2 and 3, there is shown in schematic form a fluid pressure actuated subsurface pump 11 according to the present invention. The subsurface pump 11, as shown in FIG. 1, is connected to a surface unit 12 by a tubing string 13. The surface unit 12 functions to cyclically apply pressure to the fluid in the tubing string 13 to actuate the subsurface pump 11. In addition to actuating the subsurface pump 11, the surface unit 12 includes means for converting potential energy which is stored as compression forces in the tubing string into an energy form suitable for re-applying fluid pressure to actuate the pump on the next cycle. As will be discussed, FIGS. 1, 2 and 3 each show the relative positions of the elements at a particular point in the pumping cycle of the subsurface pump 11.
The subsurface pump 11 is mounted within the tubing string 13 which extends to the top of the well G of a previously drilled bore hole B. A casing or other conduit 14 in inserted into the bore hole B to prevent the walls of the bore hole B from collapsing. The casing 14 has ports 15 formed in the side walls thereof to permit fluid to flow from a well production zone W into the casing 14 such that a fluid annulus having a level L surrounds the tubing string 13.
The subsurface pump 11 includes a pump chamber assembly 16 having a lower end securely attached to a seating nipple 17 mounted in the lower end of the tubing string 13. The nipple 17 can be a standard type commonly used for rod pump installation. Thus, the subsurface pump 11 can replace the rod pump in a standard rod pump system without pulling the tubing string 13 to install special seating nipples.
The pump 11 includes a gas spring assembly 18 which is slidable with respect to the pump chamber assembly 16. The spring assembly 18 includes a piston 19 which is connected to the lower end of an upwardly extending pull rod 21 having an upper end securely attached to a wall 22. The wall 22 is formed intermediate the ends of a cylinder 23 having a closed upper end and an open lower end.
The upper portion of the cylinder 23 between the closed upper end and the wall 22 defines a gas spring chamber 24 which is separated from an upper fluid chamber 25 by means of an elastomeric bladder 26. The bladder 26 includes an annular sealing ring (not shown) formed on the lower end thereof which is suitably sealed to the inner side walls of the cylinder 23. A passageway 27 is formed in the wall 22 and provides a fluid path between the upper fluid chamber 25 and a lower fluid chamber 28.
The gas spring chamber 24 is typically charged with an inert gas such as nitrogen, for example. The spring force can be adjusted to an optimum for any given well by simply charging the chamber 24 to different pressures.
The gas spring chamber 24 is designed to minimize any leakage of gas from the chambers. The elastomeric bladder 26 is utilized to minimize the diffusion rate of the gas into the associated fluid. Also, because the gas in the chamber 24 is surrounded by a fluid at equal pressure, the lack of pressure differential across the bladder 26 militates against the escape of gas from the chamber. Furthermore, the gas chamber 24 is designed as an inverted cup-like structure so as to trap the gas even if the bladder 26 were to rupture.
A charge valve 29 provides selective fluid communication between the interior of the tubing string 13 and the fluid chambers 25 and 28. As will be discussed, the charge valve 29 functions to recharge the upper and lower fluid chambers 25 and 28 on each pumping cycle.
The pump chamber assembly 16 includes a spring piston 31 formed on the upper end thereof which is slidably mounted within the lower portion of the cylinder 23. The lower portion of the cylinder 23 between the wall 22 and the spring piston 31 defines the variable volume lower fluid chamber 28. A piston chamber 32 is located in the lower end of the pump chamber assembly 16 for slidably receiving the piston 19. An aperture 33 is formed in the upper end of the chamber 32 for slidably receiving the pull rod 21.
A traveling check valve 34 is positioned in the piston 19 and provides selective fluid communication between the portion of the piston chamber 32 below the piston 19 and a pump cavity 35. The pump cavity 35 is the volume defined by the upper portion of the piston chamber 32 and the top surface of the piston 19. A pair of standing check valves 36 and 37 are positioned at the top of the piston chamber 32 and provide selective fluid communication between the pump cavity 35 and the interior of the tubing string 13.
The reciprocating motion of the spring assembly 18 forces fluid in the lower end of the piston chamber 32 to be transported upward into the tubing string 13. On the downstroke of the spring assembly, the standing check valves 36 and 37 are closed and the traveling check valve 34 is opened such that the fluid below the piston 19 flows through the traveling check valve 34 into the pump cavity 35. On the upstroke of the spring assembly 18, the traveling check valve 34 is closed and the standing check valves 36 and 37 are opened such that fluid in the pump cavity 35 flows through the check valves 36 and 37 into the tubing string 13.
One important advantage of the subsurface pump 11 according to the present invention is that no significant compression forces are applied to the pull rod 21 during the operation of the pump. Therefore, the rod 21 can be longer than the rods in other subsurface pumps for an increased stroke and pumping capacity. During the down stroke, the fluid flows through the traveling valve 34 and the passageway 27 to offer little resistance to the piston 19 and the wall 22 respectively. During the up stroke, the gas in the spring chamber 24 exerts pressure on the fluid in the chamber 25 and 28 resulting in a net upward force on the wall 22 placing the rod 21 in tension.
It should be noted that the subsurface pump 11 is comparatively insensitive to gas locking as a result of the location of the standing valves. Since the standing valves are positioned at the top of the pump cavity 35, any gas which is introduced into the pump cavity will be released on the up stroke of the piston 19. Thus, the subsurface pump 11 can be used in wells having a relatively high gas-liquid ratio.
The surface unit 12 includes a surface pump 38 for cyclically applying pressure to the fluid in the tubing string 13 to actuate the subsurface pump 11. The surface pump 38 includes a surface piston assembly 39 having a piston 41 slidably mounted within a piston chamber 42. The piston 41 includes a tubular piston rod 43 extending through the upper wall of the piston chamber. A helical compression spring 44 is located within the piston rod 43. The spring 44 exerts an upward force on a cam follower support 45, which is slidably positioned in the piston rod and includes a cam follower 46 rotatably mounted thereon.
The spring 44 is a force limiting spring which permits the system to automatically compensate for changes in fluid compressibility and specific gravity. The fluid received from the well W is not a homogeneous mixture, and typically includes changing mixtures of water, gas and oil, each having a different specific gravity and compressibility. These changing mixtures require different pressures and displacements from the surface piston assembly 39 in order to supply a consistent amount of energy to the subsurface pump 11. The spring 44 provides a means for achieving variable displacement from the surface piston assembly 39 which is large enough for the maximum expected fluid compressibility, while protecting the system from excessive pressures.
A cam 47 and a flywheel 48 are attached together for rotation about a common axis. The cam 47 and the flywheel 48 are rotatably mounted on a support arm 49 such that the cam follower 46 engages the cam 47.
The cam 47 permits the displacement of the piston assembly 39 to be controlled as a function of time. The cam 47 can be designed to compensate for changes in flywheel rotation rates or, in a continuous rotation flywheel system, to provide different compression and expansion cycles. Also, in some instances it may be desirous to provide a dwell at the minimum system pressure to permit production delivery without displacement of the surface piston assembly.
An electric motor 51 is connected to a source of electric power (not shown) and includes drive means which engages the flywheel 48 for resupplying energy to the system. The motor 51 can be either an A.C. or D.C. type which runs continuously or is controlled so that only the required amount of energy is added to the system.
An outlet port 52 is formed in the side wall of the surface pump piston chamber 42. The location of the port 52 in the chamber 42 is such that fluid can flow from the chamber 42 into the port 52 only when the piston assembly 39 is in the top portion of its stroke and the fluid pressure is near the minimum. A back pressure valve 53 is connected between the outlet port 52 and a production line 54. The valve 53 maintains the fluid in the system at a selected minimum pressure. Typically, the minimum pressure is selected to be above the vapor pressure of the fluid in the tubing string 13 to minimize the formation of gas in the fluid. Free gas bubbles within the tubing string 13 can cause significant volume displacement changes and unrecoverable thermodynamic losses. Thus, if the fluid pressure is maintained above the fluid vapor pressure, gas formation can be avoided.
OPERATION
FIG. 1 illustrates the portion of the pumping cycle wherein pressure is exerted on the fluid in the tubing string 13 to actuate the subsurface pump 11. As shown in FIG. 1, the cam 47 of the surface unit 12 is rotated counterclockwise to urge the cam follower 46 and the support 45 downwardly to compress the spring 44. The spring 44 exerts a downward force on the piston assembly to downwardly displace the piston assembly 39 and compress the fluid within the surface pump piston chamber 42 and the tubing string 13.
The fluid pressure in the tubing string produces a resultant downward force on the spring assembly 18. When the resultant downward force of the fluid pressure exceeds the upward force generated on the assembly 18 by the gas in the gas chamber 24, the assembly 18 is displaced downwardly. This lowers the piston 19 within the chamber 32 to draw fluid through the traveling check valve 34 and into the pump cavity 35. On the downward stroke of the piston 19, the standing check valves 36 and 37 remain closed to prevent fluid in the tubing string 13 from entering the pump cavity 35.
As the assembly 18 is forced downwardly, the volume of the lower fluid chamber 28 decreases to cause fluid in the chamber 28 to flow through passageway 27 into the upper fluid chamber 25. The volume of the fluid chamber 25 is increased and the volume of the gas chamber 24 is decreased to compress the gas within the chamber 24.
When the cam 47 has rotated such that the high point of the cam 47 engages the cam follower 46, the surface piston assembly 39 is at its lowermost position and the fluid in the tubing string is at its maximum pressure. At this time, the spring assembly 18 is also at its lowermost position, as shown in FIG. 2, such that the pump cavity 35 is filled with fluid from the production zone at a maximum volume.
In order to compensate for any fluid leakage from the lower fluid chamber 28 into the tubing string 13, the charge valve 29 permits fluid in the tubing string to flow into the fluid chambers 24 and 28 such that the fluid pressure in the chambers 24 and 28 becomes equal to the fluid pressure in the tubing string, which is at a maximum at this point. Thus, the charge valve 29 provides a means of insuring that the gas in the chamber 24 is fully compressed on each pumping cycle. As will be discussed, the charge valve is a very important feature of the present invention since it eliminates the need of providing complicated sealing means between the spring piston 31 and the inner side walls of the cylinder 23.
When the high point of the cam 47 engages the cam follower 46, the rotational velocity of the flywheel 48 is at a minimum, while the compression forces of the pressurized fluid in the tubing string 13 are at a maximum. The compression forces create a "ballooning" effect of the tubing string 13 to store potential energy in the tubing string 13, which energy is at a maximum at this point.
As the cam 47 and the flywheel 48 continue to rotate, the fluid in the tubing string expands and the tubing string contracts. This generates an upward force on the surface piston assembly 39 which causes the cam follower to accelerate the cam 47 and the flywheel 48. Hence, the potential energy stored in the tubing string 13 is transformed into kinetic energy stored in the rotating flywheel 48. This kinetic energy can be utilized to pressurize the tubing string 13 on the next pumping cycle.
As shown in FIG. 3, when the fluid pressure in the tubing string 13 acting upon the cylinder 23 falls below a predetermined value, the pressurized gas in the chamber 24 expands and forces the fluid in the upper fluid chamber 25 through the passageway 27 into the lower fluid chamber 28. This results in an upward tension force on the pull rod 21 which displaces the piston 19 upwardly such that fluid in the pump cavity 35 flows through the standing valves 36 and 37 into the tubing string 13. The upward displacement of the piston 19 also draws fluid from within the well casing 14 into the piston chamber 32.
It should be noted that during the up stroke of the spring assembly 18, there can be fluid leakage from the lower fluid chamber 28 into the tubing string 13 between the outer annular surface of the spring piston 31 and the inner side walls of the cylinder 23. However, as previously mentioned, the charge valve 29 will insure that the fluid is replaced and the pressure in the upper and lower chambers 24 and 28 is brought up to the maximum fluid pressure on the next pumping cycle.
When the surface piston assembly 39 is displaced to its uppermost position, the fluid in the pump chamber 42 flows through the port 52 and the valve 53 into the production line 54. At this time, the tubing string 13 is in a state of minimum potential energy, while the flywheel 48 is in a state of maximum kinetic energy.
In summary, as the flywheel 48 and the cam 47 rotate, the surface piston assembly applies pressure to the fluid in the tubing string 13 to actuate the subsurface pump 11 and to store potential energy in the tubing string during a portion of each revolution, and converts potential energy released from the tubing string into kinetic energy stored in the flywheel during another portion of each revolution.
The invention concerns a fluid actuated pump which can be utilized in a pumping system having a means for cyclically applying pressure fluid to the pump. The pump includes a means responsive to the cyclic application of pressure fluid for drawing fluid from a source and means for actuating the means for drawing fluid to discharge the fluid to a conduit. The means for actuating can include a cylinder, means for dividing the interior of the cylinder into a gas filled chamber and a fluid filled chamber, means responsive to the cyclic application of the pressure fluid for moving the means for dividing to increase the volume of the fluid filled chamber and decrease the volume of the gas filled chamber thereby compressing the gas, and means for permitting the flow of the pressure fluid into the fluid filled chamber.
In the preferred embodiment, the cylinder receives and is movable with respect to a stationary piston. The means for dividing is an elastomeric bladder and the means for actuating includes a second fluid filled chamber defined in the cylinder between the piston and a wall. The second fluid filled chamber is in fluid communication with the first fluid filled chamber. The pressure fluid moves the cylinder to decrease the volume of the second fluid filled chamber which forces fluid into the first fluid filled chamber moving the bladder and compressing the gas. Alternating with the applications of pressure fluid, the gas expands forcing fluid from the first to the second fluid filled chamber moving the cylinder in the opposite direction. The cylinder actuates the means for drawing fluid from a source.
Although the subsurface pump apparatus has been found to have particular utility when utilized with a cyclical surface pumping unit which stores, converts and re-uses energy, it should be understood that the apparatus may also be utilized with other pressure-applying sources, such as high pressure pipe lines or wells with suitable valving, or conventional pumping means, and the like, in numerous end uses.
Although the invention has been described in terms of specified embodiments which are set forth in detail, it should be understood that this is by illustration only that the invention is not necessarily limited thereto, since alternative embodiments and operating techniques will become apparent to those skilled in the art in view of the disclosure. Accordingly, modifications are contemplated which can be made without departing from the spirit of the described invention. | A pressure actuated, rodless pump for pumping fluid preferably from a well through a tubing string comprises a chamber and a check valved movable piston which define a pump cavity, the chamber having a check valved outlet to the tubing string on the cavity side of the piston and a fluid inlet on the other side of the piston. The piston is connected to a spring assembly by a pull rod. The spring assembly includes a cylinder having an elastomeric bladder separating a gas filled chamber from an upper fluid chamber which is separated from a lower fluid chamber by a wall having a fluid passageway formed therein. The lower fluid chamber encloses a stationary piston and both the lower and upper fluid chambers are in fluid communication with the tubing string through a charge valve. Cyclic pressure applied to the fluid in the tubing string forces the cylinder and movable piston downwardly to draw fluid into the pump cavity and to force fluid from the lower fluid chamber into the upper fluid chamber to compress the gas. Alternating with the cyclic pressure, the compressed gas expands forcing fluid from the upper to the lower fluid cavity to move the cylinder and the movable piston upwardly and release fluid from the pump cavity to the tubing. The charged valve functions during the pressure cycles to replace fluid lost from the lower fluid chamber past the stationary piston. | 5 |
This application is a continuation of application Ser. No. 08/012,684, filed on Feb. 3, 1993, now abandoned.
BACKGROUND OF THE INVENTION
The invention relates to bleaching regulator (stabiliser) compositions for bleaching with H 2 O 2 , which contain gluconic acid, nitrilotriacetic acid and magnesium in ionic form, which furthermore may be accompanied by a content of citric acid. Such bleaching regulators are employed in aqueous solution which has been rendered alkaline.
Naturally occurring plant fibres, such as cotton, sisal, jute and the like, contain, in the crude form, waxes, fats and other plant constituents which cause a yellowish-brown colouring of the fibre. As a result, not all the desired dyeings are possible; moreover the dyeing results are unlevel. These fibres are therefore subjected to a treatment in which bleaching and washing are combined, in order to remove the undesirable non-fibrous constituents and to destroy the substances which cause the yellowish-brown colouring. Such a treatment can be applied on the fibres of the origin mentioned, on yarns produced therefrom and on woven fabric, knitted fabric or nonwovens of such fibres. This treatment furthermore can be applied on mixtures of such fibres with synthetic fibres and products produced therefrom.
So-called bleaching liquors which comprise water, hydrogen peroxide, wetting agents/detergents and emulsifiers, alkali to adjust the pH and H 2 O 2 regulators (stabilisers) are employed for carrying out the combined treatment mentioned. Sodium Silicate and inorganic phosphates, for example, have been employed as regulators for a long time. Because of excessive fertilisation of the waste waters, the inorganic phosphates were later replaced by (poly)phosphonates. However, these phosphonates are difficult or even impossible to degrade, and thus pollute the waste waters again in a different manner. The non-biodegradable ethylenediaminetetraacetic acid (EDTA), which moreover is not absorbed by sewage sludge, is also unacceptable in its use as an H 2 O 2 regulator. With EDTA, moreover, remobilisation of heavy metals is not completely excluded.
There was therefore a desire to provide completely phosphorus-free and EDTA-free bleaching regulators (stabilisers). However, development has shown to date that it does not seem possible to dispense with phosphates or phosphonates or EDTA in such regulators.
SUMMARY OF THE INVENTION
Bleaching regulator compositions have now been found which are employed in aqueous solution which has been rendered alkaline and comprise, in the anhydrous and alkali-free form,
a) 0.1 to 20 parts by weight of magnesium ions, calculated as MgO,
b) 3 to 200 parts by weight of gluconic acid, calculated as the free acid,
c) 3 to 25 parts by weight of nitrilotriacetic acid, calculated as the free acid, and
d) 0 to 40 parts by weight of citric acid, calculated as citric acid monohydrate.
DETAILED DESCRIPTION OF THE INVENTION
Preferably, constituent a) is present in an amount of 0.1 to 10 parts by weight, particularly preferably 0.1 to 8 parts by weight.
Preferably, furthermore, constituent b) is present in an amount of 10 to 150 parts by weight, particularly preferably 15 to 120 parts by weight.
Preferably, furthermore, constituent c) is present in an amount of 4 to 12 parts by weight, particularly preferably 4 to 8 parts by weight.
Preferably, furthermore, constituent d) is present in an a amount of 4 to 30 parts by weight, particularly preferably 5 to 25 parts by weight.
The bleaching regulator compositions according to the invention are employed in aqueous solution which has been rendered alkaline. Constituents a), b), c) and d) are present here together in an amount of 10 to 60% by weight, preferably 25 to 40% by weight, based on the total aqueous solution which has been rendered alkaline. To render the solution alkaline, an alkali metal hydroxide is added until a pH of 7.5 to 14 is reached.
Such a wide pH range up to a strongly alkaline adjustment is possible in principle because alkali must in any case be added to the bleaching liquor to which the bleaching regulator composition according to the invention are added. However, a lower pH has proved more favourable for increasing the storage stability of the bleaching regulator compositions according to the invention. Preferably, therefore, a pH of 7.5 o 12.5, particularly preferably 7.5 to 12, is established.
Sodium hydroxide is the preferred alkali metal hydroxide for reasons of cost, although KOH or LiOH are in principle also possible: it can be added either in solid form or in an aqueous solution of, for example, 10 to 60% strength by weight, which is easy to handle.
The invention furthermore relates to a process for bleaching naturally occurring plant fibres of their mixtures with synthetic fibres, of yarns, woven fabrics, knitted fabrics of nonwovens of such fibres of their mixtures, in bleaching liquors which comprise water, alkali, hydrogen peroxide, wetting agents, detergents an emulsifiers and bleaching regulators, which is characterised in that compositions of the type described above are employed as the bleaching regulators.
The process according to the invention can be carried out in a number of various embodiments, all of which are familiar to the expert as updated techniques: bleaching in a long liquor (discontinuous or continuous); cold pad-batch process (CPB); pad steam process; pad roll process and others.
Naturally occurring plant fibres, for example cotton, jute, linen or regenerated cellulose, and animal fibres, such as silk and wool, and mixtures thereof with synthetics, can be bleached according to the invention. Fibres which may be mentioned as preferred are plant fibres, particularly preferably cotton and mixtures thereof.
In addition to water, alkali metal hydroxide, wetting agents, detergents and emulsifying agents and hydrogen peroxide, a bleaching regulator composition according to the invention is employed in the bleaching liquors to be employed in the process according to the invention. Hydrogen peroxide is present here in an amount of 0.5-100 ml/l, depending on the process. The alkali metal hydroxide is added and topped up in an amount to maintain a pH of 7.5 to 14 in the bleaching liquor. Wetting agents, detergents and emulsifiers are those which are known to the expert in this field. They are individual substances or mixtures of the known anionic, cationic or nonionic surfactants; they are preferably anionic or nonionic surfactants, such as fatty acids and salts thereof, fatty acid alkyl esters, fatty alcohols, fatty alcohol polyglycol ethers, glycerols, alkylaromaticsulphonic acids and the like.
These surfactants are chosen and composed in a manner known to the expert such that the undesirable concomitant substances of the naturally occurring plant fibres, such as fats, waxes and other plant constituents (for examples residues of seed capsules and the like) are removed. The water employed can be demineralised water or industrial water which is provided in the customary manner and is of varying hardness, depending on its occurrence.
The bleaching regulator compositions are used as stabilisers for the hydrogen peroxide. The release of oxygen for bleaching the fibres is regulated with these. Gluconic acid, nitrilotriacetic acid and, if appropriate, citric acid serve to complex and sequester alkaline earth metals, in particular the troublesome Ca ions, and heavy metals.
In principle, the complexing action of the mixture of gluconic acid and nitrilotriacetic acid is adequate. However, in many cases it is advantageous and is therefore an advantageous variant of the bleaching regulator compositions according to the invention for citric acid additionally to be employed. Gluconic acid and nitrilotriacetic acid can be employed either as the free acid or as an alkali metal salt (preferably as the sodium salt). Citric acid, if it is used, can also be employed as an alkali metal salt or as the free acid. Preferably, the citric acid is employed as the industrially available citric acid monohydrate.
Magnesium ions and calcium ions, as an example of alkaline earth metal ions, and iron, as an example of heavy metal ions, which are to be complexed, are naturally occurring constituents of the industrial water usually available. Alkaline earth metal ions and heavy metal ions furthermore can be introduced as impurities of the naturally occurring plant fibres to be bleached. If demineralised water is employed, both the complexing calcium and the magnesium desired as a co-stabiliser are lacking, while the constituents brought in by impurities of the naturally occurring plant fibres are still to be taken into consideration. If demineralised water is used, the amount of gluconic acid, nitrilotriacetic acid and, if citric acid is employed, of citric acid can be in the lower part of the stated ranges of amounts, while the missing magnesium must be compensated by using an amount in the upper part of the stated range of amounts.
These relationships, taking into consideration the water available and the quality of the fibre to be bleached, are known to the expert. The bleaching regulator compositions according to the invention are capable of meeting the entire use range described.
The bleaching regulator compositions according to the invention are prepared by simply bringing the constituents together, for example in the following sequence for the following typical composition:
1. 200 parts by weight of demineralised H 2 O are initially introduced into the mixing vessel;
2. 80 parts by weight of citric acid monohydrate are dissolved;
3. 20 parts by weight of MgO are dissolved;
4. 280 parts by weight of gluconic acid/Na gluconate (60% strength) are dissolved;
5. 50 parts by weight of nitrilotriacetic acid trisodium salt are dissolved;
6. 106 parts by weight of NaOH (50% strength) are added (pH at 8.5-9) and
7. 264 parts by weight of demineralised water are added as the remainder to make up to 1000 parts by weight.
To achieve materials which can be dyed without problems, it is usually necessary for other treatment stages also to be carried out beforehand or subsequently, beyond the bleaching:
Singeing, burning off the projecting fibre ends, in order to achieve a smooth surface. This is usually the first working operation.
Boiling off, scouring, that is to say hot alkali treatment with the aim of pre-extraction of the fibre concomitant substances or swelling of the fibres and seed husks of the cotton. This is usually carried out before bleaching.
Causticisation, mercerisation, treatment with highly concentrated alkali more or less under tension of the material to achieve a pronounced swelling of the fibres and therefore lustre and to eliminate the unripe or dead portions of cotton, which cannot be dyed or can be only poorly dyed. This can be carried out before or after bleaching.
Acid extraction is carried out before bleaching if extremely large amounts of heavy metal are present (industrial water and/or fibre substrate). The complexing agents of the bleaching regulator would be overtaxed.
Other bleaching processes before or after the hydrogen peroxide bleach are furthermore used to achieve very high whitenesses.
For example
sodium hypochlorite bleaching
sodium chlorite bleaching
reductive bleaching
with and without addition of whiteners.
If water-glass (sodium silicate) is used as a stabiliser, insoluble Ca silicate deposits occur on the machines and material, especially in association with Ca salts, which does not apply when the regulators according to the invention which are described are used.
The phosphonates which were used previously or are still used today and are regarded as irreplaceable are not biodegradable and pollute the waste waters. EDTA, which is also not degradable, moreover also pollutes waters because of the risk of remobilisation of heavy metal ions.
EXAMPLE 1
A typical bleaching regulator composition is obtained by bringing together 28% by weight of an aqueous sodium gluconate solution (60% strength): 5% by weight of nitrolotriacetic acid trisodium salt. 8% by weight of citric acid monohydrate, 2% by weight of magnesium oxide and 6% by weight of 50% sodium hydroxide solution. The remainder (51% by weight) is demineralised water. The composition had a pH of 7.5.
EXAMPLE 2
Typical bleaching liquors comprise
______________________________________ Process CPB bleaching Long 2) Pad liquor 24 hours steam 1) room 3) 60 min. tempera- 10 min. 98° C. ture 100° C.______________________________________Water of 0-20° g/l 0.1 0.2-0.4 0.2-0.4German hardnesspossibly Mg saltBleaching regulator g/l 0.5 8 4(according to theinvention)Sodium hydroxide g/l 1 25 20solution(38% strength byweight)Hydrogen peroxide g/l 2 50 40(35% strength byweight)Surfactant g/l 0.5 4 4(wetting agent/detergent)______________________________________ 1) The raw material is bleached in a ratio to the liquor of 1:10 at the boiling point for 60 minutes, rinsed and dried. 2) CPB = cold padbatch process; the material is padded with the bleaching liquor (100% liquor pickup), left at room temperature for 24 hours, washe our and dried. 3) The desized material is padded with bleaching liquor (100% liquor pickup), left in saturated steam (100° C.) for 10 minutes, washed and dried.
After the treatment, the materials are checked for damage and the brightening is measured.
EXAMPLE 3
Another typical variant of a composition of a regulator according to the invention is:
______________________________________234.10 parts by weight of demineralised water125.00 parts by weight of citric acid monohydrate 31.20 parts by weight of magnesium oxide437.50 parts by weight of gluconic acid/Na gluconate (60%) 78.20 parts by weight of nitrilotriacetic acid Na.sub.3 salt 94.00 parts by weight of sodium hydroxide solution (50%)______________________________________
The composition has a pH of 7.5.
EXAMPLE 4
Bleaching regulator according to the invention without citric acid
______________________________________618.00 parts by weight of demineralised water 20.00 parts by weight of MgO280.00 parts by weight of gluconic acid/Na gluconate (60%) 50.00 parts by weight of nitrilotriacetic acid Na.sub.3 salt 32.00 parts by weight of NaOH, 50%______________________________________ Process 1 2 3______________________________________Damage:DP values before bleaching 2400 2400 2400DP values after bleaching 2300 2250 2000WhitenessReflectance 460 nm (%) 83.8 83.4 83.6after bleaching______________________________________
The same material was bleached under the above conditions using bleaching liquors which contained no regulator, and the following results were found, in comparison with the above values:
______________________________________ Process 1 2 3______________________________________DP values 1950 2000 1590after bleachingWhiteness 79.5 79.4 78.3Reflectance 460 nm (%)after bleaching______________________________________
EXAMPLE 5
The activity of the regulator according to the invention was demonstrated in boiling experiments under a reflux condenser using a typical bleaching liquor, the bleaching liquor being contaminated with iron salt (Fe +++ sulphate 1:1000):
Procedure
200 ml of a bleaching liquor having the following composition were boiled under a reflux condenser for 30 minutes, and the contents of hydrogen peroxide were determined after 15 and 30 minutes (experiment a with a regulator according to the invention; experiment b without a regulator).
______________________________________ ExperimentLewatit water a b______________________________________Sodium hydroxide solution g/l 5 5(32% strength by weight)Regulator (according to g/l 3.5 --the invention)Hydrogen peroxide g/l 10 10(35% strength by weight)Fe.sup.+++ sulphate solution g/l 20 20(1:1000)H.sub.2 O.sub.2 content (ml/l)at the start 10.1 10.2after 15 minutes 8.3 0.5after 30 minutes 5.6 0______________________________________
EXAMPLE 6
A further bleaching regulator composition is obtained from
80 parts by weight of citric acid monohydrate
20 parts by weight of MgO
280 parts by weight of Naglusol (gluconic acid/Na gluconate, 60% strength)
50 parts by weight of nitrilotriacetic acid Na 3 salt
106 parts by weight of sodium hydroxide solution (50% strength)
464 parts by weight of demineralised water.
The composition has a pH of 11.2. | Bleaching regulator compositions of good ecological tolerance which, in the anhydrous and alkali-free form, comprise magnesium ions, for example, in the form of magnesium oxide, gluconic acid and nitrilotriacetic acid, and furthermore can contain citric acid, are described. They contain no ethylenediaminetetraacetic acid (EDTA), no phosphates and no phosphonates. | 3 |
[0001] This application is a continuation-in-part of Ser. No. 10/187,381 filed Jul. 1, 2002, which is a continuation-in-part of Ser. No. 09/898,748 filed Jul. 3, 2001 and claims priority from GB Application No. 0115986.2 filed Jun. 29, 2001.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to polymerisation process for forming light emitting polymers and networks thereof. The light emitting polymer may be used as a source of electroluminescence for use in displays for electronic products.
[0004] 2. Prior Art
[0005] Modern consumer electronics require cheap, high-contrast displays with good power efficiency and low drive voltages. Particular applications include displays for mobile phones and hand-held computers.
[0006] Conventional displays comprise twisted nematic liquid crystal displays (TN-LCDs) with active matrix addressing and super-twisted nematic liquid crystal displays (STN-LCDs) with multiplex addressing. These however require intense back lighting which presents a heavy drain on power. The low intrinsic brightness of LCDs is believed to be due to high losses of light caused by the absorbing polarizers and filters which can result in external transmission efficiencies of as low as 4%.
[0007] Among the materials that may be used in displays are those that formed by thermally inducing the crosslinking of oligomers of p-phenylenevinylene. Films of these reactive mesogens are photoluminescent and not electroluminescent. Electroluminescent materials have the advantage of being useful as the active medium in electronically powered light sources for such applications as electronic displays, electric lights, lasers, etc. In addition, materials that display electroluminescence are often also useful as the active medium in light detectors, solar cells, electronic logic devices such as transistors. Accordingly, there is a strong need in the art for a material that may be used in display devices that has good power efficiency, uses a low drive voltage, does not require a polarizer, has high transmission efficiency and/or is electroluminescent.
SUMMARY OF THE INVENTION
[0008] The Applicants have now devised a new class of light emitting polymers. These can be employed in displays which offer the prospect of lower power consumption and/or higher brightness. The combination of these new light emitting polymers with existing LCD technology offers the possibility of low-cost, bright, portable displays with the benefits of simple manufacturing and enhanced power efficiency.
[0009] The light emitting polymer is obtainable by a polymerization process. The process involves the polymerization of reactive mesogens (e.g. in liquid crystal form) via photopolymerization of suitable end-groups of the mesogens.
[0010] According to one aspect of the present invention there is provided a process for forming a light emitting polymer comprising photopolymerization of a reactive mesogen having the formula:
B-S-A-S-B (general formula 1)
wherein
A is a chromophore; S is a spacer; and B is an endgroup which is susceptible to photopolymerization.
[0014] The polymerisation typically results in a light emitting polymer comprising arrangements of chromophores (e.g. uniaxially aligned) spaced by a crosslinked polymer backbone. A typical process is shown schematically in FIG. 1 from which it may be seen that the polymerisation of reactive monomer 10 results in the formation of crosslinked polymer network 20 comprising crosslink 22, polymer backbone 24 and spacer 26 elements.
[0015] Suitable chromophore (A) groups include fluorene, vinylenephenylene, anthracene, perylene and any derivatives thereof. Useful chromophores are described in A. Kraft, A. C. Grimsdale and A. B. Holmes, Angew. Chem. Int. Ed. Eng. [1998], 37, 402.
[0016] Suitable spacer (S) groups comprise organic chains, including e.g. flexible aliphatic, amine, ester or ether linkages. The chains may be saturated or unsaturated and be linear or branched. Aliphatic spacers are preferred. The presence of spacer groups aids the solubility and lowers the melting point of the light emitting polymer which assists the spin coating thereof.
[0017] Suitable endgroups are susceptible to photopolymerization (e.g. by a radical process using UV radiation, generally unpolarized). Preferably, the polymerization involves cyclopolymerization (i.e. the radical polymerization step results in formation of a cyclic entity).
[0018] A typical polymerization process involves exposure of a reactive mesogen of general formula 1 to UV radiation to form an initial radical having the general formula as shown below:
B-S-A-S-B• (general formula 2)
wherein A, S and B are as defined previously and B• is a radicalised endgroup which is capable of reacting with another B endgroup (particularly to form a cyclic entity). The B• radicalised endgroup suitably comprises a bound radical such that the polymerisation process may be sterically controlled.
[0019] Suitable endgroups include dienes such as 1,4, 1,5 and 1,6 dienes. The diene functionalities may be separated by aliphatic linkages, but other inert linkages including ether and amine linkages may also be employed.
[0020] Methacrylate endgroups have been found to be less suitable than dienes because the high reactivity of the radicals formed after the photoinitiation step can result in a correspondingly high photodegradation rate. By contrast, it has been found that the photodegradation rate of light emitting polymers formed from dienes is much lower. The use of methacrylate endgroups also does not result in cyclopolymerization.
[0021] Where the endgroups are dienes the reaction typically involves cyclopolymerization by a sequential intramolecular and intermolecular propagation: A ring structure is formed first by reaction of the free radical with the second double bond of the diene group. A double ring is obtained by the cyclopolymerization which provides a particularly rigid backbone. The reaction is in general, sterically controlled.
[0022] Suitable reactive mesogens have the general formula:
wherein R has the general formula: X—S2-Y-Z
and wherein
X=O, CH 2 or NH and preferably X=O; S2=linear or branched alkyl or alkenyl chain optionally including a heteroatom (e.g. O, S or NH) and preferably S2=a linear alkyl chain; Y=O, CO 2 or S and preferably Y=CO 2 ; and Z=a diene (end-group) and preferably Z=a 1,4, 1,5 or 1,6 diene.
[0027] Exemplary reactive mesogens have the general formula:
wherein R is:
[0028] An exemplary reactive mesogen has the formula:
Compound 3
[0029] All of Compounds 3 to 6 exhibit a nematic phase with a clearing point (N—I) between 79 and 120° C.
[0030] Other suitable exemplary reactive mesogens have the general formula:
wherein n is from 2 to 10, preferably from 3 to 8 and as above, R has the general formula: X—S2-Y-Z
and wherein
X=O, CH 2 or NH and preferably X=O; S2=linear or branched alkyl or alkenyl chain optionally including a heteroatom (e.g. O, S or NH) and preferably S2=a linear alkyl chain; Y=O, CO 2 or S and preferably Y=CO 2 ; and Z=a diene (end-group) and preferably Z=a 1,4, 1,5 or 1,6 diene.
[0035] Suitably, R is as for any of Compounds 3 to 6, as shown above.
[0036] A particular class of exemplary reactive mesogens has the formula:
wherein:
n is from 2 to 10, preferably from 3 to 8; and m is from 4 to 12, preferably from 5 to 11.
[0039] Still further suitable exemplary reactive mesogens have the general formula:
wherein A=H or F and wherein, as above, R has the general formula: X—2-Y-Z and wherein
X=O, CH 2 or NH and preferably X=O; S2=linear or branched alkyl or alkenyl chain optionally including a heteroatom (e.g. O, S or NH) and preferably S2=a linear alkyl chain; Y=O, CO 2 or S and preferably Y=CO 2 ; and Z=a diene (end-group) and preferably Z=a 1,4, 1,5 or 1,6 diene.
[0044] Suitably, R is as for any of Compounds 3 to 6, as shown above.
[0045] Particular exemplary reactive mesogens of this type have the formula:
[0046] A light emitting or charge transporting polymer may be formed from reactive mesogens having the formula:
B-S-A-S-B
wherein:
A is a chromophore of general formula: —(Ar-Fl) n —Ar—
wherein
Ar is an aromatic diradical or a heteroaromatic diradical bonded linearly or substantially linearly to adjoining diradicals, or a single bond; Fl is a 9,9-dialkyl substituted fluorine diradical joined to adjoining diradicals at the 2 and 7 positions; the Ar and Fl diradicals may be chosen independently in each of the n subunits of the chromophore; and 1≦n≦10, preferably 2≦n≦10, more preferably 2≦n≦7; S is a spacer; and B is an endgroup which is susceptible to polymerization.
[0053] The endgroup B may be selected to be susceptible to photopolymerization and the polymer may be formed by photopolymerization. The photopolymerization may be performed substantially photoinititor free. The endgroup (B) may be a diene such as 1,4 dienes, 1,5 dienes and 1,6 dienes. The diene functionalities may be separated by aliphatic linkages and/or separated by inert linkages. The inert linkage may be ether and amine linkages. The polymer may be a light emitting electroluminescent polymer, a hole transporting polymer, or an electron transporting polymer. This light emitting or charge transporting polymer may be used in a variety of devices including, but not limited to, electronic devices, light emitting devices, organic light emitting devices, lighting elements and lasers.
[0054] In aspects, the photopolymerization process can be conducted at room temperature, thereby minimizing any possible thermal degradation of the reaction mesogen or polymer entities. Photopolymerization is also preferable to thermal polymerization because it allows subsequent sub-pixellation of the formed polymer by lithographic means.
[0055] Further steps may be conducted subsequent to the polymerization process including doping e.g. with photoactive dyes.
[0056] In preferred aspects, the polymerization process results in cross-linking e.g. to form a polymer network (e.g. an insoluble, cross-linked network).
[0057] Suitably, the electroluminescent polymer is a liquid crystal which can be aligned to emit polarised light. A suitable class of polymers includes chromophores containing one or more fluorene units substituted into the linear chromophore group at the 2 and 7 positions. Another class of polymers contains chromophores in which one or more of the fluorene units is substituted at the 9 position by either one or two alkyl goups C n H 2n+1− wherein n=3 to 8. This is because alkyl groups of this type at the fluorene 9 position tend to stabilize the desired nematic liquid crystalline phase and also reduce intermolecular aggregation of the chromophore units that leads luminescence quenching.
[0058] The reactive mesogen (monomer) typically has a molecular weight of from 400 to 2,000. Lower molecular weight monomers are preferred because their viscosity is also lower leading to enhanced spin coating characteristics and shorter annealing times which aids processing. The light emitting polymer typically has a molecular weight of above 4,000, typically 4,000 to 15,000.
[0059] The light emitting polymer (network) typically comprises from 5 to 50, preferably from 10 to 30 monomeric units.
[0060] According to another aspect of the present invention there is provided a process for applying a light emitting polymer to a surface comprising applying a reactive mesogen (as defined above) to said surface; and photopolymerizing said reactive mesogen in situ to form the light emitting polymer.
[0061] The light emitter polymers herein can in one aspect be used in a light emitter for a display comprising a photoalignment layer; and aligned on said photoalignment layer, the light emitting polymer.
[0062] The polymerization process herein can in one aspect be configured to form the light emitter by in situ polymerization of the reactive mesogens after their deposition on the photoalignment layer by any suitable deposition process including a spin-coating process.
[0063] The photoalignment layer typically comprises a chromophore attached to a sidechain polymer backbone by a flexible spacer entity. Suitable chromophores include cinnamates or coumarins, including derivatives of 6 or 7-hydroxycoumarins. Suitable flexible spacers comprise unsaturated organic chains, including e.g. aliphatic, amine or ether linkages.
[0064] An exemplary photoalignment layer comprises the 7-hydroxycoumarin compound having the formula:
[0065] Other suitable materials for use in photoalignment layers are described in M. O'Neill and S. M. Kelly, J. Phys. D. Appl. Phys. [2000], 33, R67.
[0066] In aspects, the photoalignment layer is photocurable. This allows for flexibility in the angle in the azimuthal plane at which the light emitting polymer (e.g. as a liquid crystal) is alignable and thus flexibility in its polarization characteristics.
[0067] The photalignment layer may also be doped with a hole transport compound, that is to say a compound which enables transport of holes within the photoalignment layer, such as a triarylamine. Examples of suitable triarylamines include those described in C. H. Chen, J. Shi, C. W. Tang, Macromol Symp. [ 1997] 125, 1.
[0068] An exemplary hole transport compound is 4,4′,4″-tris[N-(1-napthyl)-N-phenyl-amino]triphenylamine which has the formula:
[0069] In aspects, the hole transport compound has a tetrahedral (pyramidal) shape which acts such as to controllably disrupt the alignment characteristics of the layer.
[0070] In one aspect, the photoalignment layer includes a copolymer incorporating both linear rod-like hole-transporting and photoactive side chains.
[0071] The light emitting polymer is aligned on the photoalignment layer. Suitably, the photoaligned polymer comprises uniaxially aligned chromophores. Typically polarization ratios of 30 to 40 are required, but with the use of a clean up polarizer ratios of 10 or more can be adequate for display uses.
[0072] In one aspect, the light emitter also comprises an organic light emitting diode (OLED) such as described in S. M. Kelly, Flat Panel Displays: Advanced Organic Materials, RSC Materials Monograph, ed. J. A. Connor, [2000]; C. H. Chen, J. Shi, C. W. Tang, Macromol Symp. [ 1997] 125, 1; R. H. Friend, R. W. Gymer, A. B. Holmes, J. H. Burroughes, R. N. Marks, C. Taliani, D. D. C. Bradley, D. A. Dos Santos, J. L. Bredas, M. Logdlund, W. R. Salaneck, Nature [ 1999] 397, 121; M. Grell, D. D. C. Bradley, Adv. Mater. [ 1999] 11, 895; N. C. Greenman, R. H. Friend Solid State Phys. [ 1995]49, 1.
[0073] OLEDs may be configured to provide polarized electroluminescence.
[0074] The light emitting polymer may be aligned by a range of methods including mechanical stretching, rubbing, and Langmuir-Blodgett deposition. Mechanical alignment methods can however lead to structural degradation. The use of rubbed polyimide is a suitable method for aligning the light emitting polymer especially in the liquid crystal state. However, standard polyimide alignment layers are insulators, giving rise to low charge injection for OLEDs.
[0075] The susceptibility to damage of the alignment layer during the alignment process can be reduced by the use of a non-contact photoalignment method. In such methods, illumination with polarized light introduces a surface anisotropy to the alignment layer and hence a preferred in-plane orientation to the overlying light emitting polymer (e.g. in liquid crystal form).
[0076] The aligned light emitting polymer is in one aspect in the form of an insoluble nematic polymer network. Cross-linking has been found to improve the photoluminescence properties.
[0077] M. O'Neill, S. M. Kelly J. Appl. Phys. D [ 2000] 33, R67 provides a review of photalignment materials and methods.
[0078] The light emitter herein may comprise additional layers such as carrier transport layers. The presence of an electron-transporting polymer layer (e.g. comprising an oxadiazole ring) has been found to increase electroluminescence.
[0079] An exemplary electron transporting polymer has the formula:
[0080] Pixellation of the light emitter may be achieved by selective photopatterning to produce red, green and blue pixels as desired. The pixels are typically rectangular in shape. The pixels typically have a size of from 1 to 50 μm, For microdisplays the pixel size is likely to be from 1 to 50 μm, preferably from 5 to 15 μm, such as from 8 to 10 μm. For other displays, larger pixel sizes e.g. 300 μm are more suitable.
[0081] In one preferred aspect, the pixels are arranged for polarized emission. Suitably, the pixels are of the same color but have their polarization direction in different orientations. To the naked eye this would look like one color, but when viewed through a polarizer some pixels would be bright and others less bright thereby giving an impression of 3D viewing when viewed with glasses having a different polarization for each eye.
[0082] The layers may also be doped with photoactive dyes. In aspects, the dye comprises a dichroic or pleachroic dye. Examples include anthraquinone dyes or tetralines, including those described in S. M. Kelly, Flat Panel Displays: Advanced Organic Materials, RSC Materials Monograph, ed. J. A. Connor, [2000]. Different dopant types can be used to obtain different pixel colors.
[0083] Pixel color can also be influenced by the choice of chromophore with different chromophores having more suitability as red, green or blue pixels, for example using suitably modified anthraquinone dyes.
[0084] Multicolor emitters are envisaged herein comprising arrangements or sequences of different pixel colors.
[0085] One suitable multicolor emitter comprises stripes of red, green and blue pixels having the same polarization state. This may be used as a sequential color backlight for a display which allows the sequential flashing of red, green and blue lights. Such backlights can be used in transmissive and reflective FLC displays where the FLC acts as a shutter for the flashing colored lights.
[0086] Another suitable multicolor emitter comprises a full color pixelated display in which the component pixels thereof have the same or different alignment.
[0087] Suitable multicolor emitters may be formed by a sequential ‘coat, selective cure, wash off’ process in which a first color emitter is applied to the aligned layer by a suitable coating process (e.g. spin coating). The coated first color emitter is then selectively cured only where pixels of that color are required. The residue (of uncured first color emitter) is then washed off. A second color emitter is then applied to the aligned layer, cured only where pixels of that color are required and the residue washed off. If desired, a third color may be applied by repeating the process for the third color.
[0088] The above process may be used to form a pixelated display such as for use in a color emissive display. This process is simpler than traditional printing (e.g. ink jet) methods of forming such displays.
[0089] There is also provided a backlight for a display comprising a power input; and a light emitter as described hereinbefore.
[0090] The backlight may be arranged for use with a liquid crystal display. In aspects, the backlight may be monochrome or multicolor.
[0091] There is further provided a display comprising a screen; and a light emitter or backlight as described hereinbefore.
[0092] The screen may have any suitable shape or configuration including flat or curved and may comprise any suitable material such as glass or a plastic polymer.
[0093] The light source of the present invention has been found to be particularly suitable for use with screens comprising plastic polymers such as polyethylene or polyethylene terephthalate (PET).
[0094] The display is suitable for use in consumer electronic goods such as mobile telephones, hand-held computers, watches and clocks and games machines.
[0095] There is further provided a security viewer (e.g. in kit form) comprising a light emitter as described herein in which the pixels are arranged for polarized emission; and view glasses having a different polarization for each eye.
[0096] There is further provided a method of forming a light emitter for a display comprising forming a photoalignment layer; and aligning a light emitting polymer on said photoalignment layer.
[0097] There is further provided a method of forming a light emitter for a display comprising forming a photoalignment layer; aligning a light emitting reactive mesogen on said photoalignment layer; and forming a light emitting polymer (network) by photopolymerisation of said reactive mesogen.
[0098] There is further provided a method of forming a multicolor emitter comprising applying a first color light emitter to the photoalignment layer; selectively curing said first color light emitter only where that color is required; washing off any residue of uncured first color emitter; and repeating the process for a second and any subsequent light color emitters.
[0099] All references herein are incorporated by reference in their entirety.
BRIEF DESCRIPTION OF THE DRAWINGS
[0100] Embodiments of systems according to the invention will now be described with reference to the accompanying experimental detail and drawings in which:
[0101] FIG. 1 is a schematic representation of a polymerization process herein;
[0102] FIG. 2 is a representation of a display device in accord with the present invention;
[0103] FIG. 3 is a representation of a backlight in accord with the present invention;
[0104] FIG. 4 is a representation of a polarised sequential light emitting backlight in accord with the present invention; and
[0105] FIGS. 5 to 13 show reaction schemes 1 to 9, respectively.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0106] General Experimental Details
[0107] Fluorene, 2-(tributylstanyl)thiophene, 4-(methoxyphenyl)boronic acid and the dienes were purchased from Aldrich and used as received. Reagent grade solvents were dried and purified as follows. N,N-Dimethylformamide (DMF) was dried over anhydrous P 2 O 5 and purified by distillation. Butanone and methanol were distilled and stored over 5 Å molecular sieves. Triethylamine was distilled over potassium hydroxide pellets and then stored over 5 Å molecular sieves. Dichloromethane was dried by distillation over phosphorus pentoxide and then stored over 5 Å molecular sieves. Chloroform was alumina-filtered to remove any residual ethanol and then stored over 5 Å molecular sieves. 1 H nuclear magnetic resonance (NMR) spectra were obtained using a JOEL JMN-GX270 FT nuclear resonance spectrometer. Infra-red (IR) spectra were recorded using a Perkin Elmer 783 infra-red spectrophotometer. Mass spectral data were obtained using a Finnegan MAT 1020 automated GC/MS. The purity of the reaction intermediates was checked using a CHROMPACK CP 9001 capillary gas chromatograph fitted with a 10 m CP-SIL 5CB capillary column. The purity of the final products was determined by high-performance liquid chromatography [HPLC] (5 μm, 25 cm×0.46 cm, ODS Microsorb column, methanol, >99%) and by gel-permeation chromatography [GPC] (5 μm, 30 cm×0.75 cm, 2× mixed D PL columns, calibrated using polystyrene standards [molecular weights=1000-4305000], toluene; no monomer present). The polymers were found to exhibit moderate to high M w values (10,000-30,000) and acceptable M w /M n values (1.5-3). The liquid crystalline transition temperatures were determined using an Olympus BH-2 polarising light microscope together with a Mettler FP52 heating stage and a Mettler FP5 temperature control unit. The thermal analysis of the photopolymerisable monomers (Compounds 3 to 6) and the mainchain polymer (Compound 7) was carried out by a Perkin-Elmer Perkin-Elmer DSC 7 differential scanning calorimeter in conjunction with a TAC 7/3 instrument controller. Purification of intermediates and products was mainly accomplished by column chromatography using silica gel 60 (200-400 mesh) or aluminium oxide (Activated, Brockman 1, ˜150 mesh). Dry flash column chromatography was carried out using silica gel H (Fluka, 5-40 μm).
[0108] Electroluminescent materials were further purified by passing through a column consisting of a layer of basic alumina, a thin layer of activated charcoal, a layer of neutral alumina and a layer of Hi-Flo filter aid using DCM as an eluent. This was followed by recrystallisation from an ethanol-DCM mixture. At this stage, all glass-wear was thoroughly cleaned by rinsing with chromic acid followed by distilled water and then drying in an oven at 100° C. for 45 minutes. Purity of final products was normally confirmed by elemental analysis using a Fisons EA 1108 CHN apparatus.
[0109] Key intermediate 1: 2,7-bis[5-(4-hydroxyphenyl)thien-2-yl]-9,9-dipropylfluorene was synthesised as shown in Reaction Scheme 1. Full details each step are now given:
[0110] 9-Propylfluorene: A solution of n-Butyllithium (18.0 cm 3 , 10M solution in hexanes, 0.18 mol) was added slowly to a solution of fluorene (30.0 g, 0.18 mol) in THF (350 cm 3 ) at −50° C. The solution was stirred for 1 h at −75° C. and 1-bromopropane (23.0 g, 0.19 mol) was added slowly. The solution was allowed to warm to RT and then stirred for a further 1 h. Dilute hydrochloric acid (100 cm 3 , 20%) and water (100 cm 3 ) were added and the product extracted into diethyl ether (3×150 cm 3 ). The ethereal extracts were dried (MgSO 4 ) and concentrated to a pale yellow oil (37.5 g, yield 100%). Purity 100% (GC).
[0111] 1 H NMR (CD 2 Cl 2 ) δ: 7.75 (2H, dd), 7.52 (2H, m), 7.32 (4H, m), 3.98 (1H, t), 1.95 (2H, m), 1.19 (2H, m), 0.85 (3H, t). IR (KBr pellet cm −1 ): 3070 (m), 2962 (s), 1450 (s), 1296 (w), 1189 (w), 1030 (w), 938 (w), 739 (s). MS (m/z): 208 (M + ), 178, 165 (M100), 139.
[0112] 9,9-Dipropylfluorene: A solution of n-Butyllithium (29.0 cm 3 , 2.5M solution in hexanes, 0.073 mol) was added slowly to a solution of 9-propylfluorene (15.0 g, 0.072 mol) in THF at −50° C. The solution was stirred for 1 h at −75° C., 1-bromopropane (10.0 g, 0.092 mol) was added slowly and the temperature raised to RT after completion of the addition. After 18 h, dilute hydrochloric acid (20%, 100 cm 3 ) and water (100 cm 3 ) were added and the product extracted into diethyl ether (2 □100 cm 3 ). The ethereal extracts were dried (MgSO 4 ) and concentrated to a pale brown oil which crystallised overnight at RT. The product was purified by recrystallisation from methanol to yield a white crystalline solid (14.5 g, yield 80%) mp 47-49° C. (Lit. 49-50° C. 19 ). Purity 100% (GC).
[0113] 1 H NMR (CDCl 3 ) δ: 7.68 (2H, m), 7.31 (6H, m), 1.95 (4H, t), 0.65 (10H, m).IR (KBr pellet cm −1 ): 3068 (m), 2961 (s), 1449 (s), 1293 (w), 1106 (w), 1027 (w), 775 (m), 736 (s), 637 (m). MS (m/z): 250 (M + ), 207 (M100), 191, 179, 165.
[0114] 2,7-Dibromo-9,9-dipropylfluorene: Bromine (10.0 g, 0.063 mol) was added to a stirred solution of 9,9-dipropylfluorene (7.0 g, 0.028 mol) in chloroform (25 cm 3 ) and the solution purged with dry N 2 for 0.5 h. Chloroform (50 cm 3 ) was added and the solution washed with saturated sodium bisulphite solution (75 cm 3 ), water (75 cm 3 ), dried (MgSO 4 ) and concentrated to a pale yellow powder (11.3 g, yield 98%) mp 134-137° C.
[0115] 1 H NMR (CDCl 3 ) δ: 7.51 (2H, d), 7.45 (4H, m), 1.90 (4H, t), 0.66 (10H, m). IR (KBr pellet cm −1 ): 2954 (s), 1574 (w), 1451 (s), 1416 (m), 1270 (w), 1238 (w), 1111 (w), 1057 (s), 1006 (w), 931 (w), 878 (m), 808 (s), 749 (m). MS (m/z): 409 (M + ), 365, 336, 323, 284, 269, 256, 248, 202, 189, 176 (M100), 163.
[0116] 2,7-bis(Thien-2-yl)-9,9-dipropylfluorene: A mixture of 2,7-dibromo-9,9-dipropylfluorene (6.0 g, 0.015 mol), 2-(tributylstannyl)thiophene (13.0 g, 0.035 mol) and tetrakis(triphenylphosphine)-palladium (0) (0.3 g, 2.6×10 −4 mol) in DMF (30 cm 3 ) was heated at 90° C. for 24 h. DCM (200 cm 3 ) was added to the cooled reaction mixture and the solution washed with dilute hydrochloric acid (2□150 cm 3 , 20%), water (100 cm 3 ), dried (MgSO 4 ) and concentrated onto silica gel for purification by column chromatography [silica gel, DCM:hexane 1:1]. The compound was purified by recrystallisation from DCM: ethanol to yield light green crystals (4.3 g, yield 6 9%), mp 165-170° C. Purity 100% (GC).
[0117] 1 H NMR (CDCl 3 ) δ: 7.67 (2H, d), 7.60 (2H, dd), 7.57 (2h, d), 7.39 (2H, dd), 7.29 (2H, dd), 7.11 (2H, dd), 2.01 (4H, m), 0.70 (10H, m). IR (KBr pellet cm −1 ): 2962 (m), 2934 (m), 2872 (m), 1467 (m), 1276 (w), 1210 (m), 1052 (w), 853 (m), 817 (s), 691 (s). MS (m/z): 414 (M + , M100), 371, 342, 329, 297, 207, 165.
[0118] 2,7-bis(5-Bromothien-2-yl)-9,9-dipropylfluorene: N-Bromosuccinimide (2.1 g, 0.012 mol freshly purified by recrystallisation from water) was added slowly to a stirred solution of 2,7-bis(thien-2-yl)-9,9-dipropylfluorene (2.3 g, 5.55×10 −3 mol) in chloroform (25.0 cm 3 ) and glacial acetic acid (25.0 cm 3 ). The solution was heated under reflux for 1 h, DCM (100 cm 3 ) added to the cooled reaction mixture, washed with water (100 cm 3 ), HCl (150 cm 3 , 20%), saturated aqueous sodium bisulphite solution (50 cm 3 ), and dried (MgSO 4 ). The solvent was removed in vacuo and the product purified by recrystallisation from an ethanol-DCM mixture to yield yellow-green crystals (2.74 g, yield 86%). mp 160-165° C.
[0119] 1 H NMR (CDCl 3 ) δ: 7.66 (2H, d), 7.49 (2H, dd), 7.46 (2H, d), 7.12 (2H, d), 7.05 (2H, d), 1.98 (4H, t), 0.69 (10H, m). IR (KBr pellet cm −1 ): 3481 (w), 2956 (s), 1468 (s), 1444 (m), 1206 (w), 1011 (w), 963 (w), 822 (m), 791 (s), 474 (w). MS (m/z): 572 (M + ), 529, 500, 487, 448, 433, 420, 407, 375, 250, 126.
[0120] 2,7-bis[5-(4-Methoxyphenyl)thien-2-yl]-9,9-dipropylfluorene: A mixture of 2,7-bis(5-bromothien-2-yl)-9,9-dipropylfluorene (2.7 g, 4.7×10 −3 mol), 4-(methoxyphenyl)boronic acid (2.15 g, 0.014 mol), tetrakis(triphenylphosphine)palladium (0) (0.33 g, 2.9×10 −4 mol), sodium carbonate (3.0 g, 0.029 mol) and water (20 cm 3 ) in DME (100 cm 3 ) was heated under reflux for 24 h. More 4-(methoxyphenyl)boronic acid (1.0 g, 6.5×10 3 mol) was added to the cooled reaction mixture, which was then heated under reflux for a further 24 h. DMF (20 cm 3 ) was added and the solution heated at 110° C. for 24 h, cooled and dilute hydrochloric acid (100 cm 3 , 20%) added. The cooled reaction mixture was extracted with diethyl ether (250 cm 3 ) and the combined ethereal extracts washed with water (100 cm 3 ), dried (MgSO 4 ), and concentrated onto silica gel to be purified by column chromatography [silica gel, DCM:hexane 1:1] and recrystallisation from an ethanol-DCM mixture to yield a green crystalline solid (1.86 g, yield 63%), Cr—N, 235° C.; N—I, 265° C.
[0121] 1 H NMR (CD 2 Cl 2 ) δ: 7.71 (2H, dd), 7.61 (8H, m), 7.37 (2H, d), 7.24 (2H, d), 6.95 (4H, d), 3.84 (6H, s), 2.06 (4H, m), 0.71 (10H, m). IR (KBr pellet cm −1 ): 2961 (w), 1610 (m), 1561 (m), 1511 (s), 1474 (s), 1441 (m), 1281 (m), 1242 (s), 1170 (s), 1103 (m), 829 (m), 790 (s). MS (m/z): 584 (M + -C 3 H 7 ), 569, 555, 539, 525, 511, 468, 313, 277 (M100), 248, 234. Elemental analysis. Calculated: wt % C=78.56%, H 6.11%, S 10.23%. Found: C 78.64%, H 6.14%, S 10.25%.
[0122] 2,7-bis[5-(4-Hydroxyphenyl)thien-2-yl]-9,9-dipropylfluorene): A 1 M solution of boron tribromide in chloroform (9 cm 3 , 9.0 mmol) was added dropwise to a stirred solution of 2,7-bis[5-(4-methoxyphenyl)thien-2-yl]-9,9-dipropylfluorene (1.3 g, 2.1×10 −3 mol) at 0° C. The temperature was allowed to rise to RT overnight and the solution added to ice-water (200 cm 3 ) with vigorous stirring. The product was extracted into diethyl ether (220 cm 3 ), washed with aqueous sodium carbonate (2M, 150 cm 3 ), dried (MgSO 4 ) and purified by column chromatography [silica gel DCM:diethyl ether:ethanol 40:4:1] to yield a green solid (1.2 g, yield 96%), Cr—I, 277° C.; N—I, 259° C.
[0123] 1 H NMR (d-acetone) δ: 8.56 (2H, s), 7.83 (2H, dd), 7.79 (2H, d), 7.68 (2H, dd), 7.57 (4H, dd), 7.50 (2H, dd), 7.31 (2H, dd), 6.91 (4H, dd), 2.15 (4H, m), 0.69 (10H, m). IR (KBr pellet cm −1 ): 3443 (s, broad), 2961 (m), 1610 (m), 1512 (m), 1474 (m), 1243 (m), 1174 (m), 1110 (w), 831 (m), 799 (s). MS (m/z): 598 (M + ), 526, 419 (M100), 337.
[0124] Compound 3: 2,7-bis(5-{4-[5-(1-Vinyl-allyloxycarbonyl)pentyloxy]phenyl}thien-2-yl)-9,9-dipropylfluorene: The 1,3-pentadiene monomer (Compound 3) was synthesised as depicted in Reaction Scheme 2. Full details of each step are now given:
[0125] 1,4-Pentadien-3-yl 6-bromohexanoate: A solution of 6-bromohexanoyl chloride (3.2 g, 0.026 mol) in DCM (30 cm 3 ) was added dropwise to a solution of 1,4-pentadien-3-ol (2.0 g, 0.024 mol) and triethylamine (2.4 g, 0.024 mol) in DCM (30 cm 3 ). The mixture was stirred for 1 h and washed with dilute hydrochloric acid (20%, 50 cm 3 ), saturated potassium carbonate solution (50 cm 3 ), water (50 cm 3 ) then dried (MgSO 4 ) and concentrated to a brown oil. The product was purified by dry flash chromatography [silica gel, DCM] to yield a pale yellow oil (4.7 g, yield 75%). Purity >95% (GC).
[0126] 1 H NMR (CDCl 3 ) δ: 5.82 (2H, m), 5.72 (1H, m), 5.30 (2H, d), 5.27 (2H, d), 3.42 (2H, t), 2.37 (2H, t), 1.93 (2H, m), 1.72 (2H, m), 1.54 (2H, m). IR (KBr pellet cm −1 ): 3095 (w), 1744 (s), 1418 (w), 1371 (w), 12521 (m), 1185 s), 983 (m), 934 (m). MS (m/z): 261 (M + ), 177, 67.
[0127] 2,7-bis(5-{4-[5-(1-Vinyl-allyloxycarbonyl)pentyloxy]phenyl}thien-2-yl)-9,9-dipropylfluorene: A mixture of 2,7-bis[5-(4-hydroxyphenyl)thien-2-yl]-9,9-dipropylfluorene (0.6 g, 1.0×10 −3 mol), 1,4-pentadien-3-yl 5-bromohexanoate (0.7 g, 2.7×10 −3 mol) and potassium carbonate (0.5 g, 3.6×10 −3 mol) in acetonitrile (25 cm 3 ) was heated at 50° C. for 18 h. The mixture was then heated under reflux conditions for a further 20 h. Excess potassium carbonate was filtered off and precipitated product rinsed through with DCM (230 cm 3 ). The solution was concentrated onto silica gel for purification by column chromatography [silica gel, DCM:hexane 1:1 gradients to DCM] and recrystallisation from a DCM-ethanol mixture to yield a green-yellow solid (0.4 g, yield 40%), Cr—N, 92° C.; N—I, 108° C.
[0128] 1 H NMR (CD 2 Cl 2 ) δ: 7.69 (2H, d), 7.58 (8H, m), 7.35 (2H, d), 7.22 (2H, d), 6.91 (4H, d), 5.83 (4H, m), 5.68 (2H, m), 5.29 (2H, t), 5.25 (2H, t), 5.21 (2H, t), 5.19 (2H, t), 3.99 (4H, t), 2.37 (4H, t), 2.04 (4H, m), 1.80 (4H, quint), 1.70 (4H, quint), 1.51 (4H, quint) 0.69 (10H, m). IR (KBr pellet cm −1 ): 2936 (m), 2873 (m), 1738 (s), 1608 (m), 1511 (m), 1473 (s), 1282 (m), 1249 (s), 1177 (s), 1110 (m), 982 (m), 928 (m), 829 (m), 798 (s). APCI-MS (m/z): 958 (M + ), 892 (M100). Elemental analysis. Calculated: wt % C=76.37, wt % H=6.93, wt % S=6.68. Found: wt % C=75.93, wt % H=6.95, wt % S=6.69.
Compound 4: 2,7-bis(5-{4-[5-(1-Allylbut-3-enyloxycarbonyl)pentyloxy]phenyl}thien-2-yl)-9,9-dipropylfluorene
[0129] The 1,3-heptadiene monomer (Compound 4) was synthesised as depicted in reaction Scheme 3. Full details of each step are now given:
[0130] 1,6-Heptadien-5-yl 5-bromopentanoate: 5-Bromopentanoyl chloride (3.0 g, 0.015 mol) was added dropwise to 1,6-heptadien-4-ol (1.5 g, 0.013 mol) and triethylamine (1.4 g, 0.014 mol) in DCM (25 cm 3 ). The mixture was stirred for 2 h and washed with dilute hydrochloric acid (20%, 50 cm 3 ), saturated aqueous potassium carbonate solution (50 cm 3 ), water (50 cm 3 ) then dried (MgSO 4 ) and concentrated to a brown oil. The product was purified by dry flash chromatography [silica gel, DCM] to yield a pale yellow oil (1.7 g, yield 48%). Purity >92% (GC).
[0131] 1 H NMR (CDCl 3 ) δ: 5.74 (2H, m), 5.08 (4H, m), 4.99 (1H, m), 3.41 (2H, t), 2.31 (6H, m), 1.88 (2H, m), 1.76 (2H, m). IR (Film cm −1 ): 2952 (m), 1882 (w), 1734 (s), 1654 (m) 1563 (w), 1438 (m), 1255 (m), 1196 (s), 996 (m), 920 (s). MS (m/z): 275 (M + ), 245, 219, 191, 183, 163 (M100), 135, 95, 79.
[0132] 2,7-bis(5-{4-[5-(1-Allylbut-3-enyloxycarbonyl)pentyloxy]phenyl}thien-2-yl)-9,9-dipropylfluorene: A mixture of 2,7-bis[5-(4-hydroxyphenyl)thien-2-yl]-9,9-dipropylfluorene (0.3 9, 1.0×10 −3 mol), 1,6-heptadienyl 6-bromohexanoate (0.7 g, 2.7×10 −3 mol) and potassium carbonate (0.5 g, 3.6×10 −3 mol) in acetonitrile (25 cm 3 ) was heated under reflux for 20 h. Excess potassium carbonate was filtered off and precipitated product rinsed through with DCM (230 cm 3 ). The solution was concentrated onto silica gel for purification by column chromatography [silica gel, DCM: hexane 1:1 gradients to DCM] and recrystallisation from a DCM-ethanol mixture to yield a green-yellow solid (0.21 g, yield 21%), Cr-1,97° C., N—I, 94° C.
[0133] 1 H NMR (CDCl 3 ) 6:7.68 (2H, d), 7.60 (2H, dd), 7.58 (2H, d), 7.57 (2H, d), 7.33 (2H, d), 7.20 (2H, d), 6.91 (2H, d), 5.75 (4H, m), 5.08 (8H, m), 5.00 (2H, quint), 4.00 (4H, t), 2.33 (12H, m), 2.02 (4H, t), 1.82 (4H, quint), 1.71 (4H, quint), 1.53 (4H, m), 0.72 (10H, m). IR (KBr pellet cm −1 ): 3443 (s), 2955 (s), 1734 (s), 1643 (w), 1609 (m), 1512 (m), 1473 (s), 1249 (s), 1178 (s), 996 (m), 918 (m), 829 (m), 799 (s). APCI-MS (m/z): 1015 (M + , M100), 921. Elemental analysis. Calculated: wt % C=76.89, wt % H=7.35, wt % S=6.32%. Found: wt % C=76.96, wt % H=7.42, wt % S=6.23.
Compound 5: 2,7-bis(5-{4-[3-(1-Vinylallyloxycarbonyl)propyloxy]phenyl}thien-2-yl)-9,9-dipropylfluorene
[0134] The 1,3-pentadiene homologue (Compound 5) was synthesised as depicted in reaction Scheme 4. Full details of each step are now given:
[0135] 4-Bromobutanoyl chloride: Oxalyl chloride (15.2 g, 0.12 mol) was added dropwise to a stirred solution of 4-bromobutanoic acid (10.0 g, 0.060 mol) and DMF (few drops) in chloroform (30 cm 3 ). The solution was stirred overnight under anhydrous conditions and concentrated to a pale brown oil which was filtered to remove solid impurities (11.0 g, yield 99%).
[0136] 1,4-Pentadien-3-yl 4-bromobutanoate: 4-Bromobutanoyl chloride (3.0 g, 0.016 mol) was added dropwise to a solution of 1,4-pentadien-3-ol (1.3 g, 0.015 mol) and triethylamine (1.5 g, 0.015 mol) in DCM (30 cm 3 ). The solution was stirred for 2 h and washed with dilute hydrochloric acid (20%, 50 cm 3 ), saturated potassium carbonate solution (50 cm 3 ), water (50 cm 3 ) then dried (MgSO 4 ) and concentrated to a pale brown oil. The product was purified by dry flash chromatography [silica gel, DCM] to yield a pale yellow oil (1.8 g, yield 51%). Purity >85% (GC; decomposition on column).
[0137] 1 H NMR (CDCl 3 ) δ: 5.83 (2H, m), 5.72 (1H, m), 5.27 (4H, m), 3.47 (2H, t), 2.55 (2H, t), 2.19 (2H, quint). IR (KBr pellet cm −1 ): 3096 (w), 2973 (w), 1740 (s), 1647 (w), 1419 (m), 1376 (m), 1198 (s), 1131 (s), 987 (s), 932 (s), 557 (w). MS (m/z): 217, 166, 152, 149, 125, 110, 84, 67 (M100).
[0138] 2,7-bis(5-{4-[3-(1-Vinylallyloxycarbonyl)propyloxy]phenyl}thien-2-yl)-9,9-dipropylfluorene: A mixture of 2,7-bis[5-(4-hydroxyphenyl)thien-2-yl]-9,9-dipropylfluorene (0.25 g, 4.2×10 −4 mol), 1,4-pentadien-3-yl 4-bromobutanoate (0.40 g, 1.7×10 −3 mol) and potassium carbonate (0.20 g, 1.4×10 −3 mol) in DMF (10 cm 3 ) was heated under reflux for 4 h. The cooled solution was filtered, rinsed through with DCM (3×20 cm 3 ) and concentrated to a pale green oil which was purified by column chromatography [silica gel, DCM:hexane 2:1] followed by recrystallisation from ethanol:DCM to yield a green-yellow powder (0.20 g, yield 53%), Cr—N, 92° C.; N—I, 116° C.
[0139] 1 H NMR (CDCl 3 ) δ: 7.61 (10H, m), 7.33 (2H, d), 7.20 (2H, d), 6.92 (4H, d), 5.85 (4H, m), 5.74 (2H, m), 5.32 (4H, d, J=17 Hz), 5.24 (4H, d, J=10 Hz), 4.06 (4H, t), 2.56 (4H, t), 2.16 (4H, quint), 2.05 (4H, t), 0.72 (10H, m). IR (KBr pellet cm −1 ): 3449 (m), 2960 (m), 1738 (s), 1609 (m), 1512 (m), 1473 (s), 1380 (w), 1249 (s), 1174 (s), 1051 (m), 936 (m), 830 (m), 799 (s). APCI-MS (m/z): 903 (M + ), 837 (Ml 00), 772. Elemental analysis. Calculated: wt % C=75.80, wt % H=6.47, wt % S=7.10. Found: wt % C=76.13, wt % H=6.48%, wt % S=6.91.
Compound 6: 2,7-bis{5-[4-(8-Diallylaminooctyloxy)phenyl]-thien-2-yl}9,9-dipropylfluorene
[0140] The method of preparation of the N,N-diallylamine monomer (Compound 6) is shown in reaction Scheme 5. Full details of each step are now given:
[0141] 8-Diallylaminooctan-1-ol. A mixture of 8-bromooctan-1-ol (10.0 g, 0.048 mol), diallylamine (4.85 g, 0.050 mol) and potassium carbonate (7.0 g, 0.051 mol) in butanone (100 cm 3 ) was heated under reflux for 18 h. Excess potassium carbonate was filtered off and the solution concentrated to a colourless oil. The product was purified by dry flash chromatography [silica gel, DCM:ethanol 4:1]. (10.0 g, yield 93%).
[0142] 1 H NMR (CDCl 3 ) δ: 5.86 (2H, d), 5.14 (4H, m), 3.71 (4H, quart), 3.63 (4H, t), 3.09 (4H, d), 1.56 (4H, m), 1.45 (2H, quint), 1.30 (6H, m). IR (KBr pellet cm −1 ): 3344 (s), 2936 (s), 1453 (w), 1054 (m), 998 (m), 921 (m). MS (m/z): 225 (M + ), 198, 184, 166, 152, 138, 124, 110 (M100), 81.
[0143] Toluene-4-sulphonic acid 8-diallylaminooctyl ester. 4-Toluene-sulphonyl chloride (12.5 g, 0.066 mol) was added slowly to a stirred solution of 8-diallylaminooctan-1-ol (10.0 g, 0.044 mol) and pyridine (7.0 g, 0.088 mol) in chloroform (100 cm 3 ) at 0° C. After 24 h, water (100 cm 3 ) was added and the solution washed with dilute hydrochloric acid (20%, 100 cm 3 ), sodium carbonate solution (100 cm 3 ), water (100 cm 3 ), dried (MgSO 4 ) and concentrated to a yellow oil which was purified by column chromatography [silica gel, 4% diethyl ether in hexane eluting to DCM:ethanol 10:1] to yield the desired product (6.7 g, yield 40%).
[0144] 1 H NMR (CDCl 3 ) δ: 7.78 (2H, d), 7.34 (2H, d), 5.84 (2H, m), 5.13 (4H, m), 4.01 (2H, t), 3.41 (4H, d), 2.45 (3H, s), 2.39 (2H, t), 1.63 (2H, quint), 1.42 (2H, quint), 1.30 (2H, quint), 1.23 (6H, m). IR (KBr pellet cm −1 ): 3454 (w), 2957 (m), 1453 (s), 1402 (m), 1287 (m), 1159 (w), 1061 (m), 914 (w), 878 (m), 808 (s), 448 (m). MS (m/z): 380 (M + ), 364, 352, 338, 224, 110 (M100), 91, 79, 66.
[0145] 2,7-bis{5-[4-(8-Diallylaminooctyloxy)phenyl]-thien-2-yl}-9,9-dipropylfluorene: A mixture of 2,7-bis[5-(4-hydroxyphenyl)thien-2-yl]-9,9-dipropylfluorene (0.5 g, 8.4×10 4 mol), toluene-4-sulphonic acid-8-diallylaminooctyl ester (0.8 g, 2.1×10 −3 mol) and potassium carbonate (0.3 g, 2.2× 10 1 3 mol) in butanone (30 cm 3 ) was heated under reflux for 24 h. Excess potassium carbonate was filtered off and rinsed with DCM (3×30 cm 3 ). The solution was concentrated onto silica gel for purification by column chromatography [silica gel, DCM:hexane 2:1 eluting to DCM:ethanol 4:1]. The product was obtained as a yellow-green glass (0.35 g, yield 41%), N—I, 95° C.
[0146] 1 H NMR (CDCl 3 ) δ: 7.67 (2H, d), 7.58 (8H, m), 7.34 (2H, d), 7.20 (2H, d), 6.92 (4H, d), 5.94 (4H, m), 5.25 (8H, m), 3.99 (4H, t), 3.22 (8H, d), 2.02 (4H, t), 1.80 (4H, quint), 1.56 (4H, quint), 1.47 (4H, quint), 1.35 (12H, m), 0.71 (10H, m). IR (KBr pellet cm −1 ): 3437 (s), (2934 (s), 1609 (s), 1512 (s), 1472 (s), 1283 (m), 1249 (s), 1179 (s), 1031 (w), 918 (w), 829 (m), 798 (s). APCI-MS (m/z): 1014 (M + , M100), 973. Elemental analysis. Calculated: wt % C=79.40, wt % H=8.35, wt % N=2.76, wt % S=6.33. Found: wt % C=79.33, wt % H=8.29, wt % N=2.88, wt % S=6.17.
Compound 7: poly(phenylene-1,3,4-oxadiazole-phenylene-hexafluoropropylene)
[0147] The electron-transporting polymer (Compound 7) was prepared according to a literature method described in Li, X.-C.; Kraft, A.; Cervini, R.; Spencer, G. C. W.; Cacialli, F.; Friend, R. H.; Gruener, J.; Holmes, A. B.; de Mello, J. C.; Moratti, S. C. Mat. Res. Symp. Proc. 1996, 413 13.
[0148] In more detail the preparation details were as follows: A solution of 4,4′-(hexafluoroisopropylidine)bis(benzoic acid) (2.54 g, 6.48×10 −3 mol) and hydrazine sulphate (0.84 g, 6.48×10 −3 mol) in Eaton's reagent (25 cm 3 ) was heated under reflux for 18 h. The cooled solution was added to brine (300 cm 3 ) and the product extracted into chloroform (8×200 cm 3 ). The organic extracts were combined, dried (MgSO 4 ) and the solvent removed under reduced pressure to yield the crude product which was purified by dissolving in a minimum volume of chloroform and precipitating by dropwise addition to methanol (1000 cm 3 ). The precipitate was filtered off and washed with hot water before being dried in vacuo. The precipitation was repeated a further three times washing with methanol each time. The product was then dissolved in chloroform and passed through a microfilter (0.45 μm). The pure product was then precipitated in methanol (500 cm 3 ) and the methanol removed under reduced pressure to yield a white fibrous solid which was dried in vacuo. Yield 1.26 g (50%).
[0149] 1 H NMR (CDCl 3 ) δ H :8.19 (4H/repeat unit, d), 7.61 (4H/repeat unit, d).
[0150] IR ν max /cm −1 : 3488 (m), 1621 (m), 1553 (m), 1502 (s), 1421 (m), 1329 (m), 1255 (s), 1211 (s), 1176 (s), 1140 (s), 1073 (m), 1020 (m), 969 (m), 929 (m), 840 (m), 751 (m), 723 (s). GPC: M w :M n =258211:101054.
[0151] An alternative electron-transport copolymer is prepared according to the method described in Xiao-Chang Li et al J. Chem. Soc. Chem. Commun., 1995, 2211.
[0152] In more detail the preparation details were as follows: Terephthaloyl chloride (0.50 g, 2.46×10 −3 mol) was added to hydrazine hydrate (50 cm 3 ) at room temperature and the mixture stirred for 2 h. The precipitate was filtered off, washed with water (100 cm 3 ) and dried in vacuo. The crude hydrazide (0.25 g, 1.3×10 −3 mol), 4,4′-(hexafluoroisopropylidine)bis(benzoic acid) (2.50 g, 6.4×10 −3 mol) and hydrazine sulphate (0.66 g, 5.2×10 −3 mol) were added to Eaton's reagent and the resultant mixture heated at 100° C. for 24 h. The reaction mixture was added to water (300 cm 3 ) and the product extracted into chloroform (3×300 cm 3 ). The organic extracts were combined, dried (MgSO 4 ) and the solvent removed in vacuo before re-dissolving the product in the minimum volume of chloroform. The solution was added dropwise to methanol (900 cm 3 ) to give a white precipitate which was filtered off and dried in vacuo. The precipitation was repeated twice before dissolving the product in chloroform and passing through a microfilter (0.45 μm) into methanol (500 cm 3 ). The methanol was removed under reduced pressure and the product dried in vacuo. Yield 1.1 g (41%).
[0153] 1 H NMR (CDCl 3 ) δ H :8.18 (dd, 4H/repeat unit), 7.60 (dd, 4H/repeat unit).
[0154] IR ν max /cm −1 : 3411 (w), 2366 (w), 1501 (m), 1261 (s), 1211 (s), 1176 (s), 1140 (m), 1072 (m), 1021 (w), 968 (m), 931 (w), 840 (m), 722 (m).
[0155] GPC: M w :M n =20572:8320.
[0156] Key intermediate 2: 9,9-diethyl-2,7-bis(4-hydroxybiphenyl-4′-yl)fluorene was synthesised as shown in Reaction Scheme 7. Full details of each step are now given:
[0157] 9-Ethylfluorene: A solution of n-butyllithium (79.52 cm 3 , 0.2168 mol, 2.5M in hexane) was added slowly to a solution of fluorene (30.00 g, 0.1807 mol) in THF (300 cm 3 ) at −70° C. The solution was stirred for 1 hour at −75° C. and 1-bromoethane (17.59 cm 3 , 0.2349 mol) was added slowly. The solution was allowed to warm to room temperature and then stirred overnight. Dilute hydrochloric acid (200 ml, 20%) was added to the reaction mixture and stirred for a further 10 minutes. Water (250 cm 3 ) was added and the product extracted into diethyl ether (3×300 cm 3 ). The combined organic extracts were dried (MgSO 4 ) and the solvent removed on a rotary evaporator. The resulting oil was purified by distillation to yield a pale yellow oil (25.00 g, 71%, b.pt.-150° C. @ 1 mbar Hg).
[0158] 1 H NMR (DMSO) δ:7.70 (2H, m), 7.50 (2H, m), 7.30 (4H, m), 4.00 (1H, t), 2.02 (2H, quart), 0.31 (3H, t). IR ν max /cm −1 : 3072 (m), 2971, 1618, 1453, 1380, 1187, 759, 734. MS m/z: 170 (M + ), 94, 82, 69.
[0159] 9,9-Diethylfluorene: A solution of n-butyllithium (77.34 cm 3 , 0.1934 mol, 2.5M in hexane) was added slowly to a solution of 9-ethylfluorene (25.00 g, 0.1289 mol) in THF (250 cm 3 ) at −70° C. The solution was stirred for 1 hour at −75° C. and 1-bromoethane (17.59 cm 3 , 0.1934 mol) was added slowly. The solution was allowed to warm to room temperature and then stirred overnight. Dilute hydrochloric acid (200 cm 3 , 20%) was added to the reaction mixture and stirred for a further 10 minutes. Water (250 cm 3 ) was added and the product extracted into diethyl ether (3×300 cm 3 ). The combined organic extracts were dried (MgSO 4 ) and the solvent removed on a rotary evaporator. The resulting oil was cooled to room temperature and recrystallised with ethanol to yield white crystals (19.50 g, 68%, m.pt. 60-62° C.).
[0160] 1 H NMR (DMSO) δ: 7.76 (2H, m), 7.51 (2H, m), 7.35 (4H, m), 1.51 (4H, quart), 0.30 (6H, t), IR ν max /cm −1 : 3069, 2972, 1612, 1448, 1310, 761, 736. MS m/z: 222 (M + ), 193, 152, 94, 82, 75.
[0161] 2,7-Dibromo-9,9-diethylfluorene: Bromine (13.47 cm 3 , 0.2568 mol) was added to a stirred solution of 9,9-diethylfluorene (19.00 g, 0.0856 mol) in DCM (250 cm 3 ). The HBr gas evolved was passed through a scrubbing solution of NaOH (1.5M). The reaction mixture was stirred for 4 hours. The reaction mixture was washed with sodium metabisulphite solution and extracted into diethyl ether (3×300 cm 3 ). The combined organic extracts were dried and the solvent removed on a rotary evaporator. The crude product was recrystallised from ethanol to yield a white crystalline solid (20.00 g, 61%, m.pt. 152-154° C.).
[0162] 1 H NMR (DMSO) δ: 7.52 (2H, m), 7.45 (4H, m), 1.99 (4H, quart), 0.31 (6H, t). IR ν max /cm −1 : 2966, 1599, 1453, 1418, 1058, 772, 734. MS m/z: 380 (M + ), 351, 272, 220, 189, 176, 165, 94, 87, 75.
[0163] 4-Bromo-4′-octyloxybiphenyl: A mixture of 4-bromo-4′-hydroxybiphenyl (50.00 g, 0.2008 mol), 1-bromooctane (50.38 g, 0.2610 mol), potassium carbonate (47.11 g, 0.3414 mol) and butanone (500 cm 3 ) was heated under reflux overnight. The cooled mixture was filtered and the solvent removed on a rotary evaporator. The crude solid was recrystallised from ethanol to yield a white crystalline solid (47.30 g, 66%, m.pt. 120° C.).
[0164] 1 H NMR (DMSO): δ:7.46 (6H, m), 6.95 (2H, m), 3.99 (2H, t), 1.80 (2H, quint), 1.38 (10H, m), 0.88 (3H, t). IR ν max /cm −1 : 2927, 2860, 1608, 1481, 1290, 1259, 844. MS m/z: 362 (M + ), 250, 221, 195, 182, 152, 139, 115, 89, 76, 69.
[0165] 4-Octyloxybiphenyl-4′-yl boronic acid: A solution of n-butylithium (50.97 cm 3 , 0.1274 mol, 2.5M in hexane) was added dropwise to a cooled (−78° C.) stirred solution of 4-bromo-4′-octyloxybiphenyl (40.00 g, 0.1108 mol) in THF (400 cm 3 ). After 1 h, trimethyl borate (23.05 g, 0.2216 mol) was added dropwise to the reaction mixture maintaining a temperature of −78° C. The reaction mixture was allowed to warm to room temperature overnight. 20% hydrochloric acid (350 cm 3 ) was added and the resultant mixture stirred for 1 h. The product was extracted into diethyl ether (3×300 cm 3 ). The combined organic layers were washed with water (300 cm 3 ), dried (MgSO 4 ), filtered and the filtrate evaporated down under partially reduced pressure. The crude product was stirred with hexane for 30 minutes and filtered off to yield a white powder (26.20 g, 73%, m.pt. 134-136° C.).
[0166] 1 H NMR (DMSO) δ: 8.04 (2H, s), 7.84 (2H, m), 7.57 (4H, m), 7.00 (2H, m), 3.99 (2H, t), 1.74 (2H, quint), 1.35 (10H, m), 0.85 (3H, t). IR ν max /cm −1 : 2933, 2860, 1608, 1473, 1286, 1258, 818. MS m/z: 326 (M + ), 214, 196, 186, 170, 157, 128, 115, 77, 63.
[0167] 9,9-Diethyl-2,7-bis(4-octyloxybiphenyl-4′-yl)fluorene: Tetrakis(triphenylphosphine)palladium(0) (0.70 g, 0.0006 mol) was added to a stirred solution of 2,7-dibromo-9,9-diethylfluorene (4) (2.33 g, 0.0061 mol), 4-octyloxybiphenyl-4′-yl boronic acid (5.00 g, 0.0153 mol), 20% sodium carbonate solution (100 cm 3 ) and 1,2-dimethoxyethane (150 cm 3 ). The reaction mixture was heated under reflux overnight. Water (300 cm 3 ) was added to the cooled reaction mixture and the product extracted into DCM (3×300 cm 3 ). The combined organic extracts were washed with brine (2×150 cm 3 ), dried (MgSO 4 )), filtered and the filtrate evaporated down under partially reduced pressure. The residue was purified by column chromatography on silica gel using DCM and hexane (30:70) as eluent and recrystallisation from ethanol and DCM to yield a white crystalline solid (3.10 g, 65%, m.pt. 146° C.).
[0168] 1 H NMR (DMSO) 6:7.77 (6H, m), 7.63 (12H, m), 7.00 (4H, m), 4.01 (4H, t), 2.13 (4H, quart), 1.82 (4H, quint), 1.40 (20H, m), 0.89 (6H, t), 0.43 (6H, t). IR ν max /cm −1 : 3024, 2921, 2853, 1609, 1501, 1463, 1251, 808. MS m/z: 782 (M + ), 669, 514, 485, 279, 145, 121, 107, 83, 71. CHN analysis: % Expected C (87.42%), H (8.49%). % Found C (87.66%), H (8.56%).
[0169] 9,9-Diethyl-2,7-bis(4-hydroxybiphenyl-4′-yl)fluorene: Boron tribromide (99.9%, 1.05 cm 3 , 0.0111 mol) in DCM (10 ml) was added dropwise to a cooled (0° C.) stirred solution of 9,9-diethyl-2,7-bis(4-octyloxybiphenyl-4′-yl)fluorene (2.90 g, 0.0037 mol) in DCM (100 cm 3 ). The reaction mixture was stirred at room temperature overnight, then poured onto an ice/water mixture (50 g) and stirred (30 minutes). The crude product was purified by column chromatography on silica gel with a mixture of ethyl acetate and hexane (30:70) as the eluent and recrystallisation from ethanol to yield a white powder (0.83 g, 40%, m.pt. >300° C.).
[0170] 1 H NMR (DMSO) δ: 9.09 (2H, OH), 7.77 (6H, m), 7.64 (8H, m), 7.51 (4H, m), 6.94 (4H, m), 1.19 (4H, m), 0.42 (6H, t). IR ν max /cm −1 : 1608, 1500, 1463, 1244, 1173, 811. MS m/z: 558 (M + ), 529, 514, 313, 279, 257, 115, 77, 65.
Compound 8: 9,9-Diethyl-2,7-bis{4-[5-(1-vinyl-allyloxycarbonyl)pentyloxy]biphenyl-4′-yl}fluorene: Compound 8 was Synthesised as Follows
[0171] A mixture of 9,9-diethyl-2,7-bis(4-hydroxybiphenyl-4′-yl)fluorene (0.83 g, 0.0015 mol), 1,4-pentadienyl-3-yl 6-bromohexanoate (0.97 g, 0.0037 mol), potassium carbonate (0.62 g, 0.0045 mol) and DMF (25 cm 3 ) was heated under reflux overnight. The cooled reaction mixture was added to water (500 cm 3 ) and then extracted with DCM (3×50 cm 3 ). The combined organic extracts were washed with water (250 cm 3 ), dried (MgSO 4 ) and the filtrate evaporated down under partially reduced pressure. The crude product was purified by column chromatography using silica gel using a mixture of DCM and hexane (80:20) as the eluent and recrystallisation from DCM and ethanol to yield a white crystalline solid (0.2 g, 22%).
[0172] 1 H NMR (CDCl 3 ) δ: 7.78 (6H, m), 7.62 (12H, m), 7.00 (4H, m), 5.85 (4H, m), 5.74 (4H, m), 5.27 (4H, m), 4.03 (4H, t), 2.42 (4H, t), 2.14 (4H, quart), 1.85 (4H, m), 1.74 (4H, m), 1.25 (4H, q), 0.43 (3H, t). IR ν max /cm −1 : 3028, 2922, 2870, 1734, 1606, 1500, 1464, 1246, 1176, 812. CHN analysis: % Expected C (82.32%), H (7.24%). % Found C (81.59%), H (6.93%).
[0173] Compounds 9-15: Compounds 9 to 15, comprising the 2,7-bis{ω-[5-(1-vinyl-allyloxycarbonyl)alkoxy]-4′-biphenyl}-9,9-dialkylfluorenes compounds of Table 1 were prepared analogously to Compound 8.
n m Compound 9 3 5 Compound 10 4 5 Compound 11 5 5 Compound 12 6 5 Compound 13 8 5 Compound 14 8 7 Compound 15 8 11
[0174] All of Compounds 8 to 15 exhibit a nematic phase with a clearing point (N-1) between 58 and 143° C.
Compound 16: 4,7-bis{4-[(S)-3,7-Dimethyl-oct-6-enyloxy]phenyl}-2,1,3-benzothiadozole
[0175] Compound 16 was synthesised as depicted in Reaction Scheme 8. Full details of each step follows:
[0176] 4,7-Dibromo-2,1,3-benzothiadozole: Bromine (52.8 g, 0.33 mol) was added to a solution of 2,1,3-benzothiadozole (8.1 g, 0.032 mol) in hydrobromic acid (47%, 100 cm 3 ) and the resultant solution was heated under reflux for 2.5 h. The cooled reaction mixture reaction mixture was filtered and the solid product washed with water (200 cm 3 ) and sucked dry. The raw product was purified by recrystallisation from ethanol to yield 21.0 g (65%) of the desired product.
[0177] 1-Bromo-4-[(S)-3,7-dimethyloct-6-enyloxy]benzene: A mixture of 4-bromophenol (34.6 g, 0.20 mol), (S)-(+)-citronellyl bromide (50 g, 0.023 mol) and potassium carbonate (45 g, 0.33 mol) in butanone (500 cm 3 ) was heated under reflux overnight. The cooled reaction mixture was filtered and the filtrate concentrated under reduced pressure. The crude product was purified by fractional distillation to yield 42.3 g (68.2%) of the desired product.
[0178] 4-[(S)-3,7-Dimethyloct-6-enyloxy]phenyl boronic acid: 2.5M n-Butylithium in hexanes (49.3 cm 3 , 0.12 mol) was added dropwise to a cooled (−78° C.) solution of 1-bromo-4-[(S)-3,7-dimethyloct-6-enyloxy]benzene (35 g, 0.11 mol) in tetrahydrofuran (350 cm 3 ). The resultant solution was stirred at this temperature for 1 h and then trimethyl borate (23.8 g, 0.23 mol) was added dropwise to the mixture while maintaining the temperature at −78° C. 20% hydrochloric acid (250 cm 3 ) was added and the resultant mixture was stirred for 1 h and then extracted into diethyl ether (2×200 cm 3 ). The combined organic layers were washed with water (2×100 cm 3 ) and dried (MgSO 4 ). After filtration the solvent was removed under reduce pressure to yield 20.35 g (65%) of the desired product.
[0179] 4,7-bis{4-[(S)-3,7-Dimethyl-oct-6-enyloxy]phenyl}-2,1,3-benzothiadozole: A mixture of tetrakis(triphenylphosphine)palladium(0) (0.8 g, 0.70×10 −3 mol), 4,7-dibromo-2,1,3-benzothiadozole (2) (2 g, 6.75×10 −3 mol), 4-[(S)-3,7-dimethyloct-6-enyloxy]phenyl boronic acid (4.66 g, 1.70×10 −2 mol), 2M sodium carbonate solution (50 cm 3 ) and 1,2-dimethoxyethane (150 cm 3 ). The reaction mixture was heated under reflux overnight. The cooled reaction mixture was extracted with dichloromethane (2×150 cm 3 ) and the combined organic layers were washed with brine (2×100 cm 3 ) and dried (MgSO 4 ). After filtration the solvent was removed under reduced pressure and the residue was purified by column chromatography [silica gel, dichloromethane: hexane 1:4] followed by recrystallisation from ethanol to yield 3.2 g (79.5%) of the desired product.
[0180] 4,7-bis(4-Hydroxyphenyl)-2,1,3-benzothiadozole: Boron tribromide (1.51 cm 3 , 1.61×10 −2 mol) was added dropwise to a cooled (0° C.) stirred solution of 2,5-bis{4-[(S)-3,7-dimethyl-oct-6-enyloxy]phenyl}-2,1,3-benzothiadozole (4.0 g, 7.40×10 −3 mol) in dichloromethane (100 cm 3 ). The reaction mixture was stirred at room temperature overnight, then poured onto an ice/water mixture (200 g) and stirred (30 min). The desired product was precipitated and it was filtered off and sucked dry to yield 1.23 g (71.5%) of the desired product.
[0181] 4,7-bis(4-{5-[1-Vinyl-allyloxycarbonyl]pentyloxy}phenyl)-2,1,3-benzothiadozole: A mixture of 2,5-bis(4-hydroxyphenyl)-2,1,3-benzothiadozole (0.3 g, 0.93×10 −3 mol), 1,4-pentadien-3-yl 5-bromopentanoate (0.61 g, 2.34×10 −3 mol) and potassium carbonate (0.38 g, 2.79×10 −3 mol) in N,N-dimethylformaldehyde (30 cm 3 ) was heated (80° C.) overnight. The cooled reaction mixture was filtered and the filtrate concentrated under reduce pressure. The crude product was purified by column chromatography [silica gel, ethyl acetate:hexane 1:5] followed by recrystallisation from ethanol to yield 0.39 g (61.8%) of the desired product.
[0182] Compounds 17 and 18 are preparable by an analogous process.
Compounds 19-29
2-Bromo-7-iodofluorene (Compound 20)
[0183] A mixture of 2-bromofluorene (compound 19) (25.0 g, 0.1020 mol), glacial acetic acid (250 cm 3 ), concentrated sulphuric acid (3 cm 3 ) and water (20 cm 3 ) became homogeneous on heating to 75° C. Periodic acid dihydrate (H 5 IO 6 , 4.56 g, 0.0200 mol) and pulverised 12 (10.2 g, 0.0402 mol) were added. The initial deep-purple colour changed to a brown during 2 h of heating and stirring at 75° C. Upon dilution with sodium hydrogensulphite (2.50 g) in water (25 cm 3 ), the colour changed to yellow. The solution was subsequently diluted with water (500 cm 3 ) and cooled to 0° C. to give a yellow precipitate. The excess liquid was decanted and the solid filtered off, washed repeatedly with cold ethanol (4×50 cm 3 ), aqueous NaOH (5% solution, 4×50 cm 3 ) and with water (4×50 cm 3 ) to leave a yellow powder. The product was recrystallised from a solvent mixture of DCM and ethanol to yield a yellow powder (28.4 g, 74.9%). Melting point/° C.: 185.
2-Bromo-7-iodo-9,9-dihexylfluorene (Compound 21)
[0184] DMF (150 cm 3 ) was added to a mixture of 2-bromo-7-iodofluorene (compound 20) (15.0 g, 0.0400 mol) and powdered potassium-t-butoxide (13.4 g, 0.1200 mol). The mixture which took a deep red colour was stirred and warmed to 60° C. 1-Bromohexane (19.7 g, 0.1200 mol) was then added dropwise during 1 h. The temperature was maintained at 60° C. and the colour of the mixture progressed to a deep purple-black. The reaction mixture was heated overnight and the mixture poured into water (300 cm 3 ). The product was extracted into hexane (2×200 cm 3 ) and the combined organic layers were washed with water (3×300 cm 3 ), hydrochloric acid (10%, 300 cm 3 ), water (500 cm 3 ) and finally dried (MgSO 4 ), filtered and concentrated under reduced pressure. The residue was purified by gravity column chromatography [silica gel, hexane, 100%] to yield a white powder (13.0 g, 60.4%). Melting point/° C.:61.
2-(4-Octyloxyphenyl)thiophene (Compound 23)
[0185] A mixture of 1-bromo-4-octyloxybenzene (compound 22) (10.0 g, 0.0351 mol), 2-(tributylstannyl)thiophene (14.4 g, 0.0386 mol) and tetrakis(triphenylphosphine)-palladium (0) (1.22 g, 1.05×10 −3 mol) in DMF (200 cm 3 ) was heated at 90° C. for 24 h. The mixture was allowed to cool to RT and the solution was treated with a saturated potassium fluoride solution (100 cm 3 ) to destroy the tin side products. Hexane (2×200 cm 3 ) was added and the combined organic layers were washed with brine (2×200 cm 3 ), water (200 cm 3 ), dried (MgSO 4 ), filtered and concentrated under reduced pressure. Catalyst residues were removed by passing the crude product though a short column containing silica gel [DCM: hexane, 50%: 50%]. The product was recrystallised from ethanol, filtered and washed with cold ethanol (2×30 cm 3 ) to yield a light blue crystalline solid (5.00 g, 49.5%). Melting point/° C.: 68-70.
2-[(4-Octyloxyphenyl)-5-tributylstannyl]thiophene (Compound 24)
[0186] A solution of n-BuLi in hexanes (30.7 cm 3 , 2.5M, 0.0767 mol) was added slowly to a solution of 2-(4-octyloxyphenyl)thiophene (compound 23) (17.0 g, 0.0590 mol) in THF (dry, 200 cm 3 ) at −78° C. After stirring for 1 h at −78° C., tri-n-butyltin chloride (30.7 g, 0.0944 mol) was added slowly and the temperature of the reaction mixture was allowed to reach RT after completion of the addition. The reaction mixture was stirred overnight. Water (100 cm 3 ) was added and the product extracted into diethyl ether (2×200 cm 3 ). The combined ethereal extracts were dried (MgSO 4 ), filtered and concentrated under reduced pressure to yield a pale brown oil. The product was not purified further (28.4 g, 90.2%).
2-Bromo-7-[5-(4-octyloxyphenyl)thiophen-2-yl]-9,9-dihexylfluorene (Compound 25)
[0187] A mixture of 2-bromo-7-iodo-9,9-dihexylfluorene (compound 21) (10.0 g, 0.0180 mol), 5-[(4-octyloxyphenyl)-2-tributylstannyl thiophene (compound 24) (11.0 g, 0.0190 mol) and tetrakis(triphenylphosphine)palladium (0) (1.07 g, 0.0009 mol) in DMF (150 cm 3 ) was heated at 90° C. for 24 h. The mixture was allowed to cool to RT and the solution was treated with a saturated potassium fluoride solution (100 cm 3 ) to destroy the tin side products. DCM (2×200 cm 3 ) was added and the combined organic layers were washed with brine (4×200 cm 3 ), dried (MgSO 4 ), filtered and concentrated under reduced pressure. The crude product was purified by gravity column chromatography [silica gel, DCM: hexane, 20%: 80%] to yield a yellow powder (7.60 g, 57%).
Compound 27
[0188] Tetrakis(triphenylphosphine)palladium(0) (0.11 g, 9.80×10 −5 mol) was added to a stirred solution of 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dioctylfluorene (compound 26) (0.63 g, 9.80×10 −4 mol), 2-bromo-7-[5-(4-octyloxyphenyl)thiophen-2-yl]-9,9-dihexylfluorene (compound 25) (1.51 g, 2.16×10 −3 mol) and anhydrous tripotassium phosphate (0.62 g, 2.94×10 −3 mol) in DMF (30 cm 3 ) at RT. The reaction mixture was heated at 90° C. for 24 h. The cooled reaction mixture was added to water (100 cm 3 ) and the product extracted into DCM (2×150 cm 3 ). The combined organic extracts were washed with brine (4×100 cm 3 ), dried (MgSO 4 ), filtered and concentrated under reduced pressure. The product was purified by gravity column chromatography [silica gel, DCM: hexane, 20%: 80%] to yield a light yellow-green glassy material (0.80 g, 50%).
Compound 28
[0189] Boron tribromide (0.14 cm 3 , mol) in DCM (5 cm 3 ) was added dropwise to a cooled (0° C.) stirred solution of compound 9 (0.80 g, 4.91×10 −4 mol) in DCM (50 cm 3 ). The reaction mixture was stirred at RT overnight, then poured onto an ice/water mixture (200 g) and stirred for 30 mins. DCM (150 cm 3 ) was added and the resultant organic layer washed with water (2×100 cm 3 ), dried (MgSO 4 ), filtered and concentrated under reduced pressure. The crude product was purified by gravity column chromatography [silica gel, ethyl acetate:hexane, 30%: 70%] to yield a green glassy material (0.55 g, 79.7%).
Compound 29
[0190] A mixture of compound 10 (0.55 g, 3.92×10 −4 mol), 1,4-pentadien-3-yl 12-bromododecanoate (42) (0.34 g, 9.80×10 −4 mol) and potassium carbonate (0.16 g, 1.18×10 −3 mol) in DMF (30 cm 3 ) was heated at 90° C. for 48 h. The reaction mixture was cooled to RT, water (50 cm 3 ) was added and the product extracted into DCM (2×100 cm 3 ). The combined organic layers were washed with brine (4×100 cm 3 ), dried (MgSO 4 ), filtered and concentrated under reduced pressure. The crude product was purified by gravity column chromatography [silica gel, hexane: DCM: 20%: 80%] to yield a green liquid crystalline material (0.30 g, 39.5%). Transition temp./° C.: T g −2 Cr 80 N 39 I.
[0191] Thin Film Polymerisation and Evaluation
[0192] Thin films of Compounds 3 to 6 and Compunds 9 to 15 were prepared by spin casting from a 0.5%-2% M solution in chloroform onto quartz substrates. All sample processing was carried out in a dry nitrogen filled glove box to avoid oxygen and water contamination. The samples were subsequently baked at 50° C. for 30 minutes, heated to 90° C. and then cooled at a rate of 0.2° C. to room temperature to form a nematic glass. Polarised microscopy showed that no change was observed in the films over several months at room temperature. The films were polymerized in a nitrogen filled chamber using light from an Argon Ion laser. Most of the polymerization studies were carried out at 300 nm with a constant intensity of 100 MWcm −2 and the total fluence varied according to the exposure time. No photoinitiator was used. Temperature dependent polymerization studies were carried out in a Linkham model LTS 350 hot-stage driven by a TP 93 controller under flowing nitrogen gas. A solubility test was used to find the optimum fluence: different regions of the film were exposed to UV irradiation with different fluences and the film was subsequently washed in chloroform for 30 s. The unpolymerized and partially polymerized regions of the film were washed away and PL from the remaining regions was observed on excitation with an expanded beam from the Argon Ion laser. Optical absorbance measurements were made using a Unicam 5625 UV-VIS spectrophotometer. PL and EL were measured in a chamber filled with dry nitrogen gas using a photodiode array (Ocean Optics S2000) with a spectral range from 200 nm to 850 nm and a resolution of 2 nm. Films were deposited onto CaF 2 substrates for Fourier Transform infra-red measurements, which were carried out on a Perkin Elmer Paragon 1000 Spectrometer. Indium tin oxide (ITO) coated glass substrates, (Merck 15 Ω/□) were used for EL devices. These were cleaned using an Argon plasma. 20 A PDOT (EL-grade, Bayer) layer of thickness 45 nm±10% was spin-cast onto the substrate and baked at 165° C. for 30 minutes. This formed a hole-transporting film. One or more organic films of thickness ≈45 nm were subsequently deposited by spin-casting and crosslinked as discussed below. Film thicknesses were measured using a Dektak surface profiler. Aluminum was selectively evaporated onto the films at a pressure less than 1×10 −5 torr using a shadow mask to form the cathode.
[0193] Photopolymerisation Details
[0194] The optimum fluences required in order to polymerize the diene monomers (Compounds 3 to 6) efficiently with a minimum of photodegradation, were found to be 100 Jcm −2 , 20 Jcm −2 , 100 Jcm −2 and 300 Jcm −2 respectively, using the solubility test. As Scheme 6 shows, the 1,6-heptadiene monomer (e.g. Compound 4) forms a network with a repeat unit containing a single ring. Its polymerization rate is equal to that of the 1,4-pentadiene monomer (e.g. Compounds 3 and 5) but the increase of PL intensity after polymerization is less for Compound 4. This may be because of the increased flexibility of the C 7 ring in the backbone of the crosslinked material. The 1,4-pentadiene diene monomers (Compounds 3 and 5) are homologues and differ only in the length of the flexible alkoxy-spacer part of the end-groups. The PL spectrum of Compound 5 with the shorter spacer is significantly different to all other materials before exposure suggesting a different conformation. The higher fluence required to polymerize the 1,4-pentadiene monomer Compound 5 implies that the polymerization rate is dependent on the spacer length: the freedom of motion of the photopolymerizable end-group is reduced, because of the shorter aliphatic spacer in Compound 5. The diallylamine monomer Compound 6 has a significantly different structure to the dienes. It is much more photosensitive than the other diene monomers because of the activation by the electron rich nitrogen atom. Scheme 6 also shows (by way of comparison) that when a methacrylate monomer is employed the polymerization step does not involve the formation of a ring.
[0195] Photopolymerization Characteristics
[0196] The absorbance and PL spectra of 1,4-pentadiene monomer (Compound 3) were measured before and after exposure with the optimum UV fluence of 100 J cm −2 . The latter measurements were repeated after washing in chloroform for 30 s. The absorbance spectra of the unexposed and exposed films are almost identical and the total absorbance decreases by 15% after washing indicating that only a small amount of the material is removed. This confirms conclusively that a predominantly insoluble network is formed.
[0197] The UV irradiation was carried out in the nematic glass phases at room temperature at 300 nm. The excitation of the fluorene chromophore is minimal at this wavelength and the absorbance is extremely low. The experiment was repeated using a wavelength of 350 nm near the absorbance peak. Although the number of absorbed photons is far greater at 350 nm, a similar fluence is required to form an insoluble network. Furthermore excitation at 350 nm results in some photodegradation. UV photopolymerization was also carried out at 300 nm at temperatures of 50° C., 65° C. and 80° C. all in the nematic phase. It was anticipated that the polymerization rate would increase, when the photoreactive mesogens were irradiated in the more mobile nematic phase. However, the fluence required to form the crosslinked network was independent of temperature, within the resolution of our solubility test. Furthermore, the integrated PL intensity from the crosslinked network decreases with temperature indicating a temperature dependent photodegradation.
[0198] Bilayer Electroluminescent Devices
[0199] Bilayer electroluminescent devices were prepared by spin-casting the 1,4-pentadiene monomer (Compound 3) onto a hole-transporting PEDT layer. The diene functioned as the light-emitting and electron-transporting material in the stable nematic glassy state. Equivalent devices using cross-linked networks formed from Compound 3 by photopolymerisation with UV were also fabricated on the same substrate under identical conditions and the EL properties of both types of devices evaluated and compared. The fabrication of such bilayer OLEDs is facilitated by the fact that the hole-transporting PEDT layer is insoluble in the organic solvent used to deposit the electroluminescent and electron-transporting reactive mesogen (Compound 3). Half of the layer of Compound 3 was photopolymerized using optimum conditions and the other half was left unexposed so that EL devices incorporating either the nematic glass or the cross-linked polymer network could be directly compared on the same substrate under identical conditions. Aluminum cathodes were deposited onto both the cross-linked and non cross-linked regions. Polarized electroluminescent devices were prepared by the polymerization of uniformly aligned Compound 3 achieved by depositing it onto a photoalignment layer doped with a hole transporting molecule. In these devices external quantum efficiencies of 1.4% were obtained for electroluminescence at 80 cd m −2 . Three layer devices were also prepared by spin-casting an electron transporting polymer (Compound 7), which shows a broad featureless blue emission, on top of the crosslinked nematic polymer network. In the case of both the three layer and bilayer devices the luminescence originates from the cross-linked polymer network of the 1,4-pentadiene monomer (Compound 3). The increased brightness of the three-layer device may result from an improved balance of electron and hole injection and/or from a shift of the recombination region away from the absorbing cathode.
[0200] Multilayer Device
[0201] A multilayer device configuration was implemented as illustrated in FIG. 2 . A glass substrate 30 (12 mm×12 mm×1 mm) coated with a layer of indium tin oxide 32 (ITO) was cleaned via oxygen plasma etching. Scanning electron microscopy revealed an improvement in the surface smoothness by using this process which also results in a beneficial lowering of the ITO work function. The ITO was coated with two strips (˜2 mm) of polyimide 34 along opposite edges of the substrate then covered with a polyethylene dioxthiophene/polystyrene sulfonate (PEDT/PSS) EL-grade layer 36 of thickness 45±5 nm deposited by spin-coating. The layer 36 was baked at 165° C. for 30 min in order to cure the PEDT/PSS and remove any volatile contaminants. The doped polymer blend of Compounds 1 and 2 was spun from a 0.5% solution in cyclopentanone forming an alignment layer 40 of thickness ˜20 nm. This formed the hole-injecting aligning interface after exposure to linearly polarized CV from an argon ion laser tuned to 300 nm. A liquid-crystalline luminescent layer 50 of Compound 3 was then spun cast from a chloroform solution forming a film of ˜10 nm thickness. A further bake at 50° C. for 30 min was employed to drive off any residual solvent. The sample was heated to 100° C. and slowly cooled at 02° C./min to room temperature to achieve macroscopic alignment of chromophores in the nematic glass phase. Irradiation with UV light at 300 nm from an argon ion laser was used to induce crosslinking of the photoactive end-groups of the Compound 3 to form an insoluble and intractable layer. No photoinitiator was used hence minimizing continued photoreaction during the device lifetime. Aluminium electrodes 50 were vapor-deposited under a vacuum of 100 mbar or better and silver paste dots 52 applied for electrical contact. A silver paste contact 54 was also applied for contact with the indium tin oxide base electrode. This entire fabrication process was carried out under dry nitrogen of purity greater than 99.99%. Film thickness was measured using a Dektak ST surface profiler.
[0202] The samples were mounted for testing within a nitrogen-filled chamber with spring-loaded probes. The polymide strips form a protective layer preventing the spring-loaded test probes from pushing through the various layers. Optical absorbance measurements were taken using a Unicam UV-vis spectrometer with a polarizer (Ealing Polarcaot 105 UV-vis code 23-2363) in the beam. The spectrometer's polarization bias was taken into account and dichroic ratios were obtained by comparing maxima at around 370-380 nm.
[0203] Luminescence/voltage measurements were taken using a photomultiplier tube (EMI 6097B with S11 type photocathode) and Keithley 196 multimeter with computer control. Polarized EL measurements were taken using a photodiode array (Ocean Optics S2000, 200-850 nm bandwidth 2 nm resolution) and polarizer as described above. The polarization bias of the spectrometer was eliminated by use of an input fiber (fused silica 100 μm diameter) ensuring complete depolarisation of light into the instrument.
[0204] Monochrome Backlight
[0205] FIG. 3 shows a schematic representation of a polarised light monochrome backlight used to illuminate a twisted nematic liquid crystal display. The arrows indicate the polarisation direction. An inert substrate 30 (e.g. glass coated with a layer of indium tin oxide (ITO) as in FIG. 2 ) is provided with a layer 50 of a polarised light emitting polymer (e.g. comprising Compound 3 as in FIG. 2 ). The assembly further includes a clean up polariser 60 comprising a high transmission low polarisation efficiency polariser; a twisted nematic liquid crystal display 70; and a front polariser 80. It will be appreciated that the light emitting polymer layer 50 acts as a light source for the liquid crystal display 70.
[0206] Polarised Light Sequential Tri-Color Backlight
[0207] FIG. 3 schematic of a polarised light sequential red, green and blue light emitting backlight used to illuminate a fast liquid crystal display (ferroelectric display). The arrows indicate the polarisation direction. An inert substrate 30 (e.g. glass coated with a layer of indium tin oxide (ITO) as in FIG. 2 ) is respectively provided with red 52, green 54 and blue 56 striped layers of a polarised light emitting polymer (e.g. comprising Compound 3 as in FIG. 2 and a suitable dye molecule as a dopant). The assembly further includes a clean up polariser 60 comprising a high transmission low polarisation efficiency polariser; a fast (ferroelectric) liquid crystal display 70; and a front polariser 80. It will be appreciated that the striped light emitting polymer layer 52, 54, 56 acts as a light source for the fast liquid crystal display 70. The sequential emission of the RGB stripes corresponds with the appropriate colour image on the fast liquid crystal display. Thus, a colour display is seen.
[0208] Alignment Characteristics
[0209] The PL polarization ratio (PL η /PL ⊥ ) of the aligned polymer formed from Compound 3 in its nematic glass phase can be taken as a measure of the alignment quality. Optimum alignment is obtained with the undoped alignment layer for an incident fluence of 50 mJ cm −2 . The alignment quality deteriorates when higher fluences are used. This is expected because there are competing LC-surface interactions giving parallel and perpendicular alignment respectively. When the dopant concentration is 40% or higher there is a detrimental effect on alignment. However with concentrations up to 30% the polarization ratio of emitted light is not severely effected although higher fluences are required to obtain optimum alignment. The EL intensity reaches its peak for the ˜50% mixture. A 30% mixture offers a good compromise in balancing the output luminescence intensity and polarization ratio. From these conditions and using the 30% doped layer we have observed strong optical dichroism in the absorbance (D˜6.5) and obtained PL polarization ratios of 8:1.
[0210] Electroluminescence Characteristics
[0211] Devices made with compound 3 in the nematic glassy state showed poor EL polarization ratios because the low glass transition temperature compromised the alignment stability. Much better performance was achieved when compound 3 was crosslinked.
[0212] A brightness of 60 cd m −2 (measured without polarizer) was obtained at a drive voltage of 11V. The threshold voltage, EL polarization ratio and intensity all depend on the composition of the alignment layer. A luminance of 90 cd m −2 was obtained from a 50% doped device but with a reduction in the EL polarization ratio. Conversely a polarized EL ratio of 11:1 is found from a 20% doped device but with lower brightness. A threshold voltage of 2V is found for the device with a hole-transporting layer with 100% of the dopant comprising compound 2. Clearly a photo-alignment polymer optimised for both alignment and hole-transporting properties would improve device performance. This could be achieved using a co-polymer incorporating both linear rod-like hole-transporting and photoactive side chains. | There is provided a process for forming a light emitting polymer comprising photopolymerization of a reactive mesogen having an endgroup which is susceptible to photopolymerization e.g. by a radical polymerization process. Also provided are methods for using the light emitter in displays, backlights, electronic apparatus and security viewers. | 2 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional Patent Application No. 62/209,804 filed Aug. 25, 2015. The text and contents of that provisional patent application are hereby incorporated into this application by reference as if fully set forth herein.
FIELD OF THE INVENTION
[0002] The present invention generally relates to the field of nutritional supplements. Specifically, embodiments of the present invention relate to nutritional supplements formulated and administered for the prevention and relief of muscle cramps.
DISCUSSION OF THE BACKGROUND
[0003] Muscle cramps, a sudden and involuntary contraction of one or more muscles, can cause excruciating pain and make it temporarily impossible to use the affected muscle. Such cramps may be caused by long periods of exercise or physical labor, particularly in hot weather, or may be caused by certain medical conditions or medications.
[0004] Skeletal muscle cramps that occur during or shortly following exercise in healthy individuals with no underlying metabolic, neurological, or endocrine pathology have been termed “exercise-associated muscle cramps” (EAMC). EAMC may be recognized by acute pain, stiffness, visible bulging or knotting of the muscle, and possible soreness that can last for a varying duration of time (from a few seconds to several days) after the initial cramping event. EAMC is common in both recreational and competitive athletes. The cause of EAMC continues to be unresolved, although some health care professionals believe it to be caused by a decreased supply of oxygen, lactic acid build up, dehydration and/or electrolyte imbalance. Other health care professionals believe the cause to be neuromuscular, in other words, caused by muscle overload and neuromuscular fatigue. Yet others believe that muscle cramps are caused by the nerve—when motor neurons in the spinal cord fire spontaneously and repetitively. In any case, the electrolyte imbalance theory of causation for muscle cramping is not the sole mechanism, but appears to play a role in muscle cramping in situations of excessive heat or dehydration.
[0005] The result of the occurrence of EAMC is that professional and amateur athletes have been removed from competition and game play. The inability of athletes to continue in competitions produces disruptions, frustration and disappointment. For a swimmer, the consequences can be even more dire. Although there have been extensive medical, nutritional and dietary studies conducted and published, previously there has been no consistent, reliable solution to EAMC.
[0006] Regardless of the cause, current treatments and prevention strategies for EAMC such as ingesting fluids containing electrolytes, stretching and other treatment and prevention strategies have been largely unsuccessful. As a result, it is desirable to provide nutritional supplement formulations and methods for the effective prevention and rapid relief of EAMC and other types of muscle cramping.
SUMMARY OF THE INVENTION
[0007] Embodiments of the present invention advantageously provide nutritional supplements and methods for formulating and administering such nutritional supplements for the prevention and relief of EAMC and other forms of muscle cramping. These supplements are unique mixtures most typically comprising cholecalciferol (as Vitamin D3), magnesium glycinate, one or more potassium salts (e.g., potassium chloride, potassium bicarbonate and/or potassium citrate) and/or creatine monohydrate. The supplements and methods disclosed herein rapidly provide nutritional elements and electrolytes at the neuromuscular junction in order to facilitate efficient muscle energy production (adenosine triphosphate (ATP), nutrient uptake and tendon relaxation via the Golgi tendon organ (GTO) inhibitory activity.
[0008] Also disclosed are methods for formulating the nutritional supplements, typically comprising weighing the appropriate quantities of base compounds, pouring the compounds into a resealable bag or a mixing machine, shaking the bag and/or appropriately mixing the base compounds until they are thoroughly blended, breaking up any large particles, if necessary, and re-shaking or re-mixing. In some embodiments, the method may also comprise pouring the mixture into a capsule filling machine, and encapsulating the formulation in an appropriate size capsule.
[0009] Further disclosed are methods of storing and using the nutritional supplements comprising, for an athlete under 200 lbs., taking two (2) capsules at least fifteen (15) minutes before exercise with about 300-500 ml (12-16 fl. oz.) of water or a sports drink. For persons over 200 lbs., three (3) capsules should be taken at least fifteen minutes before exercise. In some instances, the method may also include taking an additional two capsules (or three capsules if over 200 lbs) for high intensity sustained exercise such as marathon running or soccer every two (2) to three (3) hours during continued exercise.
[0010] In very hot or high humidity playing conditions the first repeat dose should taken after 45-60 minutes then 2-3 hourly thereafter. However, the maximum number of doses which may be taken in a 24-hour period is twelve capsules.
[0011] Embodiments of the present invention advantageously provide nutritional supplements for preventing and rapidly relieving muscle cramps by addressing the multiple mechanisms of muscle cramp generation, including neuromuscular junction activity (especially stimulating the Golgi tendon organ inhibitory action) and electrolyte repletion, which are thought to be the cause of muscle cramping, including cramping during exercise.
[0012] It is to be understood that both the foregoing general description and the following detailed description are exemplary, but not restrictive, of the invention. A more complete understanding of the embodiments of the nutritional supplements and methods disclosed herein will be afforded to those skilled in the art.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] FIG. 1 shows the chemical structure of cholecalciferol, a compound used in embodiments of the supplements of the present invention.
[0014] FIG. 2 shows the chemical structure of magnesium glycinate, a compound used in embodiments of the supplements of the present invention.
[0015] FIG. 3 shows the chemical structure of potassium chloride, a compound used in embodiments of the supplements of the present invention.
[0016] FIG. 4 shows the chemical structure of potassium bicarbonate, a compound used in embodiments of the supplements of the present invention.
[0017] FIG. 5 shows the chemical structure of creatine monohydrate, a compound used in embodiments of the supplements of the present invention.
[0018] FIG. 6 shows the chemical structure of potassium citrate, a compound used in embodiments of the supplements of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Reference will now be made in detail to the preferred embodiments of the invention. While the invention will be described in conjunction with the preferred embodiments, it will be understood that they are not intended to limit the invention to these embodiments. On the contrary, the invention is intended to cover alternatives, modifications, and equivalents that may be included within the spirit and scope of the invention. Furthermore, in the following detailed description of the present invention, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will readily be apparent to one skilled in the art that the present invention may be practiced without these specific details.
[0020] Embodiments of the present invention advantageously provide nutritional supplement formulations and methods for preventing and rapidly relieving exercise-associated (and other) muscle cramps. Painful cramps occur when a muscle contracts while in a shortened state. These typically occur in a single group of large muscles that span 2 joints such as the hamstrings, quadriceps, and triceps, but are also seen in the small muscles subjected to repetitive excessive use, such as the calf muscles, and hands, as with writer's cramp.
[0021] It is well known that muscle cramps occur in differing environmental conditions (e.g. hot ambient temperatures, cold temperatures, humid conditions [e.g. such as those to which miners are exposed]), but cramping may also occur in dry conditions (e.g., writer's cramping in dry indoor environments), and in diverse populations. Therefore, it is unlikely that a single factor is causal in all instances.
[0022] Embodiments of the present invention are novel and unobvious combinations of substances which act on the neuromuscular junction and increase adenosine triphosphate (ATP) uptake and utilization, which is the primary source of energy in all living cells. Although the subject specification refers to exercise-associated muscle cramps (EAMC), the formulations and methods described herein may also be effective for the relief of cramping unrelated to active exercise.
[0023] The nutritional supplements of the present invention rapidly provide the critical elements and electrolytes at the neuromuscular junction to facilitate efficient muscle energy uptake and muscle relaxation via the Golgi tendon organ inhibitory activity.
[0024] The basic components of the formulations typically comprise (i) cholecalciferol (as Vitamin D3), (ii) magnesium glycinate, (iii) one or more potassium compounds/salts (e.g., potassium chloride, potassium bicarbonate, potassium citrate, potassium malate, potassium glutamate, etc.) and/or (iv) creatine monohydrate. Preferably, all of these components are used in the formulation as they contribute to the formulation's uniquely efficacious activity in reducing occurrence of cramping during muscle activity. However, in some embodiments, less than all of the components may be used.
[0025] Referring now to FIG. 1 , therein is shown the chemical structure of cholecalciferol. Cholecalciferol (Vitamin D3) receptors have been demonstrated in muscle fibers and the neuromuscular junction. Deficiency of Vitamin D is associated with muscle weakness, increased frequency of falls, and with muscle cramps. Ingested Vitamin D is transferred from the circulation and body fluids into tissues and the bone for storage from where slow release occurs over time to meet the body's basal needs. With rampant Vitamin D insufficiency demonstrated in many populations studied, and the significant increase in demand during vigorous exercise, functioning of the Golgi tendon organs (GTOs) is often hampered.
[0026] GTOs are responsible for inhibitory impulses to the muscle spindle which produces muscle relaxation after contraction. Providing a readily available source of cholecalciferol immediately prior to exercise maintains blood levels (prior to transfer to storage forms) and helps maintain the balance between excitatory impulses from muscle spindles and the critical inhibitory impulses from GTOs, ensuring normal contraction-relaxation signaling of the alpha motor neuron. The unique formulations of the present invention ensure rapid uptake of recently ingested cholecalciferol before distribution into storage forms, producing enhanced muscle and nerve calcium coupling and signal transduction.
[0027] Referring now to FIG. 2 , therein is shown the chemical structure of magnesium glycinate. Magnesium glycinate is a combination of magnesium, an essential mineral and glycine, a non-essential amino acid. It is easily absorbed by the body, and provides a high level of bioavailability. Magnesium deficiency has been described as a major cause of muscle cramps. The immediate availability of magnesium glycinate in delivering this essential cation (carries a net positive electrical charge), to the exercising muscle end plate and ATP-ase pump is an important component of the activity of embodiments of the present invention. Although magnesium glycinate is typically used in preferred embodiments, one or more other forms of magnesium (e.g., magnesium L-threonate, magnesium taurate, magnesium chloride, magnesium lactate, magnesium carbonate, magnesium citrate, etc.) may be used in some embodiments or may be used in combination with magnesium glycinate.
[0028] Embodiments of the present invention may also utilize one or more potassium compounds. For example, in preferred embodiments, one or more of potassium chloride, potassium citrate and/or potassium bicarbonate are utilized. However, other embodiments may also comprise potassium gluconate, potassium sulfate, potassium malate and/or potassium bitartrate.
[0029] Potassium is an important element, the lack thereof which is implicated in electrolyte imbalance culminating in muscle cramps. Potassium is involved in every cellular function and is a critical component of nerve and muscle activity and ATP utilization. The “recommended daily allowance” suggested for potassium is high and very difficult to attain with the modern American diet. The Food and Nutrition Board of the Institute of Medicine suggests an adequate intake of potassium is about 4.7 grams/day and the FDA suggest an intake of 3.6 grams/day. The typical diet contains less than 2 grams/day.
[0030] Most of the body's potassium is stored inside the cells and transported in small amounts to the extracellular compartment by carrier molecules in the cell wall. Potassium and sodium exchange is a dynamic process which is coupled with ATP production. A pre-exercise potassium, cholecalciferol and creatine monohydrate combination optimizes extracellular potassium availability at the neuromuscular spindle to meet the increased demand during vigorous exercise.
[0031] At least 20 milliequivalents (mEq) of potassium is generally recommended for athletes weighing up to 200 lbs. An additional 10 mEq should be added for 200-300 lb. body weight (hence 30 mEq).
[0032] Potassium supplementation at these levels raises no safety concerns in individuals that are healthy enough for sporting activity. Individuals with kidney failure and heart disease must be cleared by their health provider before using the nutritional supplements of the instant invention, or engaging in vigorous sporting activity. The instant nutritional supplements should not be used for any other purpose aside from pre-exercise enhancement of muscle energy production and cramp prevention.
[0033] In FIG. 3 is shown the chemical structure of potassium chloride. Potassium chloride is a metal halide salt composed of potassium and chloride. It is odorless and has a white or colorless vitreous crystal appearance. Potassium chloride dissolves easily in water and has a salty taste when so dissolved. Potassium chloride is used in the treatment of hypokalemia (low concentration of potassium in the blood) and as an electrolyte replenishment.
[0034] Referring now to FIG. 4 , therein is shown the chemical structure of potassium bicarbonate. Potassium bicarbonate is a colorless, odorless, slightly basic, salty substance. It occurs as a soft white granular powder and it is very rarely found in its natural form as a mineral called kalicinite. This is used in some East African tribes as a native salt for cooking, and it may be an environmental factor that contributes to the superior endurance of African long distance runners. Potassium bicarbonate is an important physiologic buffer of organic acids in the body and may be important in reducing the effects of lactic acid generation from anerobic respiration in actively working muscles.
[0035] The U.S. Food and Drug Administration (FDA) recognizes potassium bicarbonate as safe. There is no evidence of human carcinogenicity, no adverse effects of overexposure and it is often added to bottled water for taste enhancement. There are three (3) oxygen atoms in each molecule of potassium bicarbonate and these are readily released with hydrolysis in the stomach.
[0036] FIG. 5 shows the chemical structure of creatine monohydrate. Creatine (as creatine monohydrate) enhances muscle phosphocreatine and increases efficiency of energy metabolism in the form of ATP (adenosine triphosphate) production and utilization. In small amounts, the weight gain, cramping and diarrhea associated with the high dose creatine is avoided (usual maintenance dosing for body building is about 2 gm per day of creatine). The nutritional supplements disclosed herein are not designed for building muscle mass. The low dose creatine enhances uptake and delivery of cholecalciferol, potassium and magnesium by Golgi tendon organs because creatine is actively utilized for ATP production in vigorously exercising muscles.
[0037] Referring now to FIG. 6 , therein is shown the chemical structure of potassium citrate. Potassium citrate appears as a white, odorless, crystalline powder that is water soluble, and is rapidly absorbed when given by mouth. It is an alkaline salt that is often used to reduce the pain and frequency of urination caused by high acidic urine and to treat kidney stones. It is also an important physiologic buffer for organic acids in the body.
[0038] Embodiments of the nutritional supplements disclosed enhance performance, particularly for high intensity activity of relatively short duration (2-3 hours). Repeat dosing is recommended after 1-3 hours of intense activity in order to maintain efficiency of Golgi tendon organ inhibitory cycling.
[0039] The nutritional supplements of the present invention may be formulated as a mixture comprising up to 5.0% cholecalciferol (as Vitamin D3), from 7.5% to 35.0% magnesium glycinate (or other magnesium compounds; e.g., magnesium L-threonate, magnesium taurate, magnesium chloride, magnesium lactate, magnesium carbonate, magnesium citrate, etc.), from 60% to 85.0% potassium salts (e.g., potassium chloride, potassium bicarbonate, potassium citrate, potassium malate, potassium glutamate, etc. providing from 25.0% to 35.0% elemental potassium), and from 7.5% to 25% creatine monohydrate. Percentages shown are by weight compared to the total weight of the formation.
[0040] Most preferably, the nutritional supplements are formulated as a dry mixture comprising up to 1.0% cholecalciferol (as Vitamin D3), from 9.0% to 10.0% magnesium glycinate, from 70.0% to 82.0% potassium compounds/salts (providing from 25.0% to 30.0% elemental potassium) and from 9.0% to 21.0% creatine monohydrate. Percentages shown are by weight compared to the total weight of the formation.
[0041] It is expressly intended that all ranges broadly recited in this document include all narrower ranges that fall within the broader ranges.
[0042] In some aspects, the potassium compounds in the nutritional supplement mixtures of the present invention comprise one or more of potassium citrate, potassium bicarbonate and potassium chloride. However, other potassium compounds may also be used in the formulation (e.g., potassium chloride, potassium bicarbonate, potassium citrate, potassium malate, potassium glutamate, etc.) In typical embodiments, potassium citrate, potassium bicarbonate and potassium chloride are used in the formulation, the combination providing at least 25% elemental potassium when compared to the total weight of the nutritional supplement mixtures. Most preferably, elemental potassium comprises between 29.0% and 30% of the total weight of the nutritional supplement mixtures. The potassium compounds are most typically used in their granular form.
[0043] The weight of Vitamin D3 is calculated based on the use of Vitamin D3 powder having 102,900 International Units (IU) per gram. However, the IU per gram may vary for different lots of the D3 powder and for different manufacturers. Consequently, the weight of Vitamin D3 in the formulation may be adjusted accordingly.
[0044] The weight of magnesium glycinate is based on 15% weight of elemental magnesium to weight of magnesium glycinate (w/w). However, if the weight of elemental magnesium in the magnesium glycinate compound varies or one or more other magnesium compounds are utilized (e.g. magnesium L-threonate, magnesium taurate, magnesium chloride, magnesium lactate, magnesium carbonate, magnesium citrate, etc.) having a different w/w, then the formulation may be adjusted accordingly.
[0045] Creatine monohydrate is typically used in the formulation in a powder form.
Exemplary Formulations
Per 100 Capsules
[0046] The following examples of particular embodiments are given for illustrative purposes only. The examples are not intended to be a limitation on the scope or practice of the invention. Numerous variations of the present invention are possible without departing from the spirit and scope of the invention. The following examples are given on a per 100 capsule basis and are prepared by a simple mixing procedure.
Example 1
[0047] Vitamin D3 powder (102,900 IU/gm): 0.750 gm; magnesium glycinate (15% w/w): 9.500 gm; potassium chloride (USP granular): 4.500 gm; potassium bicarbonate (USP granular): 80 gm; and creatine monohydrate powder: 25.700 gm.
Example 2
[0048] Vitamin D3 powder (102,900 IU/gm): 1.151 gm; magnesium glycinate (15% w/w): 12.500 gm; potassium chloride (USP granular): 6.300 gm; potassium bicarbonate (USP granular): 75.500 gm; and creatine monohydrate powder: 15.000 gm.
Example 3
[0049] Vitamin D3 powder (102,900 IU/gm): 0.972 gm; magnesium glycinate (15% w/w): 10.000 gm; potassium chloride (USP granular): 5.000 gm; potassium bicarbonate (USP granular): 3.000 gm; potassium citrate (USP granular): 76.500 gm; and creatine monohydrate powder: 12.500 gm.
Example 4
[0050] Vitamin D3 powder (102,900 IU/gm): 1.250 gm; magnesium glycinate (15% w/w): 11.900 gm; potassium chloride (USP granular): 4.800 gm; potassium bicarbonate (USP granular): 38.000 gm; potassium citrate (USP granular) 42.500 gm and creatine monohydrate powder: 22.730 gm.
Example 5
[0051] Vitamin D3 powder (102,900 IU/gm): 1.000 gm; magnesium glycinate (15% w/w): 10.000 gm; potassium chloride (USP granular): 5.00 gm; potassium citrate (USP granular): 80 gm; and creatine monohydrate powder: 25.00 gm.
Example 6
[0052] Vitamin D3 powder (102,900 IU/gm): 0.972 gm; magnesium glycinate (15% w/w): 10.000 gm; potassium citrate (USP granular): 80.000 gm; potassium bicarbonate (USP granular): 2.500 gm; potassium chloride (USP granular): 2.500 gm; creatine monohydrate powder: 10.000 gm.
Example 7
[0053] Vitamin D3 powder (102,900 IU/gm): 1.000 gm; magnesium glycinate (15% w/w): 15.00 gm; potassium citrate (USP granular): 75 gm; potassium bicarbonate (SP granular): 5.00 gm; creatine monohydrate powder 15.000 gm.
[0054] As indicated above, these are just a few examples of the compositions of the nutritional supplements of the present invention and are for illustrative purposes only.
Exemplary Methods of Formulating
[0055] Equipment and devices that may be utilized to prepare the formulation comprise an analytical or precision laboratory balance, (e.g., Ohaus™ Explorer balance, Adam Equipment™ Nimbus, Mettler Toledo™ Excellence, etc.), weigh boats, one or more mixing containers such as reclosable bags (e.g., Zip Loc™ or similar) or mixing machine (e.g., Ross™ Pharmaceutical Mixer, Design Integrated Technology (DIT)™, etc.), a capsule filling machine and vibrator (e.g., Jaansum™, Torpac™ or similar), acrylic roller (or other appropriate device for breaking up large particles), if necessary, and 20 dram amber vials (or other appropriate vials). In some embodiments (e.g., when the supplements are not encapsulated), a capsule filling machine and vibrator may not be necessary.
[0056] Methods for formulating the nutritional supplements of the present invention comprise: (1) weighing the appropriate quantities of cholecalciferol (as Vitamin D3), magnesium glycinate (and/or one or more other magnesium compounds), potassium compounds/salts (e.g. potassium chloride, potassium bicarbonate, potassium citrate, potassium malate, potassium glutamate, etc.) and/or creatine monohydrate; (2) pouring the dry compounds into a mixing container (e.g. reclosable bag) or mixing machine; and (3) mixing and/or shaking the compounds (in some embodiments, continuously) until all compounds are thoroughly blended. In some embodiments, the method may also comprise: (4) breaking up any large particles using an acrylic roller or similar device; and (5) re-mixing. In some further embodiments, the method may also comprise: (6) pouring and/or otherwise transferring the contents into a capsule machine; and (7) encapsulating in the appropriate size capsule. For example, capsule #00 clear with a clear capsule cap or other suitable capsule may be utilized. The compounds may be mixed and added in any order, and in some embodiments, steps of the method (e.g., breaking up large particles by rolling an acrylic roller or other device) may be performed on the individual compounds before they are weighed and added. The filled capsules should be stored in an air-tight container and protected from light and/or heat.
[0057] Most typically the nutritional supplements of the present invention are encapsulated, wherein each capsule comprises approximately 1000 IU of Vitamin D3 (approximately 9.72 mg), 850 mg of one or more potassium compounds (most typically a combination of potassium citrate, potassium bicarbonate and potassium chloride providing at least 300 mg of elemental potassium), 100 mg of creatine monohydrate and 100 mg of magnesium glycinate. However, in other embodiments, other quantities of the compounds may be formulated as described above and may be encapsulated. When the formulation is not encapsulated, a dose typically comprises approximately 1050 mg to 1250 mg of the mixture depending on the exact formulation utilized.
Exemplary Methods of Using
[0058] Typically, the nutritional supplements of the present invention should be used within one year of filling. For best results, the nutritional supplements should be taken at least fifteen (15) minutes before exercise with about 300-500 ml (12-16 fl. oz.) of a hypnotic solution such as water or a sports drink. Two (2) capsules (or the equivalent) are recommended for athletes weighing less than 200 lbs. For weight between 200 and 300 lbs., 3 capsules (or the equivalent) are recommended. If high intensity activity is undertaken for long periods of time, or in high humidity and heat, the dose may be repeated one (1) to two (2) hours after the initial dose up to the maximum of twelve capsules in a 24-hour period. Cramping in children less than 12 years of age is uncommon in the absence of medical illness, and thus, parents of children under 12 should consult a physician before use. | Nutritional supplements that reduce the occurrence of and/or prevent and relieve exercise-associated muscle cramps (EAMC) as well as other forms of skeletal muscle cramping are disclosed. The supplements typically comprise Vitamin D3, one or more potassium compounds, creatine monohydrate and magnesium glycinate (and/or other magnesium compounds), and advantageously reduce or eliminate the acute pain, disruptions in the ability to compete, and the associated frustration and disappointment of EAMC and other muscle cramps Aspects of the present invention also provide methods of formulating and using such nutritional supplements for the prevention and relief of muscle cramping. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to space frame systems utilizing nodal connectors and interposed struts for creating structural configurations, and more particularly to such space frame systems that typically are used as construction toys, creative sculptures and educational aids.
2. Brief Description of the Prior Art
The prior art discloses a variety of structural systems having connectors and struts for assembling different space frame configurations. These prior art configurations suffer from such problems as confusion due to connectors and struts of different sizes and shapes, lack of versatility in relationships among the struts and connectors, unduly heavy and bulky components causing difficulties in shipment and storage, and lack of dimensional stability when assembled.
SUMMARY OF THE INVENTION
The primary object of the present invention is to provide a novel system of nodal connectors and interposable struts, which provide versatile relationships among the connectors and struts, which are composed of compact and light materials, which occupy restricted space during shipment and storage, but nevertheless can be assembled readily into dimensionally stable configurations of very large size.
Each of the nodal connectors is an assemblage of three flat, semi-rigid elements all of which have exterior peripheries of particular design and at least two of which have interior passages of particular design. The exterior peripheries and interior passages provide internal and external interacting profiles including notches and slots by which the three elements may be snapped together into three orthogonal planes. Each of these elements provides prongs by which the nodal connectors may be joined by struts. When a connector is assembled, the prongs project outwardly from a common geometrical center. The struts, in one form, are elongated tubular straws, which have oppositely positioned punctures or apertures along diameters that are near the ends of the struts. The ends of these struts receive the prongs in such a way that oppositely directed catches on the prongs project into the apertures, whereby the struts and the connectors become joined. In one embodiment of the invention, there are 12 prongs and the basic space frame structure is tetrahedral or octahedral. In another embodiment, there are 18 prongs and the basic space frame structure is parallelepiped, although tetrahedral and octahedral configurations are not precluded.
Other objects of the present invention will in part be obvious and will in part appear hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
For a fuller understanding of the nature and objects of the present invention, reference is made to the following description, which is to be taken in connection with the accompanying drawings wherein:
FIG. 1a is a plan view of an inner flat element of the present invention;
FIG. 1b is a plan view of a medial flat element of the present invention;
FIG. 1c is a plan view of an outer flat element of the present invention;
FIG. 2 is a perspective view showing a partial assembly of the inner and medial elements, ready for assembly with the outer element;
FIG. 3 is a perspective view showing a complete assembly of the inner, medial and outer elements forming one preferred embodiment of a three dimensional connector;
FIG. 4 is a perspective view of a strut in accordance with the present invention;
FIG. 5 is a perspective view of a minimal three dimensional structure in the form of a pyramidal configuration in accordance with the present invention;
FIG. 6 is a perspective view of a compact kit containing components that embody the present invention;
FIG. 7a is a plan view of another inner flat element of the present invention;
FIG. 7b is a plan view of another medial flat element of the present invention;
FIG. 7c is a plan view of another outer flat element of the present invention;
FIG. 8 is a perspective view showing a partial assembly of the inner and medial elements of FIGS. 7a and 7b, ready for assembly with the outer element of FIG. 7c.
FIG. 9 is a perspective view showing a complete assembly of the inner, medial and outer elements of FIGS. 7a, 7b and 7c, forming a three dimensional connector;
FIG. 10 is a perspective view of a minimal three dimensional structure, utilizing connectors of the type shown in FIG. 9, in the form of a cubical configuration in accordance with the present invention; and
FIG. 11 is a perspective view of another compact kit containing components that embody the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The Embodiment of FIGS. 1 to 6
FIGS. 1a, 1b and 1c are plan views of an inner element 30, a medial element 32 and an outer element 34, in accordance with the present invention. In one embodiment, each of these elements is stamped from a sheet of a semi-rigid sheet material that quickly resumes its original flatness after being slightly deformed. Preferred sheet materials are composed of plastic or cardboard. In another embodiment, each of these elements is stamped from a sheet of thin aluminum that quickly resumes its original flatness after being slightly deformed. The polymeric composition and thickness of the polymeric elements is such that they may be manually deformed or flexed slightly without cracking to permit them to be assembled in a manner to be described below. The thickness of the aluminum is such that the slight deformation necessary during assembly does not exceed the elastic limit of the aluminum sheet.
As shown, inner element 30 has an annulate body with: a circular opening that provides an internal profile 36, and an external periphery that provides an external profile 38. Internal profile 36, which is uninterrupted, is developed about a geometrical center 40. In an alternative embodiment inner element 30 has no opening. External profile 38 has four shallow notches, one being shown at 42, which are positioned along orthogonal diameters 39, 43 that intersect at geometrical center 40. External profile 38 has four outwardly projecting prongs 44, which are positioned along orthogonal diameters 41, 45 that intersect at geometrical center 40. Any diameter that lies along a notch 42 is angularly spaced by 45 degrees from an adjacent diameter that lies along a prong 44. It will be noted that each prong 44 has an inner stem 46 and an outer cap 48. In the illustrated embodiment, the edges of stem 46 continue as slits through periphery 38 into the annulate body of element 30 to facilitate slight movement of prong 44 into and out of the plane of element 30. In an alternative embodiment, these slits are omitted. Because stem 46 is narrower than cap 48, two oppositely directed catches 50 are provided at the junctions of stem 46 and cap 48.
As shown in FIG. 1b, medial element 32 has an annulate body with a generally circular opening that provides an internal profile 52, and an external periphery that provides an external profile 54. Internal profile 52, which is developed about a geometrical center 56, is interrupted by two relatively deep slots, one being shown at 58, which are oppositely directed along a diameter 62 through geometrical center 56. External profile 54 has two shallow notches, one being shown at 60, along a diameter 64 through geometrical center 56. Diameters 62 and 64 are at right angles with respect to each other. External profile 54 has four prongs, one being shown at 61, each of which is shaped like a counterpart prong 44 in FIG. 1a. Pairs of prongs 61 are oppositely directed along diameters 63 and 65, which intersect at geometrical center 56 and are at right angles with respect to each other. The angular spacing between diameters 63 and 64 is 45 degrees. The angular spacing between diameters 62 and 65 is 45 degrees.
As shown in FIG. 1c, outer element 34 has an annulate body with a generally circular opening that provides an internal profile 66, and an external periphery that provides an external profile 68. Internal profile 66, which is developed about a geometrical center 70, is interrupted by four relatively deep slots, one being shown at 72. Diametrically opposed pairs of slots 72 are directed along two mutually perpendicular axes 74, 76, which intersect at geometrical center 70. External profile 68 has four prongs, one being shown at 78, each of which is similar to a counterpart prong 44 in FIG. 1a. Diametrically opposed pairs of prongs are oppositely directed along diameters 80 and 82, which intersect at geometrical center 70 and are at right angles with respect to each other. The angular spacing between diameters 76 and 82 is 45 degrees.
It is to be noted that the radial distances from geometric center 40 to the four notches 42 of element 30 are equal; the radial distances from geometrical center 56 to the two notches 60 of element 32 are equal; and the radial distance from geometrical center 40 to any notch 42 is equal to the radial distance from geometrical center 56 to any notch 60. Also, the radial distances from the geometrical center to the outer extremities of the two slots 58 are equal; and the radial distances from the geometrical center to the outer extremities of the four slots 72 are equal. Also, radial distances from geometrical center 40 to the outer extremity of each prong 44, the radial distances from geometrical center 56 to the outer extremity of each prong 61, and the radial distances from geometrical center 70 to the outer extremity of each prong 78 all are equal to each other. The inner ends of all notches are the same distance from the center as the outer ends of all slots, so that the pieces spring back to an undeflected state when assembled.
Aside from their prongs and notches, the different external profiles of elements 30, 32 and 34 are recognizably different, external profile 38 being generally circular, external profile 54 being generally oblate, and external profile 68 being generally square. FIG. 2 illustrates the sequence by which the three elements 30, 32 and 34 are assembled. First, circular element 30 and oblate element 32 are oriented in perpendicular planes. Next, circular element 30 is manually deformed sufficiently to permit it to be inserted through the opening in oblate element 32 in such a way that two diametrically opposed notches 42 of circular element 30 snap into the two diametrically opposed slots 58 of oblate element 32 to form an intermediate assemblage 59. Then, square element 34 is oriented in a plane that is perpendicular to the planes of both circular element 30 and oblate element 32. Finally, the intermediate assemblage is manually deformed sufficiently for insertion into the central opening of square element 34 in such a way that the exposed diametrically opposed notches of circular element 30 and oblate element 32 snap into the four slots 72 of square element 34.
The completed assemblage is shown in FIG. 3 as a dimensionally stable three-dimensional structure having 12 prongs, of which any three present outer caps that can rest on a plane to establish a fixed orientation for the structure. Each of these prongs is adapted for seating within the end of a strut of the type shown in FIG. 4 at 84. In the illustrated embodiment, strut 84 is in the form of a thin-walled elongated narrow tube composed of a semi-rigid polymer. Adjacent to each end of the polymeric strut are pairs of diametrically opposed punctures or apertures 86. When the cap of one of the prongs is inserted into an end of strut 84, the circular cross-section at the end of the strut is deformed to accommodate the cross-sectional width of the cap, which is slightly greater than the normal internal diameter of the strut. Further insertion of the cap into the end of the strut causes opposed catches 50 to snap into the opposed punctures 86. In an alternative embodiment, for use in connection with aluminum flat elements, struts composed of solid wood with slotted ends are used.
FIG. 5 illustrates a simple tetrahedral structure which has been assembled from four connectors 88, 90, 92 and 94 and six struts 96, 98, 100, 102, 104 and 106, embodying the present invention. It will be observed that each of the three innermost prongs of each connector is joined by a strut to one of the three innermost prongs of another connector. The arrangement also is such that the three lowermost prongs of each of the three lower connectors contact the flat surface on which it rests. FIG. 6 shows a stack 106 of circular elements 30, a stack 108 of oblate elements 32, a stack 110 of square elements 34, and a supply 112 of parallel struts 84, confined within compartments of a box 114 for storage and shipment as a light, compact product.
The Embodiment of FIGS. 7a to 11
FIGS. 7a, 7b and 7c are plan views of an inner element 130, an medial element 132 and an outer element 134, in accordance with the present invention. Each of these elements is stamped from a sheet of a semi-rigid polymer. The polymeric composition and thickness of these elements is such that they may be manually flexed slightly without cracking to permit them to be assembled in a manner to be described below.
As shown, inner element 130 has an annulate body with a circular opening that provides an internal profile 136, and an external periphery that provides an external profile 138. Internal profile 136, which is uninterrupted is developed about a geometrical center 140. External profile 138 has four shallow notches, one being shown at 142, which are positioned along perpendicular diameters 139, 143 that intersect at geometrical center 140. External profile 138 has four outwardly projecting prongs one being shown at 144, which are positioned along perpendicular diameters 141, 145 that intersect at geometrical center 140. Any diameter that lies along a notch 142 is angularly spaced from an adjacent diameter that lies along a prong 144 by 45 degrees. It will be noted that each prong 144 has an inner stem and an outer cap that are identical to their counterparts in FIGS. 1a, 1b, 1c. Because the stem is narrower than the cap, two oppositely directed catches are provided at the junction of the stem and the cap.
As shown, medial element 132 has an annulate body with a generally circular opening that provides an internal profile 152, and an external periphery that provides an external profile 154. Internal profile 152, which is developed about a geometrical center 156, is interrupted by two relatively deep slots, one being indicated at 158, which are oppositely directed along a diameter 162 through geometrical center 156. External profile 154 has two shallow notches, one being shown at 160, along a diameter 164 through geometrical center 156. Diameters 162 and 164 are at right angles with respect to each other. External profile 154 has six prongs, one being shown at 161, each of which is similar to a counterpart prong 44 in FIG. 1(a). Pairs of prongs 161 are oppositely directed along diameters 163, 162 and 165, which intersect at geometrical center 156 and are angularly spaced in sequence from each other and from diameter 164 by 45 degrees.
As shown, outer element 134 has an annulate body with a generally circular opening that provides an internal profile 166, and an external periphery that provides an external profile 168. Internal profile 166, which is developed about a geometrical center 170, is interrupted by four relatively deep slots, one being shown at 172, which are oppositely directed along two mutually perpendicular axes 174, 176 that intersect at geometrical center 170. External profile 168 has eight prongs, one being shown at 178, each of which is similar to a counterpart prong 44 in FIG. 1(a). Pairs of prongs are oppositely directed along diameters 174, 180, 176, and 182, which intersect at geometrical center 170 and are spaced at sequential angular intervals of 45 degrees.
It is to be noted that the radial distances from geometric center 140 to the four notches 142 of inner element 130 are equal, that the radial distances from geometrical center 156 to the two notches 160 of medial element 132 are equal, and that the radial distances from geometrical center 140 to a notch 142 is equal to the radial distance from geometrical center 156 to a notch 160. Also, the radial distances from the geometrical center to the outer extremities of the two slots 158 are equal; and the radial distances from the geometrical center to the outer extremities of the four slots 172 are equal. Also, the radial distances from geometrical center 140 to the outer extremity of each prong 144, the radial distance from geometrical center 156 to the outer extremity of each prong 161, and the radial distance from geometrical center 170 to the outer extremity of each prong 178 all are equal to each other.
Aside from their prongs and notches, the different external profiles of elements 130, 132 and 134 are recognizably different from each other external profile 138 of inner element 130 being four-pronged, external profile 154 of medial element 132 being six-pronged, and external profile 168 of outer element 134 being eight-pronged.
FIG. 8 illustrates the sequence by which the three elements are assembled. First, inner element 130 and medial element 132 are oriented in perpendicular planes. Next inner element 130 is manually deformed sufficiently to permit it to be inserted through the opening in medial element 132 in such a way that two diametrically opposed notches 142 of inner element 130 snap into the two diametrically opposed slots 158 of medial element 132 to form an intermediate assemblage. Then outer element 134 is oriented in a plane that is perpendicular to the planes of both inner element 130 and medial element 132. Finally, the intermediate assemblage is manually deformed sufficiently for insertion into the central opening of outer element 134 in such a way that the exposed diametrically opposed notches of inner element 130 and medial element 132 snap into the four slots 172 of outer element 134.
The complete assemblage is shown in FIG. 9 as a dimensionally stable solid structure having 18 prongs, of which a set of outer caps can rest on a plane to establish a fixed orientation for the structure. Each of these prongs is adapted for seating within the end of a strut of the type shown in FIG. 4 at 84 and described earlier.
FIG. 10 illustrates a simple cubic structure which has been assembled from eight connectors 188, 190, 192, 194, 196, 198, 200, 202 and sixteen struts 204, 206, 208, 210, 212, 214, 216, 218, 220, 222, 224, 226, 228, 230, embodying the present invention. It will be observed that each of a set of innermost prongs of each connector is joined by a strut to one of a set of the innermost prongs of another connector. It will be observed that the struts are of two lengths in accordance with the edges and diagonals of a cube. The arrangement is such that each of the prongs of the lower connectors contact the flat surface on which they rest. FIG. 11 shows stacks of inner, medial and outer elements 130, 132 and 134, together with a supply of struts of two lengths, confined within compartments of a box 232 for storage and shipment as a light, compact product.
OPERATION
The operation of the elements of FIGS. 1a, 1b and 1c is similar to the operation of elements 7a, 7b and 7c. In each case a supply of the elements together with connectors, is shipped and stored in a compact box. A model connector is assembled by slight deformation of the inner member and insertion into the intermediate member, and then by slight deformation of the inner and intermediate members and insertion into the outer member. All three members then are manipulated until their notches and slots map into engagement. When several of such model connectors have been assembled, a space frame can be erected connecting the outwardly projecting prongs of paired nodes together with struts.
In a typical system of the present invention, the distance between the extremities of diametrically opposed prongs is 6.1 centimeters, the width of a cap is 0.7 centimeters, the length of a strut is 20 centimeters, the depth of a notch is 0.1 centimeter, the depth of a slot is 0.7 centimeters the thickness of an element is 0.5 centimeter, and the diametric thickness of a straw is 0.2 centimeter. In one form the elements of FIGS. 1a, 1b, 1c, 7a, 7b and 7c all are stamped from a semi-rigid polymer such as polycarbonate having a thickness ranging from 5 to 25 mils. In another form, the elements of FIGS. 1a, 1b, 1c, 7a, 7b and 7c all are stamped from aluminum sheet having a thickness of approximately 125 mils. The maximum outer diameter of these elements typically ranges from 3 to 5 inches. Strut 84 is composed of a semi-rigid polymer such as polypropylene.
With components of the foregoing dimensions, a three dimensional space frame filling a sizable room can be constructed from a box of inner, medial and outer elements and struts as shown in FIGS. 6 and 11. | The construction system of the present invention comprises a plurality of connectors and a plurality of struts, each of the connectors including three discrete flat elements interconnected in three mutually perpendicular planes, each of the three flat elements being composed of a semi-rigid material, each of the three flat elements having a plurality of outwardly directed prongs, and each of the struts being tubes into which the prongs project. The three flat elements are connected by engaging notches and slots. The prongs and the struts are connected by engaging catches and apertures. At least two of the elements have central openings presenting internal profiles and outer peripheries presenting external profiles. | 8 |
BACKGROUND OF THE INVENTION
The invention is directed to a process for the resolution of the racemate S-(carboxymethyl)-(RS)-cysteine, especially for the purpose of recovery of S-(carboxymethyl)-(R)-cysteine. This substance is needed for pharmaceutical purposes and serves for example, as a mucolyticum.
It is known to produce S-(carboxymethyl)-(R)-cysteine by reacting (R)-cysteine--also called L-cysteine--with chloroacetic acid in alkali medium (Armstrong, J. Org. Chem., Vol. 16 (1951), pages 749 to 753).
The (R)-cysteine needed for this purpose as starting material is generally obtained from keratin containing natural materials. For this purpose these are hydrolyzed; the (RR)-cystine set free is separated and reduced to (R)-cysteine (Org. Synth., Vol. 5 (1925), pages 39 to 41); German OS No. 2653332 (and related Scherberich U.S. Pat. No. 4,245,117), Vigneaud, J. Amer. Chem. Soc., Vol. 52 (1930), pages 4500-4504). However, suitable natural materials are only available to a limited extent.
In the synthetic production of cysteine, for example from thiazolines-3 substituted in the 2-position via the corresponding thiazolidin-4-carbonitrile the racemate (RS)-cysteine is formed (German OS No. 2645748). It is known to obtain (R)-cysteine by reacting the (RS)-cysteine with dicyanidiamide to form (RS)-2-guanidine-1,3-thiazolidin-4-carboxylic acid, from this with the help of the copper complex salt of (R)-aspartic acid there is separated the (R)-2-guanidin-1,3-thiazolidin-4-carboxylic acid and subsequently there is split off from this the (R)-cysteine (German AS No. 1795021). This process for the recovery of the (R)-cysteine thus is cumbersome and expensive which is unsuited for use on an industrial scale.
SUMMARY OF THE INVENTION
It has now been found that the racemate S-(carboxymethyl)-(RS)-cysteine is resolved by means of the optical isomers of 1-phenyl-ethylamine. While in the previous process first (R)-cysteine is obtained in a given case through the cumbersome resolution of the racemate (RS)-cysteine, and the (R)-cysteine reacted to S-(carboxymethyl)-(R)-cysteine, rather now there is first reacted (RS)-cysteine to S-(carboxymethyl)-(RS)-cysteine and then this racemate resolved. This resolution can be carried out in a simple manner and yields the optical isomers of the S-(carboxymethyl)-cysteine in high yields in outstanding optical and chemical purity.
The S-(carboxymethyl)-(RS)-cysteine is produced from the (RS)-cysteine in the same and known manner as S-(carboxymethyl)-(R)-cysteine from the (R)-cysteine, namely for example, by conversion by means of chloroacetic acid in alkaline medium according to the process set forth in Armstrong, J. Org. Chem., Vol. 16 (1951), pages 749-753.
According to the invention the S-(carboxymethyl)-(R)-cysteine is separated from the racemate by means of (R)-1-phenyl-ethylamine and the S-(carboxymethyl)-(S)-cysteine by means of (S)-1-phenyl-ethylamine. The salts formed from (R)-1-phenyl-ethylamine and S-(carboxymethyl)-(R)-cysteine as well as from (S)-1-phenyl-ethylamine and S-(carboxymethyl)-(S)-cysteine previously have not been described. The salt of (R)-1-phenyl-ethylamine and S-(carboxymethyl)-(R)-cysteine is considerably less soluble than the diastereomer salt thereto from (R)-1-phenyl-ethylamine and S-(carboxymethyl)-(S)-cysteine; the salt from (S)-1-phenyl-ethylamine and S-(carboxymethyl)-(S)-cysteine is considerably less soluble than the diastereomer salt thereto from (S)-1-phenyl-ethylamine and S-(carboxymethyl)-(R)-cysteine.
To carry out the process of the invention the procedure is as customary in the resolution of a racemate. The racemate S-(carboxymethyl)-(RS)-cysteine in the presence of a solvent is brought together with the desired optical isomer of 1-phenylethylamine, and then the diastereomer salts formed are separated.
The salts which are diastereomers to each other show sufficiently large differences in solubility in numerous solvents. For example water belongs to this class of solvents. Preferably there are used as solvents primary or secondary alkanols having up to 6 carbon atoms or ethers and among these solvents especially those which are unlimitedly miscible with water. For example, there can be used hexan-1-ol, butan-1-ol, methyl tert.butyl ether and especially methanol, ethanol, propan-2-ol, dioxane and tetrahydrofuran. Other solvents include propan-1-ol, butan-2-ol, 2-methyl-propan-1-ol. The solvents can also be used in mixtures with each other or in mixtures with water, but the mixtures are suitably so selected that the solvents form a single phase.
The racemate S-(carboxymethyl)-(RS)-cysteine can be employed in solid form or as a suspension or solution in the solvent, the optical isomer of the 1-phenyl-ethylamine either diluted with a solvent or undiluted. The optical isomer of 1-phenyl-ethylamine and the racemate S-(carboxymethyl)-(RS)-cysteine can be employed in any desired proportion to each other. However, generally it is suitable to employ per mole of the racemate not less than about 0.5 and not more than about 5.0 moles of the optical isomer. Preferably, per mole of the racemate there is used 0.8 to 1.1, especially 1.0 mole of the optical isomer. There can be employed all temperatures at which the solvent is present in liquid form.
For separation of the diastereomer salts the preferred procedure is by a fractional crystallization in the customary manner. The mixture is brought to elevated temperatures, preferably to temperatures near the boiling point, so much solvent used that all materials are dissolved, and subsequently the solution cooled for the crystallization.
The concerned S-(carboxymethyl)-cysteine enantiomer is separated from the precipitated salts from S-(carboxymethyl)-(R)-cysteine and (R)-1-phenyl-ethylamine or S-(carboxymethyl)-(S)-cysteine and (S)-1-phenylethylamine by treating the salts with strong acids, preferably strong mineral acids such as hydrochloric acid. Other mineral acids include hydrobromic acid and sulfuric acid.
Unless otherwise indicated all parts and percentages are by weight.
The compositions can comprise, consist essentially of, or consist of the stated materials and the process can comprise, consist essentially of, or consist of the stated materials.
DETAILED DESCRIPTION
Examples
The optically active materials obtained in each case were examined as to their specific rotation [α] D 20 . This is given in degrees·cm 3 /dm.g. Percent data are weight percents.
A. PRODUCTION OF S-(CARBOXYMETHYL)-(RS)-CYSTEINE
As starting material there served (RS)-cysteine hydrochloride which was produced by the process of German OS No. 2645748. 140 grams (1 mole) of this material together with 160 grams (4 moles) of sodium hydroxide were dissolved in 1000 ml of water. To this solution there was first added 3 grams of sodium hydrogen sulfide and then in the course of 45 minutes 95 grams (1 mole) of monochloroacetic acid. The temperature of the mixture in the meanwhile was held at 20° C. and after that held for 3 hours at 20° to 30° C. The reaction mixture was subsequently adjusted to a pH of 3.0 by addition of concentrated, aqueous hydrochloric acid. Hereby the S-(carboxymethyl)-(RS)-cysteine separated out. It was filtered off at 10° C. and washed with water until it was free from chloride ions. Then it was dried under reduced pressure at 105° C. The yield was 173 grams, corresponding to 97% based on the cysteine hydrochloride employed. The melting point (decomposition point) of the S-(carboxymethyl)-(RS)-cysteine was 188° to 192° C.
B. RESOLUTION OF THE RACEMATE S-(CARBOXYMETHYL)-(RS)-CYSTEINE
Example 1
100 grams (0.56 mole) of the racemate S-(carboxymethyl)-(RS)-cysteine obtained according to process A were suspended in 1500 ml of methanol. There were added to the suspension 50 ml of water and 1000 ml (0.78 mole) of (S)-1-phenyl-ethylamine. The mixture was held for one hour under reflux at the boiling point, then slowly cooled to 25° C. and filtered with suction. The residue was washed with 150 ml of methanol and dried at 30° C. and 25 mbar. The material recovered was the salt of S-(carboxymethyl)-(S)-cysteine and (S)-1-phenyl-ethylamine. The yield was 42.5 grams, corresponding to 50%, based on the S-(carboxymethyl)-(S)-cysteine contained in the racemate. The specific rotation of the salt obtained was +20.5° (c=1 in water). The elemental analysis showed C=51.81% (51.98%); H=6.69 (6.71%); N=9.58% (9.32%); S=10.79% (10.68%). (In parantheses calculated for C 13 H 20 N 2 O 4 S).
36.5 grams of the salt of S-(carboxymethyl)-(S)-cysteine and (S)-1-phenyl-ethylamine were dissolved in 100 ml of water. There were mixed into the solution 300 ml of methanol and the mixture adjusted to a pH of 3.0 with concentrated, aqueous hydrochloric acid. Hereby the S-(carboxymethyl)-(S)-cysteine precipitated. It was filtered off under suction, washed with 30 ml of cold water and dried at 105° C. and 25 mbar. The yield was 21.9 grams, corresponding to 100% based on the salt employed. The melting point (decomposition point) of the S-(carboxymethyl)-(S)-cysteine was 188° to 192° C. and the specific rotation +33.6° (c=10 in aqueous sodium hydroxide solution, pH 6.0).
EXAMPLE 2
The procedure was as in Example B1 but instead of (S)-1-phenyl-ethylamine there were employed 100 ml of (R)-1-phenyl-ethylamine..sup.(*) The yield was 42.2 grams, corresponding to 50%. The rotation of the salt was -20.4° (c=1 in water). The elemental analysis was C=51.79% (51.98%); H=6.58% (6.71%); N=9.30% (9.32%); S=10.60% (10.68%). (In parantheses calculated for C 13 H 20 N 2 O 4 S.)
From 36.5 grams of the salt of S-(carboxymethyl)-(R)-cysteine and (R)-1-phenyl-ethylamine there were obtained 21.9 grams, corresponding to 100% yield of S-(carboxymethyl)-(R)-cysteine. The melting point (decomposition point) was 187° to 190° C. and the rotation -33.6° (c=10 in aqueous sodium hydroxide solution, pH 6.0).
The entire disclosure of German priority application No. P 3134106.3 is hereby incorporated by reference. | There is described the resolution of the racemate S-(carboxymethyl)-(RS)-cysteine. It is carried out by means of the optical isomers of 1-phenyl-ethylamine. This process makes it possible to obtain in a simple manner S-(carboxymethyl)-(R)-cysteine which is important for pharmaceutical purposes and is made from synthetically produced cysteine. | 2 |
BACKGROUND OF THE INVENTION
1. Technical Field
The present invention relates generally to lane markers for swimming pools and, more particularly, to a swimming pool lane marker that may be used by a visually impaired swimmer. Specifically, the invention relates to a swimming pool lane marker for the visually impaired that creates a line of bubbles down the middle of the swimming lane that may be felt by the swimmer allowing the swimmer to identify his position in the pool.
2. Background Information
Exercising by swimming laps in a swimming pool is a healthy activity enjoyed by many people. The swimmers typically swim between lane markers that segregate a swimming pool into discreet swimming lanes to prevent the swimmers from running into each other. These lane markers float on the water and are disposed on either side of a line painted on the bottom of the pool. The swimmers use the line and the markers to align themselves while swimming. The alignment process relies largely on visual input.
Blind or visually impaired swimmers cannot rely on such a visual input to align themselves within a swimming lane. Blind swimmers thus find it difficult to easily swim laps without constantly adjusting their position in the swimming lane by physically touching the lane markers on either side of the swimming lane. Although the physical contact with the lane marker allows the swimmer to swim laps, such contact is generally undesirable and is specifically undesirable when the swimmer desires to compete against another swimmer or a clock. The contact breaks the swimmer's rhythm causing him to lose valuable momentum and thus time.
One method of maintaining a blind swimmer's position in a swimming lane is to have a partner walk along side of the swimmer and provide position feedback by touching the swimmer. Although this method is functional along the sides of the pool, the method encounters problems when the blind swimmer must swim in the center of the pool. The method also undesirably requires a partner for each swimmer. It is thus desired in the art to provide a lane marking system that allows a blind swimmer to feel his position in a swimming lane without requiring the swimmer to touch the side lane markers or the bottom of the pool. The system should also function without requiring a partner for each swimmer.
SUMMARY OF THE INVENTION
In view of the foregoing, it is an objective of the present invention to provide a swimming pool lane marker for the visually impaired.
Another objective of the present invention is to provide a swimming pool lane marker for the visually impaired that can be easily installed into and removed from existing swimming pools.
Another objective of the present invention is to provide a swimming pool lane marker for the visually impaired that disperses a line of bubbles along the center of a swimming lane that can be used by a swimmer to feel his way down the swimming lane.
Another objective of the present invention is to provide a swimming pool lane marker that is held below the water surface of the pool and suspended above the bottom wall of the pool.
Another objective of the present invention is to provide a swimming pool lane marker for the visually impaired that can be built into the bottom wall of a swimming pool.
Another objective of the present invention is to provide a swimming pool lane marker for the visually impaired that includes an end-of-lane marker that tells the swimmer when the swimmer is approaching an end of the pool.
Another objective of the present invention is to provide a swimming pool lane marker for the visually impaired that includes a removable pad disposed at each end of the swimming lane.
Another objective of the present invention is to provide a swimming pool lane marker for the visually impaired that connects with the existing hardware or lane markers in existing pools.
A further objective of the present invention is to provide a swimming pool lane marker for the visually impaired that is of simple construction, that achieves the stated objectives in a simple, effective, and inexpensive manner, that solves the problems and that satisfies the needs existing in the art.
These and other objectives and advantages of the present invention are obtained by a lane marker for a swimming pool including a tube having a sidewall defining a passageway and a plurality of perforations that extend through the sidewall; and a supply of gas in fluid communication with the passageway.
Other objectives and advantages of the present invention are obtained by a swimming pool and first lane marker in combination; the swimming pool having a sidewall and a bottom wall defining a cavity having at least one swimming area; the lane marker including a tube extending across a portion of the swimming area; the tube having a sidewall defining a passageway and a plurality of perforations; and a source of gas in fluid communication with the passageway.
BRIEF DESCRIPTION OF THE DRAWINGS
The preferred embodiments of the invention, illustrative of the best modes in which the applicant has contemplated applying the principles of the invention, are set forth in the following description and are shown in the drawings and are particularly and distinctly pointed out and set forth in the appended claims.
FIG. 1 is a side view of the first embodiment of the lane marker of the present invention installed in a swimming pool;
FIG. 2 is a top plan view of the swimming pool of FIG. 1;
FIG. 3 is a sectional view taken along line 3--3 of FIG. 1;
FIG. 4 is an end view showing a swimmer using the first embodiment of the lane marker;
FIG. 5 is an end view similar to FIG. 4 showing a swimmer using a second embodiment of the present invention;
FIG. 6 is an end view of the pad and frame of the present invention;
FIG. 7 is a side view of the pad and frame of FIG. 6;
FIG. 8 is a side view similar to FIG. 1 showing a third embodiment of the present invention; and
FIG. 9 is a top plan view similar to FIG. 2 showing a fourth embodiment of the present invention.
Similar numbers refer to similar elements throughout the specification.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The first embodiment of the swimming pool lane marker for the visually impaired made in accordance with the concepts of the present invention is indicated generally by the numeral 10 in the accompanying drawings. Lane marker 10 is used in a typical swimming pool 12 that includes a sidewall 14 and a bottom wall 16. Sidewall 14 and bottom wall 16 cooperate to define a cavity that is substantially filled with water to define a swimming area. In typical arrangements, lane marker 10 of the present invention is disposed across a longitudinal expanse of swimming pool 12 as depicted in the drawings. It is understood that lane marker 10 may be disposed in other configurations with respect to pool 12 and that the swimming area of pool 12 does not have to be substantially rectangular as shown in the drawings.
In the past, swimming lanes 18 were defined by a pair of floating lane markers 20 or one floating lane marker 20 and a portion of sidewall 14 of pool 12. Floating lane markers 20 generally include a longitudinal cable 22 that carries a plurality of individual floats 24. Cable 22 is connected to a lane marker attachment post 26 that is mounted on sidewall 14 of swimming pool 12. Lane markers 20 may be selectively disconnected from posts 26 and removed from pool 12 by winding them on a large barrel. Such removal allows pool 12 to be selectively configured for lap swimming. As shown in the drawings, floating lane markers 20 float at the water surface 28.
First embodiment of lane marker 10 generally includes a tube 30 having a sidewall that defines a passageway 32 and a plurality of perforations 34. Tube 30 extends longitudinally at approximately the center of swimming lane 18 substantially centered between floating lane markers 20. Tube 30 may be fabricated from a generally lightweight plastic or rubber but also may be fabricated from other suitable materials that are known in the art. Passageway 32 is in fluid communication with a source of gas 36 that provides gas to passageway 32 where it exits passageway 32 through perforations 34 to form bubbles 38. Bubbles 38 are felt by a swimmer 40 so that swimmer 40 may determine his position with respect to lane markers 20. Source of gas 36 is preferably an air compressor or air blower that delivers air to tube 30 in a volume sufficient to fill the entire length of tube 30 with air causing bubbles 38 to rise from tube 30 along the entire length of pool 12. When the length of pool 12 or the diameter of tube 30 exceeds the capacity of a single air compressor 36 a second air compressor 36 (or additional sources 36), may be provided in fluid communication with passageway 32 at the other end of pool 12 as depicted in FIGS. 1 and 2. Each source 36 may be provided with a check valve (not shown) that prevents water from damaging source 36.
As described above, tube 30 may be fabricated from a material that typically floats. In addition, tube 30 is filled with a gas, such as air, that is lighter than water. As such, tube 30 must be anchored below water surface 28 or it would float and interfere with swimmer 40. In the first embodiment of lane marker 10, a wire 42 extends through passageway 32 and holds tube 30 suspended above bottom wall 16 but below water surface 28 so as to not interfere with swimmer 40. Wire 42 may also be clipped to the outside of tube 30 with a suitable clip that wraps about at least a portion of tube 30. Wire 42 extends between two portions of sidewall 14 of pool 12 or, as shown in the drawings, extends between a pair of frame assemblies that are mounted on sidewall 14 of swimming pool 12. Other suitable weights may also be used to hold tube 30 below the surface.
Each frame assembly 44 includes a hook 46 that fits over the edge of pool 12 and a cross bar 48 that extends between floating lane markers 20. Each frame assembly 44 further includes a wire attachment post 50 that positions wire 42 far enough below water surface 28 to prevent tube 30 from interfering with swimmer 40. Each frame assembly 44 may be attached to swimming pool 12 by appropriate connectors that may be secured to sidewall 14. One manner of making such a connection is by connecting the ends of cross bar 48 to lane marker attachment posts 26. Another manner of forming the connection is to connect the ends of cross bar 48 to cable 22 of floating lane markers 20.
In addition to supporting wire 42 that maintains the position of tube 30, each frame assembly 44 may also carry a pad 52 that protects swimmer 40 from accidentally injuring himself on sidewall 14 of pool 12. Each pad 52 may be removably mounted on frame assembly 44 by connectors such as hook and loop fasteners 54. Pad 52 may have floatation capabilities so that it may be used in a life saving situation.
Another feature of lane marker 10 is an end-of-lane marker 56 that is disposed above each end of swimming lane 18. In the first embodiment of lane marker 10, end-of-lane marker 56 includes a support 58 that extends over swimming lane 18 and carries a perforated water pipe 60. Perforated water pipe 60 is in fluid communication with a source of water 62 to create a curtain of water droplets at the end of swimming lane 18 as shown in FIG. 3. The curtain of water droplets tells swimmer 40 that sidewall 14 of swimming pool 12 is near and swimmer 40 can anticipate contact with pad 52.
A second embodiment of the swimming pool lane marker for the visually impaired made in accordance with the concepts of the present invention is indicated generally by the numeral 70 in FIG. 5. Lane marker 70 is substantially similar to lane marker 10 except that lane marker 70 includes a pair of substantially parallel tubes 30. Each tube 30 is in fluid communication with gas source 36 to form a pair of spaced curtains of bubbles 38. Swimmer 40 thus feels bubbles 38 when he starts to move out of the ideal swimming lane. The frame assembly 72 that supports tubes 30 of lane marker 70 includes a pair of wire attachment posts 50 extending down from cross bar 48. Lane marker 70 is otherwise substantially similar to lane marker 10.
A third embodiment of the swimming pool lane marker of the present invention is indicated generally by the numeral 80 in FIG. 8. In this embodiment, tube 30 is integrally formed with bottom wall 16 of swimming pool 12 such that perforations 34 are formed in bottom wall 16. A pair of tubes 30 may also be used with this embodiment. In this embodiment, wire 42 is not required to hold tube 30 below water surface 28. Frame assemblies 44 still may be used to carry pads 52.
A fourth embodiment of the lane marker is indicated generally by the numeral 90 in FIG. 9. Lane marker 90 includes a pair of tube branches 92 that extend substantially perpendicularly from tube 30 adjacent the end of swimming lane 18. Each branch 92 includes perforations 34 that allow bubbles to escape from branches 92. Branches 92 thus form curtains of bubbles adjacent the ends of swimming lane 18 to warn swimmer 40 that sidewall 14 of swimming pool 12 is near. Tube 30 and branches 92 may be integrally formed in bottom wall 16 or may be supported on appropriate wires 42 as described above.
Accordingly, the improved swimming pool lane marker for the visually impaired is simplified, provides an effective, safe, inexpensive, and efficient device that achieves all the enumerated objectives, provides for eliminating difficulties encountered with prior devices, and solves problems and obtains new results in the art.
In the foregoing description, certain terms have been used for brevity, clearness, and understanding; but no unnecessary limitations are to be implied therefrom beyond the requirement of the prior art, because such terms are used for descriptive purposes and are intended to be broadly construed.
Moreover, the description and illustration of the invention is by way of example, and the scope of the invention is not limited to the exact details shown or described.
Having now described the features, discoveries, and principles of the invention, the manner in which the swimming pool lane marker for the visually impaired is constructed and used, the characteristics of the construction, and the advantageous new and useful results obtained; the new and useful structures, devices, elements, arrangements, parts, and combinations are set forth in the appended claims. | A swimming pool lane marker for the visually impaired generally includes a perforated tube that extends the length of a swimming pool. The perforated tube is in fluid communication with a source of compressed gas, such as an air compressor. The air compressor delivers pressurized air to the tube. The pressurized air escapes through the perforations forming a line of bubbles along the swimming lane. The blind swimmer can feel these bubbles and determine his position in the swimming lane. The perforated tube is held under the water by a wire that extends between a pair of frame assemblies that connect the wire to the sidewall of the pool. Pads may be carried on the frame assemblies to protect the swimmer from the sidewall. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of priority of U.S. Provisional Patent Application No. 61/848,549 filed 7 Jan. 2013, which is incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates generally to the field of construction. More particularly, the present invention relates to installation of construction items, such as windows and doors, into a rough opening.
BACKGROUND OF THE INVENTION
In the construction trade, it has long been known that items such as window and door jambs require adjustment in order to fit properly within a rough opening framed for such item. Window jambs are typically known to be installed after a window unit is in place, whereas door jambs are typically known to be provided integrated with the door unit. In either instance, the jambs require squaring up within the rough opening. Typically, beveled shims fabricated from split wood such as cedar are placed around the given item (i.e., window or door jamb) during installation and lodged in place between the item's outer edges and the rough opening. This method of “shimming” in order to square up the installed jamb is therefore well known by builders. However, this known method of shimming is inexact, awkward, and time-consuming. Moreover, it can be very difficult to shim up a jamb with precision in this manner.
Another known technique used by builders is the installation of one or more screws into the rough opening prior to placement of the jamb therein. Such screw(s) are engaged with the rough opening only as far as deemed necessary to provide spacing for the jamb. If adjustments are needed to provide more space or less space for the jamb placement, then the jamb (in the instance of a window) or frame/jamb (in the instance of a door) can be taken out of the rough opening and set aside while the screw(s) are readjusted into or out of the side(s) of the rough opening. Once the screw(s) are readjusted, the jamb or frame/jamb can be placed back into the rough opening. This trial and error cycle of adjustment can be repeated until proper spacing and squaring up is attained. It should therefore be realized that this construction method may be rather tedious and time-consuming. Moreover, the screw(s) are often knocked or tapped out of place by the jamb if precise care is not taken in placement of the window or door jamb, thereby necessitating further time-consuming iterations of adjustments.
It is, therefore, desirable to provide an apparatus and related method for quickly and easily shimming up window or door jambs during its installation into a rough opening.
SUMMARY OF THE INVENTION
It is an object of the present invention to obviate or mitigate at least one disadvantage of previous shimming apparatus and methods.
In a first aspect, the present invention provides a method of installing a construction unit within a pre-framed rough opening, the method including: embedding a plurality of adjustment mechanisms within an inner edge of a rough opening; inserting a construction unit within the rough opening for abutment with the plurality of adjustment mechanisms; and engaging each one of the plurality of adjustment mechanisms with a wrench in a rotating manner so as to adjust the abutment of the construction unit with the one or more adjustment mechanisms; wherein iteratively engaging of each one of the plurality of adjustment mechanisms serves to shim the construction unit within the rough opening until the construction unit is squarely secured within the rough opening.
In a further embodiment, there is provided an apparatus for installation of a construction unit within a pre-framed rough opening, the apparatus including: a head section including a screw interface for operative engagement with a screwdriver, a first disk-like surface for abutting engagement with the construction unit, a nut-like structure for operative engagement with a wrench; a threaded section affixed to the head section, the threaded section including a threaded surface for retained engagement with a rough opening, a screw head forming the screw interface flush with the first disk-like surface; and wherein adjustment of the apparatus via the wrench in operative engagement with the nut-like structure provides support to the construction unit within the rough opening via the first disk-like structure.
In further aspect, the present invention provides a kit for installation of a construction unit within a pre-framed rough opening, the kit including: a plurality of adjustment mechanisms each capable of shimming an outer edge of a construction unit against an inner surface of a rough opening, each one of the adjustment mechanisms having a head section including a screw interface for operative engagement with a screwdriver, a first disk-like surface for abutting engagement with the construction unit, a nut-like structure; a threaded section affixed to the head section, the threaded section including a threaded surface for retained engagement with a rough opening, a screw head forming the screw interface flush with the first disk-like surface; and a wrench capable of rotation of each the adjustment mechanism by way of operative engagement with the nut-like structure such that the first disk-like surface provides support to the construction unit within the rough opening.
Other aspects and features of the present invention will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the present invention will now be described, by way of example only, with reference to the attached Figures, wherein:
FIG. 1A is an elevation view of a window in place with adjustment mechanisms in accordance with the present invention with one corner of such window circled in enlargement.
FIG. 1B is the enlargement shown circled in FIG. 1A .
FIG. 2 is a partially cut-away three-dimensional illustration of the embodiment illustrated in FIG. 1B with adjustment mechanisms in accordance with the present invention and further being tightened via a wrench.
FIG. 3 is a three-dimensional view of the first embodiment of an adjustment mechanism in accordance with the present invention.
FIG. 4 is a three-dimensional view of the second embodiment of an adjustment mechanism in accordance with the present invention.
DETAILED DESCRIPTION
Generally, the present invention provides a method and apparatus that fulfills rapid installation of a construction unit which may be varied construction items, such as jambs of windows and doors, into a rough opening. Moreover, the present invention advantageously enables accurate adjustment of the given construction item being installed including shimming and squaring-up of the construction items relative to the rough opening into which it is being installed. This improves repeatability of quick installations with reduced errors such that quality of construction can be maintained and improved without time-consuming and costly labor. Still further, the present invention also serves to reduce the necessary construction skills required during, for example, window jamb or door jamb installation into a rough opening thereby enabling do-it-yourself homeowners to undertake work typically otherwise done by skilled carpenters.
With reference to FIG. 1A , there is illustrated an elevation view 100 of a window unit 10 in place with adjustment mechanisms (several being labeled as elements 11 a through 11 d ) in accordance with the present invention with one corner of such window 10 circled in enlargement. FIG. 1B is the enlargement shown circled in FIG. 1A . It is clear, therefore, from FIGS. 1A and 1B that the window unit 10 is shown within the rough opening of a section of a framed wall shown in the enlargement by studs 12 , 13 , and 14 . Such roughed-in framing construction is well known in the carpentry art and will not be further described herein. The window unit 10 typically includes a trim board which forms the jamb 10 a whereby a gap exists between the inner surfaces of the rough opening and the trim board of the window unit. It is within this gap that the inventive adjustment mechanism resides. In this particular arrangement as shown, there are ten adjustment mechanisms (several being labeled as elements 11 a through 11 d ) placed at even intervals around the periphery of the jamb 10 a . It should be understood that while ten such adjustment mechanisms are shown, there may be more or fewer used depending upon the dimensions of the given window unit. For example, a large window unit may require many more such adjustment mechanisms. Likewise, a very wide but short window unit may requirement many adjustment mechanisms on the longer top and bottom gaps, but much fewer on the shorter side gaps. Thus, the given window unit will dictate the precise placement and number of adjustment mechanisms.
It should further be understood that although a window unit is shown and described in conjunction with the present invention, the inventive adjustment mechanisms may indeed be used in any other implementation including, but not limited to, installation of door units within rough openings. Moreover, the common feature of a framed unit (e.g., window, door, or other similar structures requiring squaring up) being installed within a rough opening is a requirement for applicability of the present invention.
With regard to FIG. 2 , there is illustrated a partially cut-away three-dimensional illustration which corresponds to the structure of FIG. 1B and whereby an adjustment mechanism in accordance with the present invention being tightened via a wrench 20 . In particular, this illustrates a first embodiment 30 of the inventive adjustment mechanism which is further illustrated in the three dimensional view of FIG. 3 . In this first embodiment 30 , the adjustment mechanism includes a threaded section 32 with self-tapping tip 31 , and a head section 35 . The threaded section 32 is configured to engage the inner surface of the rough opening. Commonly, the rough opening will be provided in terms of wooden studs. In such instance, the threaded section 32 would be configured to include larger threads suitable for engagement with wood. However, if the rough opening was formed via some other material such as steel framing or concrete material (e.g., cinder blocks), then it should be readily apparent that the threaded section 32 would include, respectively, finer metal threads or hardened masonry threads and for example a self-tapping tip 31 with a hardened carbide tip (not shown). Overall, it should be readily apparent that different sized threads may be required for different rough opening materials.
With further reference to FIG. 3 , the head section 35 is seen to include two disk-like surfaces 33 and 34 with an intermediate portion 36 situated there between. While the two disk-like surfaces 33 and 34 include a circumferential periphery, the intermediate portion 36 includes a sectioned outer periphery having six (6) flat edges which preferably forms a hexagonal nut structure. The intermediate portion 36 is therefore able to be engaged with a standard wrench so long as the hexagonal nut structure formed is dimensioned for the given wrench used. The two disk-like surfaces 33 and 34 basically form a slot there between such that the wrench is slotted therein. In other words, the present invention may include an intermediate portion 36 which corresponds to a standardized wrench size using, for example, ISO Metric, American/English, British Standard, or any other standardized sizes. Thus, it should be understood that the particular dimensions of the intermediate portion 36 may vary without straying from the intended scope of the present invention. Likewise, though a hexagonal nut formation is described herein as preferred, it should be readily apparent that variations in the shape of the nut formed (e.g., square nut) may occur without straying from the intended scope of the present invention.
The gap between the two disk-like surfaces 33 and 34 in which the intermediate portion resides should be sufficiently dimensioned so as to allow a standard wrench to fit therein. However, while such standardization is desirable, it should also be understood that a proprietary width may be useful such that a non-standard, thin gap between the two disk-like surfaces 33 and 34 would therefore require a correspondingly non-standard, thin wrench. It should be understood that the benefit to a proprietary thin gap with related proprietary thin wrench would be an advantageous ability of the present invention to be used within tight workspaces where very little room is available in the gap between the window jamb's outer edge and the rough opening's inner surface. In such instance, the present invention may be provided in the form of a kit where such kit would be made available with a minimum set of adjustment mechanisms combined with a correspondingly sized, non-standard wrench. It should therefore be readily apparent that such wrench provided within the kit may be non-standard in both its thickness and also with regard to the sizing and engagement with the nut-like intermediate portion. Thus, the intermediate portion 36 may also be a non-standard nut size and/or dimension (e.g., a 7-sided nut having a maximum radius of 3.875 mm or any other proprietary configuration).
With further reference to FIG. 4 , there is illustrated a three-dimensional view of the second embodiment 40 of an adjustment mechanism in accordance with the present invention. This second embodiment 40 is similar to the first embodiment 30 except that only one disk-like surface 43 is provided in the head section 45 of the adjustment mechanism. Here, the single disk-like surface 43 exists on the head position at the extreme opposite from the tip 41 of the threaded section 42 which itself screws into the inner edge of the rough opening. A nut-like portion 46 , which mirrors the intermediate portion 36 in form and function, is disposed below the disk-like surface 43 . Engagement with a wrench (either standard sizing or non-standard sizing) is accomplished in a manner similar to that described hereinabove with regard to the first embodiment 30 . However, it should be understood that because only one disk-like surface 43 exists, there is no slot to retain a wrench. Rather, a user would require somewhat more dexterity in manipulating the wrench during use of the second embodiment 40 versus the first embodiment 30 . Notwithstanding this minor difference, one benefit of a single disk-like surface 43 resides in reduced materials required during manufacture of the second embodiment 40 .
In either embodiment 30 or 40 with either the single or double disk-like surface(s), the same principles of installation apply. Both embodiments involve a threaded section which first engages the inner edge of the rough opening. Preferably, the threaded section is self-tapping such that a minimal amount of pressure exerted by the user may initially embed the adjustment mechanism. The threaded section may be a metal screw (for example only—a zinc 8×1¼″ phillips hex washer full thread self-drilling screw—though other sizes are possible) whereby the head section (of either embodiment) may be formed of a hardened resin shaped into the nut-like structure with either the single or double disk-like surface(s). It should be readily apparent that more durable screws may be used for installations where steel studs will need to be penetrated. In either embodiment, the metal screw Phillips head would present itself flush with the outer disk-like surface. In this manner, a user could utilize a standard Phillips head screwdriver to initially set the adjustment mechanisms at spaced intervals along the inner edge of the rough opening. While a manual screwdriver is possible, it should be understood that a motorized device may be used such as, but not limited to, air impact drivers or battery operated screwdrivers. Once the adjustment mechanisms were set firmly in place, the user would set in the jamb to generally rest upon each outer disk-like surface. Because the metal screw Phillips head would therefore no longer be accessible buy the user, a suitable wrench would then be used to fine tune the adjustment of each adjustment mechanism thereby shimming up the installed jamb within the rough opening until the jamb is squared up and firmly seated. The adjustment mechanisms would therefore remain permanently in place and the window framing completed.
As mentioned, in either embodiment the head section is formed integrally of a hardened resin material. High impact plastic may be a suitable material for this, though any moldable and suitably durable material may be used for the head section without straying from the intended scope of the present invention. Likewise, in either embodiment the threaded section is formed of a metal screw. The head of the screw should be held exposed but flush within the head section to enable a screwdriver access to initially embed the threads within the inner edge of the rough opening. It should be readily apparent that although a phillips head metal screw is shown and described, any particular screw head and related screwdriver may be utilized such as flat, star, hex, or any other configuration without straying from the intended scope of the present invention.
In manufacture of the present invention, the size of the disk-like surface(s) of either embodiment may be variable. For example, some implementations may involve use with windows that may be relatively large and/or weighty. In such instances, the disk-like surface(s) would be molded to be relatively larger in diameter so as to provide more surface area abutting, and thereby supporting, the window jamb. Likewise, smaller windows may require smaller disk-like surface(s). Still further, the threaded section may vary in size depending upon the given application. Yet still further, it should be readily apparent that when the embodiment as seen in FIG. 3 is provided having two disk-like surfaces each surface may vary in diameter relative to one another—i.e., the first disk-like surface abutting the jamb may be larger or smaller than second disk-like surface. Accordingly, changes in sizes should not vary the intended scope of the present invention.
It should also be apparent to those well versed in the materials art that the adjustment mechanism in accordance with the present invention should be manufactured in such a manner so as to avoid decoupling of the head section's material with the threaded section's material. A variety of methods may be useful in appropriately joining the head section with the threaded section. These methods may include providing the metal screw head with scoring or knurling prior to molding of the head section thereon. Likewise, the metal screw may be of non-standard type that is customized with protrusions which assist in anchoring the screw to the molded head section. It has also been found to be useful with regard to manufacture of the present invention to first heat treat the metal screw of the threaded section for embedding within the pre-molded head section. In this manner, the seating of the metal screw is markedly improved thus improving the integrity of the joint between differing materials.
The above-described embodiments of the present invention are intended to be examples only. Alterations, modifications and variations may be effected to the particular embodiments by those of skill in the art without departing from the scope of the invention, which is defined solely by the claims appended hereto. | A method, apparatus, and kit for adjustment of a construction unit with a rough opening. The construction unit may be a window, door, or similar construction element that requires shimming and squaring up within a rough opening. An adjustment mechanism is included that has a head section and threaded section. The head section engages the construction unit by abutment and the threaded section engages the rough opening by threaded retention. After initial embedding of the adjustment mechanism within the inner surface of the rough opening, the adjustment mechanism is rotationally engaged via a wrench for fine-tuned shimming of the construction unit. | 5 |
[0001] The present application claims priority from PCT Patent Application No. PCT/EP2012/000822 filed on Feb. 26, 2012, which claims priority from German Patent Application No. DE 20 2011 004 951.5 filed on Apr. 6, 2011, the disclosures of which are incorporated herein by reference in their entirety.
FIELD OF THE INVENTION
[0002] The invention is directed to a pivot lever actuation unit comprising an actuating handle which can be folded out of a recess and then swiveled.
[0003] It is noted that citation or identification of any document in this application is not an admission that such document is available as prior art to the present invention.
[0004] A pivot lever actuation unit of the general type mentioned above is already known, for example, from DE 20 2006 007 700 U1.
[0005] The actuating handle can drive a locking bar via a toothed rack or, when a sash fastener is arranged thereon, can form a sash lock.
[0006] It is noted that in this disclosure and particularly in the claims and/or paragraphs, terms such as “comprises”, “comprised”, “comprising” and the like can have the meaning attributed to it in U.S. Patent law; e.g., they can mean “includes”, “included”, “including”, and the like; and that terms such as “consisting essentially of” and “consists essentially of” have the meaning ascribed to them in U.S. Patent law, e.g., they allow for elements not explicitly recited, but exclude elements that are found in the prior art or that affect a basic or novel characteristic of the invention.
[0007] It is further noted that the invention does not intend to encompass within the scope of the invention any previously disclosed product, process of making the product or method of using the product, which meets the written description and enablement requirements of the USPTO (35 U.S.C. '112, first paragraph) or the EPO (Article 83 of the EPC), such that applicant(s) reserve the right to disclaim, and hereby disclose a disclaimer of, any previously described product, method of making the product, or process of using the product.
SUMMARY OF THE INVENTION
[0008] it is the object of the invention to further develop the known pivot lever actuation unit and to make it more versatile.
MODES OF CARRYING OUT THE INVENTION
[0009] The above-stated object is met in that the actuation unit has a modular construction allowing certain external component parts to be exchanged, which also enables a flexible rebuild.
[0010] Accordingly, the actuation unit can have flap windows with an exchangeable viewing panel at the ends of the recess. The ends of the recess are exchangeable and can be replaced, for example, by a fold-out backlit logo panel.
[0011] The ends of the recess may be designed as LCD screen.
[0012] Further, the ends of the recess can be designed as exchangeable cover or sleeve for purposes of modular incorporation of additional components such as fingerprint reader, key pad and iris detection.
[0013] On the other hand, multi-colored, optionally blinking or non-blinking LEDs can be provided at the ends of the recess.
[0014] In particular, the ends of the recess can serve to supply information which shows the state of a quantity of hardware devices.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1A shows a detailed view of components of a pivot lever actuation unit according to the invention;
[0016] FIG. 1B shows another form;
[0017] FIG. 2 shows an assembled actuation unit according to FIG. 1A ;
[0018] FIGS. 3A and 3B show a back side of the actuation unit shown in FIG. 2 ;
[0019] FIG. 4A shows the actuation unit with folded-out hand lever;
[0020] FIG. 4B shows the actuation unit according to the invention with folded-out, swiveled hand lever;
[0021] FIG. 5A shows a top view of the actuation unit according to FIGS. 4A and 4B with folded-in handle;
[0022] FIG. 5B shows an axial section through the arrangement according to FIG. 5A ;
[0023] FIGS. 6A and 6B show a top view and a sectional view of the pivot lever actuation unit with folded-out lever;
[0024] FIGS. 7A and 7B show the same arrangement as in FIGS. 6A and 6B , but with folded-out, swiveled lever;
[0025] FIGS. 8A and 8B show an actuation unit with and without cover;
[0026] FIG. 9 shows an actuation unit by which a sash fastener or a double bar can be driven;
[0027] FIGS. 10 to 12 show various enlarged views of the one (lower) end of the recess.
DETAILED DESCRIPTION OF EMBODIMENTS
[0028] It is to be understood that the figures and descriptions of the present invention have been simplified to illustrate elements that are relevant for a clear understanding of the present invention, while eliminating, for purposes of clarity, many other elements which are conventional in this art. Those of ordinary skill in the art will recognize that other elements are desirable for implementing the present invention. However, because such elements are well known in the art, and because they do not facilitate a better understanding of the present invention, a discussion of such elements is not provided herein.
[0029] The present invention will now be described in detail on the basis of exemplary embodiments.
[0030] FIG. 1A shows an actuation unit 10 with recess 12 , adapter part 14 and base part 16 and a slot 44 therein. A projection 45 of the slide 42 projects through this slot 44 and is used for driving a lock bar. Alternatively, pinion 38 can be coupled with a pinion 138 to drive a shaft 18 which carries a sash fastener tab 28 , for example. The shaft 18 or 118 can project through the opening 48 .
[0031] The two embodiment forms shown in FIGS. 1A and 1B make it possible to drive rotary locks such as sash fasteners ( FIG. 1A ) and to drive lock bars, i.e., axially displaceable bars for locking and unlocking ( FIG. 1B ) sash fasteners and bars, not shown.
[0032] While FIG. 1A shows an embodiment form having a rotary drive (see pinion 38 ), FIG. 1B is made for a slot-shaped drive with toothed rack 42 .
[0033] FIGS. 7A and 7B show a lock case, shown in FIG. 9 , for bearing support of the drive shaft 218 , wherein the pinion 38 is first ( FIGS. 1A , 1 B) screwed to the recess in the aperture 36 (see FIG. 1A ), screws 34 being provided for this purpose. Next, the base part 16 can be screwed on, screws 35 being provided for this purpose.
[0034] The embodiment form of the recess shown in FIGS. 1A and 1B is outfitted with a flap 52 with an exchangeable viewing panel. This can also be a backlit logo panel. Alternatively, an LCD screen can be provided behind the window at the ends of the recess.
[0035] According to another alternative, the ends of the recess can be designed as exchangeable cover or sleeve for modular incorporation of additional components such as fingerprint reader, key pad or iris detection.
[0036] Multi-colored, optionally blinking or non-blinking LEDs can sometimes be provided at the ends of the recess; an LED (light emitting diode) is shown by way of example at 74 in FIG. 6B .
[0037] The case 54 which can be seen in FIG. 4A shows an oblique view of the recess part 12 with raised handle 46 which has been released beforehand by a hook 56 (see also FIG. 7B ). Component part 50 is part of a slide 50 which can be released by a lift magnet 58 . The hand lever 46 is U-shaped in cross section. The legs of the U extend on the left-hand side and right-hand side of a case 54 when the handle 46 is swiveled in. When swiveled in, the hand lever 46 locks automatically by insertion in the component part 50 .
[0038] As can be seen in FIGS. 4A and 4B , the hand lever 46 can only fold in when it is aligned with respect to the recess 12 . This is ensured in that a projection 60 of the hand lever 46 can only penetrate into a corresponding recess surface 62 in this position, but not when it is swiveled out of the fold-in area as in FIG. 4B .
[0039] Unauthorized folding out and actuation of the hand lever is also prevented in that the side walls 64 of the hand lever penetrate into the recess and extend between the recess wall and the case wall 54 .
[0040] The adapter part 14 which can be seen in FIGS. 1A and 1B is symmetrical around its transverse axis and thus allows the recess part to be displaced by 180 degrees, which is useful when changing the fastening arrangement of a switch cabinet door.
[0041] The swivel lever is articulated at a shaft 18 as is shown, for example, in FIG. 9 . This shaft 18 , 118 has at its end a bore hole 20 for fitting the lever 22 ; a square drive 24 and a screw thread 26 are located at the other end of the shaft 18 . Square drive 24 receives a sash fastener 28 fixed by screwing on the nut 30 or a threaded blind hole for head screw 130 . Shaft 18 has a bearing portion by which it is supported in a bearing 32 so as to be rotatable but axially fixed. The bearing 32 is in turn provided in a lock case which can be inserted onto an aperture and screwed tight by two screws 34 .
[0042] Alternatively, a shaft 218 can be provided which cooperates with a lock case which fits exactly into the aperture 36 (see FIG. 9 ).
[0043] Two lock bars (see FIG. 1B and FIG. 9 ) project out of the lock case, where a pinion 238 meshes with a toothed slide. This toothed slide 42 is guided through projections 44 into a slot.
[0044] FIG. 2 shows a perspective view of the lever lock according to the invention in the folded-in state, while FIG. 3A shows the same lever lock viewed from the rear, wherein it is arranged in such a way that it can actuate a rotary latch such as a sash latch. This projection 44 is implemented in such a way in the arrangement shown in FIG. 3B that two projecting noses 44 can be seen which drive and displace a locking bar which is located on the other side of the sheet metal wall also having a slot so that this projection 44 can reach through.
[0045] The flexibility in the application of the new pivot lever actuation unit also results from the following:
[0046] The actuation unit can serve to drive a locking bar located on the door leaf (see the arrangement according to FIG. 4B ).
[0047] However, locking bar(s) which is (are) arranged upright with respect to the door leaf plane can also be operated by selecting the arrangement in FIG. 9 with the lock case 40 .
[0048] But a sash fastener can also be operated, e.g., by combining FIG. 9 with the component parts 28 , 32 or through the arrangement according to FIG. 3A ; the recess is arranged on the door leaf in the first case and on the base plate 16 in the second case.
[0049] Versatility is enhanced even further by electronic add-on devices.
COMMERCIAL APPLICABILITY
[0050] The invention is commercially applicable in switch cabinet construction.
[0051] While this invention has been described in conjunction with the specific embodiments outlined above, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, the preferred embodiments of the invention as set forth above are intended to be illustrative, not limiting. Various changes may be made without departing from the spirit and scope of the inventions as defined in the following claims.
LIST OF REFERENCE NUMERALS:
[0000]
10 pivot lever actuation unit
12 recess part
14 adapter part
16 base part
18 , 118 shaft
20 articulation
22 hand lever
24 square drive
26 thread
28 sash fastener
30 nut
32 bearing part
34 screw
36 aperture
38 , 138 pinion
40 lock case
42 toothed slide
44 projection
46 slot
48 slot expanded to form a round bore hole
50 slide
52 flap
54 case
56 hook
58 lift magnet
60 projection
62 offset
64 side wall
66 emergency access, button
68 emergency pin
70 door leaf
72 cable
74 LED | A pivot lever actuation unit including an actuating handle which can be folded out of a recess and then swiveled, and an adapter part which can be screwed on under the recess. The actuation unit has a modular construction allowing certain external component parts to be exchanged, and also enables a flexible rebuild. | 8 |
BACKGROUND OF THE INVENTION
The present invention relates to a new and improved construction of a controlled deflection roll.
In its more particular aspects, the present invention relates to a new and improved construction of controlled deflection roll comprising a stationary or non-rotating roll support member or beam and a roll shell which is rotatable about the stationary roll support member and which is supported at the stationary roll support member by means of hydraulic support or pressure elements. The roll shell defines an outer roll shell surface and there is provided in the interior space of the roll shell a predetermined number of traveling rings each of which is associated with a related one of the support elements. The inner traveling ring surface of each one of the traveling rings provides a travel path for the related support element.
Controlled deflection rollers of the classical type as described, for example, in U.S. Pat. No. 3,885,283, granted May 27, 1975, and U.S. Pat. No. 3,802,044, granted Apr. 9, 1974, are used to roll band-shaped materials, for example, metal bands, like aluminum foils or steel sheet material, paper webs or similar materials.
In the arrangement as described, for example, in U.S. Pat. No. 3,921,514, granted Nov. 25, 1975, the controlled deflection roll cooperates with a counter roll and the contact or pressing force by means of which the two rollers are pressed against each other along a pressure or pressing line is generated by the pressure of a pressure fluid supplied to hydrostatic support elements. The use of controlled deflection rolls in such arrangement affords the advantage that the outer surface thereof adapts itself to the shape of the counter roll along the pressure or pressing line and follows any deformation of the counter roll. Furthermore, the contact or pressing force acting along the pressure or pressing line can be individually controlled and regulated by suitably adjusting the pressure of the pressure fluid effective at the individual hydrostatic support elements in accordance with a desired contact or pressing force profile along the pressure or pressing line, i.e. in axial direction of the rolls.
In order to ensure a desired surface quality of the rolled material, for example, of aluminum foils, steel bands or paper webs, the controlled deflection roll must be provided with a solid and sufficiently smooth outer surface. Preferably, therefore, roll shells made of a suitable type of steel are used in such controlled deflection rolls. Additionally, and in order to achieve the desired effect, the roll shell must have sufficient flexibility in lengthwise as well as in circumferential direction and the material as well as the wall thickness of the roll shell of the controlled deflection roll must be correspondingly selected. As a matter of fact, a small wall thickness would be advantageous with respect to a good transverse flexibility, i.e. a deformability of the roll shell transversely to the pressure or pressing line or to the axis thereof. However, due to the partially significant forces exerted by the support elements, the deformation of the roll shell in circumferential direction would become so large that the yield strength or elastic limit of the material can be reached. Therefore, the wall thickness of the roll shell may not fall short of a predetermined value in order to preclude any undue deformations.
In the known controlled deflection rolls in which the support elements directly act upon the inner surface of the roll shell it is, therefore, impossible to achieve optimum flexibility of the roll shell transversely to the pressure or pressing line as well as in circumferential direction and a compromise must be made with respect to the wall thickness of the roll shell. The roll shell thus can not be selected with any desired thinness in consideration of maintaining sufficient circumferential stability. Consequently, a variation in the contact or pressing force at the location of one support element becomes effective at the adjacent support elements due to the inherently prevailing longitudinal stiffness of the roll shell. A predetermined desired contact or pressing force profile, therefore, can not be adjusted and regulated sufficiently precisely for many kinds of applications at the necessarily required high wall thicknesses and the line force can not be varied sufficiently precisely at the desired locations. There are further required, for the deformation of a roll shell having great wall thickness, a considerable force and a correspondingly greater amount of input power.
A controlled deflection roll as known, for example, from U.S. Pat. No. 4,058,877, granted Nov. 22, 1977, and from German Pat. No. 1,155,750, granted Oct. 17, 1963, comprises a thin elastic roll shell at the inner surface of which traveling rings are provided which are fixedly connected to the roll shell and synchronously rotate conjointly with the roll shell. The traveling rings form travel paths for related hydrostatic support elements or anti-friction or roller bearings hydrostatically pressed thereagainst.
The use of such features in rolls having a hard surface as required, for example, for the rolling of metal foils, i.e. providing traveling rings which are fixedly connected to and rotate conjointly with the roll shell, however, would not eliminate the prior art disadvantages mentioned hereinbefore because the deformation in circumferential direction would remain unchanged, and thus, also the danger of undesirably reaching the yield strength or elastic limit as well as the need for a greater force.
SUMMARY OF THE INVENTION
Therefore, with the foregoing in mind, it is a primary object of the present invention to provide a new and improved controlled deflection roll which is not afflicted with the aforementioned drawbacks and limitations of the prior art constructions heretofore discussed.
Another and more specific object of the present invention is directed to the provision of a new and improved controlled deflection roll having a hard outer surface and an improved flexibility in lengthwise as well as in circumferential direction.
Still a further significant object of the present invention is directed to a new and improved construction of a controlled deflection roll which despite its improved flexibility in lengthwise and in circumferential direction permits the generation of a higher contact or pressing force without the occurrence of undue deformations and yet requires smaller force and power.
Another, still important object of the present invention is directed to a new and improved construction of a controlled deflection roll in which the adjustment of the line force for the individual support or pressure elements is improved and in which the force exerted by the individual support or pressure elements becomes less effective at the adjacent support or pressure elements.
Now in order to implement these and still further objects of the invention, which will become more readily apparent as the description proceeds, the controlled deflection roll of the present development is manifested by the features that, the traveling rings are structured such that their outer diameter is somewhat smaller than the inner diameter of the roll shell and that the traveling rings are loosely placed into the interior space or inner region of the roll shell so as to be rotatable independently thereof.
The subdivision of the travel path for the support elements into a predetermined number of traveling rings or ring members which are rotatable independently of each other and of the roll shell causes an improved transverse flexibility of the inventive controlled deflection roll. Since the outer diameter of the traveling rings is somewhat smaller than the inner diameter of the roll shell, the traveling rings which are loosely placed into the interior space of the roll shell roll along the inner surface of the roll shell.
The main portion of the deformation under the action of the force generated by the support elements is absorbed in this arrangement by the traveling rings and the wall thickness of the actual roll shell can be selected so small that a sufficiently good transverse flexibility as well as circumferential flexibility of the roll shell are achieved.
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 throughout the various figures of the drawings there have been generally used the same reference characters to denote the same or analogous components and wherein:
FIG. 1 shows a longitudinal section through a first embodiment of the controlled deflection roll according to the invention;
FIG. 2 is a cross-section through the controlled deflection roll shown in FIG. 1 taken substantially along the line II--II in FIG. 1;
FIG. 3 shows a section of the roll shell and of some of the traveling rings in a second embodiment of the controlled deflection roll according to the invention;
FIG. 4 shows a section of the roll shell and of some of the traveling rings in a third embodiment of the controlled deflection roll according to the invention;
FIG. 5 shows a section of the roll shell and of some of the traveling rings in a fourth embodiment of the controlled deflection roll according to the invention;
FIG. 6 is a section of the roll shell and of some of the traveling rings in a fifth embodiment of the controlled deflection roll according to the invention;
FIG. 7 is a section of the roll shell and of some of the traveling rings in a sixth embodiment of the controlled deflection roll according to the invention;
FIG. 8 is a section of the roll shell and of some of the traveling rings in a seventh embodiment of the controlled deflection roll according to the invention; and
FIG. 9 is a section through part of the roll shell and part of the traveling rings in an eighth embodiment of the controlled deflection roll according to the invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Describing now the drawings, it is to be understood that only enough of the construction of the controlled deflection roll has been shown as needed for those skilled in the art to readily understand the underlying principles and concepts of the present development, while simplifying the showing of the drawings. Turning attention now specifically tO FIG. 1, there has been illustrated in section a first embodiment of the inventive controlled deflection roll comprising a stationary or non-rotating roll support member or beam 1 which is fixed in an appropriate manner at a conventional roll stand which is not particularly illustrated. A roll shell 2 is mounted for rotation about the roll support member or beam 1 and comprises a solid and hard outer roll shell surface 3, an inner roll shell surface 3' and an interior space or inner region 20. The roll shell 2 can be made of a suitable metal, for example, an alloyed and/or hardened steel. The roll shell 2 is supported at the stationary roll support member or beam 1 by a predetermined number of hydrostatic support or pressure elements 4 1 . . . 4 7 which are arranged in a row one beside the other in axial direction of the controlled deflection roll. The hydrostatic support elements 4.sup. 1 . . . 4 7 , for example, may be structured like the support elements described in the initially mentioned U.S. Pat. No. 3,802,044, to which reference may be had and the disclosure of which is incorporated herein by reference, or may be structured in any other known and appropriate manner.
The hydrostatic support elements 4 1 . . . 4 7 are provided with related bearing surfaces 5 1 . . . 5 7 on their side which faces the roll shell 2. Contrary to the known controlled deflection rolls discussed hereinbefore, the hydrostatic support elements 4 1 . . . 4 7 do not directly cooperate or interact with the inner roll shell surface 3' of the roll shell 2. In the inventive arrangement traveling rings or ring members 6 1 . . . 6 7 are provided in the interior space 20 of the roll shell 2 and each of these traveling rings 6 1 . . . 6 7 contains a related inner traveling ring surface 7 1 . . . 7 7 . Each of the inner traveling ring surfaces 7 1 . . . 7 7 is associated with a related one of the support elements 4 1 . . . 4 7 and constitutes a travel path for the related support element. The traveling rings 6 1 . . . 6 7 are also made of an appropriate metal, for example, alloyed and/or hardened steel. The traveling rings 6 1 . . . 6 7 each have an outer traveling ring diameter d 2 which is somewhat smaller that the inner roll shell diameter d 1 of the roll shell 2, see FIG. 2. The traveling rings 6 1 . . . 6 7 are loosely inserted into the interior space 20 defined by the roll shell 2.
During operation of the controlled deflection roll the hydrostatic support elements 4 1 . . . 4 7 are supplied with pressure fluid from a suitable pressure fluid supply 30 via pressure lines 8 and are urged in the direction of the rotating roll shell 2. The traveling rings 6 1 . . . 6 7 are pressed against the roll shell 2 by the related support elements 4 1 . . . 4 7 and rotate conjointly with the roll shell 2, however, at a slightly different rotational speed in accordance with the difference Δd of the inner roll shell diameter d 1 and the outer traveling ring diameter d 2 . The traveling rings 6 1 . . . 6 7 thus roll along the inner roll shell surface 3' of the roll shell 2. Due to the different diameters of the roll shell 2 and the traveling rings 6 1 . . . 6 7 , firstly only the traveling rings 6 1 . . . 6 7 are deformed into a slightly elliptical shape under the action of the forces generated by the related support elements 4 1 . . . 4 7 . Since the roll shell 2 has a greater radius of curvature than the traveling rings 6 1 . . . 6 7 , no deformation of the roll shell 2 occurs up to a predetermined force, so that the disadvantages due to a deformation of the roll shell which occurs in the known controlled deflection rolls, are a priori avoided or eliminated. Preferably, the difference Δd in the diameters d, and d 2 is selected such that the maximum forces are absorbed as exclusively as possible by the traveling rings 6 1 . . . 6 7 .
Prior art controlled deflection rolls having a length of about 2 meters and a diameter in the range of 35-40 cm hitherto have required a wall thickness of the roll shell in a range of magnitudes extending between 50 mm and 80 mm. It has been shown that, when traveling rings 6 1 . . . 6 7 having a wall thickness of about 50 mm are loosely inserted into the roll shell 2, the controlled deflection rolls can be manufactured with roll shells 2 having a wall thickness in the range of only 10 mm to 15 mm. Due to the wall thickness which is smaller by a factor of 3 to 4, the roll shell 2 has a significantly improved flexibility in lengthwise direction as well as in circumferential direction and a sufficient stiffness in circumferential direction is insured due to the presence of the traveling rings 6 1 . . . 6 7 . Due to the thinner roll shell 2, the line force can be adjusted with greater precision than hitherto has been possible since the effect of the force exerted by the individual support elements 4 1 . . . 4 7 on its neighboring regions is considerably reduced. The number of support elements and thus the number of control or regulation points therefore can be increased as compared with the prior art controlled deflection rolls. Furthermore, the force required for a deflection of the roll along the pressure or pressing line or axis is also distinctly smaller than in the prior art controlled deflection rolls due to the lower wall thickness of the roll shell 2.
FIG. 2 is a cross-section in the plane II--II in FIG. 1 and the same elements are generally conveniently designated by the same reference characters in these two figures of the drawings. The difference Δd between the inner roll shell diameter d 1 of the roll shell 2 and the outer traveling ring diameter d 2 of the traveling ring 6 7 can be distinctly recognized. In the illustrated embodiment the hydrostatic support element 4 7 is radially displaceable within a cylindrical bore or chamber 9 in the stationary, non-rotating roll support member or beam 1 and is provided with a bearing surface 5 7 and a pressure pocket or chamber 10. The pressure pocket or chamber 10 communicates, via a throttling passage or bore 11, with the cylindrical bore or chamber 9 which, in turn, is connected to one of the pressure fluid lines 8.
In the first embodiment illustrated in FIGS. 1 and 2 the traveling rings 6 1 . . . 6 7 and the related support elements 4 1 . . . 4 7 are arranged in the interior space 20 of the roll shell 2 in a densely or an almost closely packed manner. These traveling rings 6 1 . . . 6 7 can be retained in their correct position by, for example, not particularly illustrated spring means arranged at the ends of the roll. In such simple arrangement it is of advantage that the roll shell 2 as well as the traveling rings 6 1 . . . 6 7 can be constructed as purely cylindrical tubes which can be easily exchanged at favorable costs.
Instead, the maintenance of a defined position of the traveling rings, now generally designated by reference character 6, during the operation of the controlled deflection roll and during rotation of the roll shell 2 can also be achieved in a different manner by additional measures like, for example, annular guide elements, which is explained hereinafter with reference to FIGS. 3 to 8.
FIG. 3 shows a section of the roll shell 2 of a second embodiment of the inventive controlled deflection roll. The roll shell 2 is provided at its inner surface 3' with annular grooves or flutes 12 along which the traveling rings 6 roll and by means of which these traveling rings 6 are retained in their intended or predetermined position.
FIG. 4 shows a section of the roll shell 2 of a third embodiment of the inventive controlled deflection roll in which annular guide elements are provided at the roll shell 2 and further annular guide elements are provided at the traveling rings 6 in such a manner that the annular guide elements and the further annular guide elements cooperate in the manner of a groove-and-tongue relationship. Specifically, the annular guide elements at the roll shell 2 constitute annular webs 13 provided at the inner surface 3' of the roll shell 2. The further annular guide elements constitute complementary annular grooves 13' which are formed at the outer traveling ring surfaces 7' of the traveling rings 6. The annular webs 13 and the interacting annular grooves 13' cooperate such that there is once again insured the intended or predetermined position of the traveling rings 6.
Instead of this design the position of the traveling rings 6 can also be, however, insured by elastic spacer elements. In the fourth embodiment of the inventive controlled deflection roll illustrated in FIG. 5 the roll shell 2 is of a purely cylindrical structure and spacer rings 14 are provided intermediate the traveling rings 6. The spacer rings 14 may be made of, for example, a rubber-elastic or elastomeric material or an appropriate plastic material.
In the fifth embodiment of the inventive controlled deflection roll which is shown in FIG. 6 and which is similar to the embodiment shown in FIG. 5, the spacer rings 15 are of circular cross-section and engage lateral grooves 16 which are provided at the traveling rings 6.
A sixth embodiment of the inventive controlled deflection roll is illustrated in FIG. 7. As shown, the elastic spacer elements therein constitute metal rings 17 of a slightly resilient or springy nature which is due to their U-profile but which property also can be obtained by providing any other appropriate profile.
In the further modified seventh embodiment of the inventive controlled deflection roll illustrated in FIG. 8, the metallic spacer rings 18 are structured such as to form an S-shaped profile which results in an improved resiliency.
In the embodiments of the inventive controlled deflection roll described hereinbefore the roll shell has been structured as a substantially cylindrical tube. In the eight embodiment of the inventive controlled deflection roll shown in FIG. 9 particularly the transverse flexibility, i.e. the flexibility along the pressure or pressing line, is still further improved by providing a helically-shaped slot 19 in the roll shell 2. Accordingly, the roll shell 2 forms a helically-wound band. Also in this embodiment the stiffness in circumferential direction required during operation of the controlled deflection roll is again insured by traveling rings 6 which are provided in the interior space 20 of the roll shell 2. The helically-shaped slot 19 may be continuously formed throughout the entire length of the roll shell 2 but can also be constituted by individual sections. In most cases the slot 19 in the surface of the roll shell 2 does not interfere with the use of the controlled deflection roll since this slot 19 continuously travels along the entire length of the controlled deflection roll during operation thereof.
It is further noted that, within the scope of the invention, instead of the heretofore described construction of controlled deflection rolls with hydrostatic support or pressure elements also other types of controlled deflection rolls can be used with similar advantages, for example, controlled deflection rolls provided with hydrodynamic support or pressure elements or controlled deflection rolls with pressure chambers which constitute the support elements.
While there are shown and described present preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto, but may be otherwise variously embodied and practiced within the scope of the following claims. ACCORDINGLY, | The controlled deflection roll comprises a stationary, non-rotating roll support member and a roll shell mounted to rotate about the stationary roll support member. The roll shell is not directly supported at the stationary roll support member by means of hydraulic support elements, but through the intermediary of additionally provided traveling rings each of which defines a travel path for the related hydraulic support element. The traveling rings have an outer diameter slightly smaller than the inner diameter of the roll shell and they are arranged to be rotatable independently of the roll shell. During operation of the controlled deflection roll the traveling rings, therefore, roll along the inner surface of the roll shell. As a result, the flexibility of the roll shell is improved in circumferential direction as well as transversely to the pressing line of the controlled deflection roller. In this arrangement stiffness of the roll shell in circumferential direction is insured by the traveling rings. Undue deformations of the roll shell are thereby prevented and the force requirements are reduced. | 5 |
This is a division of application Ser. No. 07/543,115, filed Jun. 21, 1990, now abandoned.
SUMMARY OF THE INVENTION
The present invention relates to new terpene derivatives of formula I: ##STR2## and to their preparation and use.
In formula I, R represents a hydrogen atom or an alkanoyl radical containing 1 to 4 carbon atoms, such as an acetyl radical, and R' represents a hydrogen atom or an aliphatic hydrocarbon radical containing 1 to 20 carbon atoms. Optionally, the aliphatic hydrocarbon has one or more double bonds, such as, a prenyl or geranyl radical.
Of very special interest are the terpene derivatives of formula I wherein R' represents a hydrogen atom or a prenyl radical (CH 3 C(CH 3 )═CH--CH 2 --).
DETAILED DESCRIPTION OF THE INVENTION
A. According to the present invention, the new terpene derivatives of formula I, wherein R represents an alkanoyl radical, are obtained from an α-halo-β-keto ester of formula II: ##STR3## wherein R' is defined as above, X represents a halogen atom, preferably a chlorine atom, and R 1 represents an alkyl radical containing 1 to 4 carbon atoms, preferably a methyl or ethyl radical. The terpene derivatives of formula I are formed from the ester of formula II either by (1) acylation followed by decarboxylation, or (2) by decarboxylation followed by acylation of a compound of formula II.
In method (1), acylation is performed using a compound of formula II to obtain a compound of formula III: ##STR4## wherein R', R and R 1 are defined as above. Preferably, an alkali metal salt of an aliphatic acid of formula IV:
R.sub.2 --CO--OM IV
wherein R 2 represents a hydrogen atom or an alkyl radical containing 1 to 3 carbon atoms and M represents an alkali metal atom such as a sodium or potassium atom, is combined with a compound of formula II, in a polar organic solvent such as N-methylpyrrolidone, at a temperature of between about 50° C. and 200° C.
Decarboxylation is performed using a compound of formula III to obtain a compound of formula I by heating at a temperature of between about 20° C. and 200° C., preferably between about 50° C. and 100° C., in a polar organic solvent, such as N-methylpyrrolidone, in the presence of lithium chloride and a tertiary amine salt such as lutidine hydrochloride. This process is optionally prepared in situ.
In method (2), decarboxylation is performed using a compound of formula II to obtain a compound of formula V: ##STR5## wherein R' and X are defined as above. This process is performed under the conditions described above for the decarboxylation of a compound of formula III to a compound of formula I.
Acylation of a compound of formula V to a compound of formula I is performed under the conditions described above for the acylation of a compound of formula II to a compound of formula III.
B. According to the present invention, the new terpene derivatives of formula I, wherein R represents a hydrogen atom are obtained by saponification of a compound of formula I wherein R represents an alkanoyl radical which is obtained as described above.
The saponification is preferably performed by means of a base, such as sodium hydroxide or potassium hydroxide, in an aqueous-alcoholic medium, such as a water/methanol mixture, at a temperature of between about 0° C. and 40° C.
The present invention relates to compounds of formula I, namely compounds of formula Ia and Ib: ##STR6## taken alone or in the form of a mixture.
Compounds of formula II are obtained by halogenation of a β-keto ester of formula VI: ##STR7## wherein R' and R 1 are defined as above, under the conditions described in European Patent EP 82,781.
Compounds of formula VI may be obtained by the action of an alkyl acetyl acetate on myrcene under the conditions described in European Patent EP 44,771. Compounds of formula V may also be obtained according to the processes described in U.S. Pat. Nos. 4,097,531 or 4,806,280.
The new terpene derivatives of formula I are especially useful intermediates in terpene synthesis. For example, compounds of formula I in which R represents a hydrogen atom or a prenyl radical are useful for preparing methylheptadienone or pseudoionone, which are especially important intermediates used in perfumery or in the synthesis of vitamin A. J. M. Defer et al., "Terpenoids", in Kirk-Othmer Encyclopedia 22, 709; H. Pommer et al., Pure and Appl. Chem. 43, 527 (1975).
For example, pseudoionone of formula: ##STR8## is obtained by pyrolysis of a compound of formula I wherein R' represents a prenyl radical and R represents an acetyl radical, or by dehydration, in the vapour phase over an acid catalyst (HOLDERICH, Angew. Chemie Int. Ed., 1988, 226) or in the liquid phase by means of phosphorus oxychloride, of a product of formula I in which R' represents a prenyl radical and R represents a hydrogen atom.
The examples which follow, given without implied limitation, show how the invention may be put into practice.
EXAMPLE 1
100 cc of N-Methylpyrrolidone and then 1.7 g (46.6 mmol) of gaseous hydrochloric acid were introduced under an argon atmosphere into a 250-cc three-necked round-bottomed flask. 1.36 g of anhydrous lithium chloride and 3.47 g (32 mmol) of 2,6-lutidine were added. The mixture was maintained at 25° C., and 5.36 g (17.4 mmol) of a 45:55 mixture of 3-chloro-3-carbomethoxy-6,10-dimethyl-5,9-undecadien-2-one and 3-chloro-3-carbomethoxy-10-methyl-6-methylene-9-undecen-2-one, having a purity of 98%, was added. Then the mixture was heated for 1 hour to 90° C. The mixture was extracted with a pentane/water mixture, and the organic phase was evaporated. 4.3 g of an oily orange-colored residue was obtained. The 3-chlorogeranylacetone content, determined by the proton nuclear magnetic resonance spectrum and by gas chromatography, was about 85%, and the degree of conversion was about 100%.
50 cc of N-methylpyrrolidone, 3.6 g (36.7 mmol) of potassium acetate; and 1.90 g of a portion of the product obtained above were introduced into a 100-cc three-necked flask. The mixture was heated for 1 hour to 88° C. under an argon atmosphere.
The mixture was extracted with a pentane/water mixture, and the organic phase was evaporated. A yellow oil was obtained, the analysis of which by thin-layer chromatography shows that the degree of conversion was about 100%.
The yellow oil was purified by flash chromatography, and then eluted with a pentane/ethyl acetate mixture. 1.6 g of a pale yellow oil was obtained consisting of a 40:60 mixture of 3-acetoxy-6,10-dimethyl-5,9-undecadien-2-one and 3-acetoxy-10-methyl-6-methylene-9-undecen-2-one, the structure of which was confirmed by the proton nuclear magnetic resonance spectrum, 13 C nuclear magnetic resonance spectrum, and infrared spectrum.
EXAMPLE 2
1.26 g (5 mmol) of 3-acetoxygeranylacetone in 20 cc methanol was introduced under an argon atmosphere into a 100-cc three-necked flask. 3.8 cc 38% (w/v) aqueous potassium hydroxide solution was added at 5° C. The mixture was stirred for 3 hours at 20° C. and then neutralized by the addition of hydrochloric acid.
The reaction mixture was extracted with pentane. After flash chromatography, 0.98 g of a colorless oil was isolated, the analysis of which, by the proton nuclear magnetic resonance spectrum, infrared spectrum and mass spectrum showed that was a 35:65 mixture of a compound of formulas: ##STR9##
EXAMPLE 3
1.2 cc of pyridine and a 0.2 g (0.95 mmol) portion of the mixture of the compounds obtained in Example 2 was introduced into a 50-cc round-bottomed flask, and 0.1 cc phosphorus oxychloride was then added slowly at 0° C. Formation of a precipitate was observed. The mixture was neutralized and extracted with ether and then maintained for 2 hours at 0° C. 150 mg an orange-colored oil was obtained, of which the pseudoionone (EE+ZE) content was 80%. The structure of the product obtained was confirmed by the proton nuclear magnetic resonance spectrum, infrared spectrum and mass spectrum in comparison with an authentic sample. The degree of conversion was 100% and the yield of crude product was 66%. | Terpene derivatives of formula I, their preparation and their use. In formula I, R represents a hydrogen atom or an alkanoyl radical and R' represents a hydrogen atom or an aliphatic hydrocarbon radical. ##STR1## | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a perfection of Provisional Patent Application Ser. No. 61/822,537, filed May 13, 2013, the disclosure of which is incorporated herein.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] This invention relates to the field of highway barriers. Particularly, it relates to center median barriers especially those made from prefabricated concrete. Such devices are commonly known as “Jersey barriers”.
[0004] A Jersey barrier (or sometimes called Jersey wall) is a modular divider used to separate lanes of traffic, either vehicles from one another, or vehicles from pedestrians and/or cyclists. The shape of such barriers was designed to minimize damage to a car, truck or other vehicle that makes incidental contact with it while preventing lane crossovers and avoiding head-on collisions. Jersey barriers are also used to reroute vehicular traffic and/or protect pedestrians during road construction. More recently, they have served as temporary or semi-permanent protection against land born attacks from suicide car bombers.
[0005] According to Wikipedia, the Jersey barrier was developed at the Stevens Institute of Technology in 1950's but introduced in its most current form in 1959. Per the auspices of the New Jersey State Highway Department, such barriers were meant to divide multiple lanes of a highway, particularly the flow of traffic in a first direction, from the opposite flow of traffic in the other (oncoming) direction. A typical Jersey barrier stands 32 inches (81 cm) tall and is made of steel-reinforced poured concrete. Some barriers are purposefully constructed with embedded steel protruding from each end. Those protrusions allow adjoining barriers to be linked to one another as part of a more permanent emplacement.
[0006] The widespread use of such barriers on roads has led to wider applications including: use as a generic, portable barrier during construction projects and/or for temporary traffic re-routing as part of a stopgap carpool or “rush hour” bridge/highway lane reversal.
[0007] The original Jersey barrier profile was intended to minimize vehicular damage through incidental contact. In “shallow” angle hits, car fender/sheet metal damage should be reduced as the vehicle's tires are meant to ride up the lower sloped faces of such barriers before falling back onto the lane/road surface. Such barriers should minimize the chances of a head-on crash by gradually lifting the vehicle that contacts same and pivoting it away from oncoming traffic in the opposite direction.
[0008] In 1968, the Ontario, Canada Department of Highways introduced a taller variation of barrier standing 42 inches (107 cm), or about 10 inches (25 cm) higher than the common U.S. barrier size. Thereafter, the New Jersey Turnpike Authority developed and tested a similar, more heavily reinforced design. It has been credited with effectively containing and redirecting larger vehicles, including semi-trailer (tractor-trailer) trucks. While the benefits of a taller highway barrier may be known, there has not been a cost-effective impermeable means for modifying existing (shorter) barriers to make them “safer” let alone in an aesthetically pleasing manner.
[0009] 2. Relevant Art
[0010] One of the first known barrier improvements was patented by Camomilla et al. in U.S. Pat. No. 6,840,706. It included a double dampening effect that used ductile anchor components, including rigidly connected steel plates at the barrier base.
[0011] A different construction of barrier style was the subject of Ceccarelli U.S. Pat. No. 7,226,237. It employed a plurality of tubular modules extending upwardly from a ground connect.
[0012] Yet another set of interconnecting modular elements was the subject of Serafin U.S. Pat. No. 8,172,204.
[0013] There have also been proposals for making a continuous screen barrier using interconnecting panels. See, Borgnini U.S. Pat. No. 5,149,061. Continuous uprights on Jersey barrier was the focus of European Patent Application Serial No. 1,619,311. And in McNally et al., U.S. Published Application No. 20050135878, Jersey barriers were fitted with temporary, “bolt on” risers. Lastly, in White et al. U.S. Pat. No. 8,001,880, it was proposed to make more attack resistant (especially bulletproof) protectors using add-ons to Jersey style barrier frame.
SUMMARY OF THE INVENTION
[0014] A primary object of this invention is to provide an improved cap or add-on for raising the protectable height/protection range of an existing (i.e. previously installed) roadway Jersey barrier. It is critical that any such “adapter” be cost effective, quick to install, not labor intensive and yet have greater structural significance that known temporarily erected panels or those string of continuous vertical slats sometimes situated atop super highway/turnpike dividers for reducing opposing traffic headlight glare.
[0015] The heavy, permanent cap toppers of this invention are preferably made from concrete but with proper weighting could be made from fiberglass, composites, rubber and/or recycled plastic materials in the alternative. Regardless of material, they will surely provide the advantages of the integrally formed, higher barriers mentioned above, such as significant opposing headlight glare reduction. In addition, it is less likely that a whole vehicle or major parts of same (such as a tire, side mirror, etc.) will rise up and fully cross over these extra-high, purposefully raised center barriers for then crossing over and into unsuspecting traffic traveling the other way on the opposite side of such barriers. Upon impacting such barrier extensions, the cars and/or their major components will more likely stay on the same side of traffic flow where later following vehicles may have a greater chance of swerving to avoid impact.
[0016] These barrier add-on's are also structurally more sound/substantial than the flat panel and/or flimsy multi-slat barrier additions being used in some locations. The latter known varieties can also be more prone to “sailing” because of their vulnerability to high winds and greater possibility of individual slat separations from the top of existing highway barriers.
[0017] This invention also provides means for communities/municipalities to impart some degree of creative “flair” to the central barriers on those sections of highways/thruways extending through their respective communities. It enables the addition of particular raised cap configurations to their existing Jersey barriers, said cap additions having special patterns and/or colors or possibly distinctive reflector means added in spaced distances.
SUMMARY OF THE DRAWINGS
[0018] Further features, objectives and advantages of this invention will become clearer with the following detailed description made with reference to the accompanying drawings in which:
[0019] FIG. 1 is a perspective view of a first embodiment of Jersey barrier cap according to this invention;
[0020] FIG. 2 is a front plan view of the cap from FIG. 1 ;
[0021] FIG. 3 is a sectional view taken along lines A-A of FIG. 2 ;
[0022] FIG. 4 is a top plan view of the same first embodiment as in FIGS. 1-3 ;
[0023] FIG. 5 is a perspective view of a second embodiment of barrier addition;
[0024] FIG. 6 is a front plan view of the barrier addition from FIG. 5 ;
[0025] FIG. 7 is a left side plan view of the barrier addition from FIG. 6 ;
[0026] FIG. 8 is a top plan view of the barrier addition from FIGS. 5-7 ;
[0027] FIG. 9 is a perspective view of an alternate second embodiment showing different attachment means;
[0028] FIG. 10 is a perspective view of a third embodiment of barrier cap according to this invention; and
[0029] FIG. 11 is a perspective view showing a plurality of the FIG. 10 type caps installed over several existing Jersey highway barriers aligned in series.
DESCRIPTION OF PREFERRED EMBODIMENTS
[0030] Jersey barriers have become an acceptable method for preventing traffic from penetrating the barrier and crossing the highway median into oncoming traffic where such barriers are installed. Each individual barrier has a widened base, sides with two sloping sections, and a flattened top surface. Usually made from concrete, the Jersey barrier is heavy and durable, yet possesses the proper shape and mass to deflect most small vehicles back into the lane from whence they came. They require little or no periodic maintenance. And even in today's shorter heights, standard barriers provide some security by deterring pedestrian traffic from wanting to straddle or otherwise cross over a whole series of such dividers.
[0031] Known Jersey barriers are relatively easy to move or install. Common barrier designs include two rectangular notches at the bottom (through the short axis). Those notches allow individual barriers to be raised by a forklift or pronged front-end loader. Barriers intended for short-term placement, especially in military and security uses, might include one or more steel rebar loops at or near their top surface for rapid hook-and-cable lifting.
[0032] Lately, there have been Jersey barrier additions designed to reduce, minimize or eliminate the blinding effects of opposing traffic headlights. One solution was to provide multiple slat-like extensions, each individually affixed, to the top surface of each Jersey barrier so that the lights of oncoming traffic are not readily visible. Such “blinders” actually allow opposing traffic to be seen in the distance AND when immediately adjacent the car opposite the barrier from the nearly 90 degree angle for each slat/blind. That has to be at or near perpendicular since it must block the headlight penetration from BOTH sides of the highway divider. A solid sheet might accomplish the same result, but it would be more difficult to attach, maintain AND render itself more vulnerable to damage as elongated plastic sheet separators would have a greater tendency to sail and dislodge in stronger wind gusts.
[0033] With the nominal physical divide from one or more plastic extensions, there is little to no additional protection afforded by a series of angled slats. Should a heavier vehicle, trailer, bus or the like plop over and onto such extensions in an accident, they will crack and/or crumble.
[0034] This invention seeks to modify the standard Jersey barrier by providing a quick and easy installation of a supplemental physical (permanently installed) vertical addition that will increase the difficulty (i.e. eliminate the likelihood) of pedestrians scaling, straddling and/or climbing over same. The invention also affords protection against the intimidating headlights of opposing traffic . . . regardless of angling. And a raised barrier via the extension varieties depicted herein will keep break off components, if not whole vehicles, from crossing over and “surprising” traffic flowing past in the opposite direction. It does so with no fear of “sailing” or otherwise blowing away. These caps are sufficiently weighty to stay onto the underlying barrier bottoms over which they will be installed and/or permanently mounted.
[0035] Referring to FIGS. 1 through 4 , there is shown a first embodiment of barrier cap/adapter, generally 10 , in various views. Particularly, cap 10 comprises a flat base 12 , from which upwardly extends a pair of opposed sidewalls 14 and 16 , the latter two tapering upwardly and inwardly to a top surface 18 . The essence of this invention is to provide a permanent adapter that raises the vertical (useful) height of an existing Jersey highway barrier (JB), a representative example of which is also seen in FIG. 1 . Particularly, that standard sized/shaped barrier JB includes a flat base J 12 , beveled sidewalls J 14 and J 16 with its top surface J 18 extending therebetween.
[0036] In the first embodiment shown in FIGS. 1-4 , there is a supplemental support system that not only requires the cap's flat base 12 to rest atop Jersey top surface J 18 but to further have side supporting, downward leg extensions, 24 and 26 respectively, for straddling the existing Jersey barrier's body construction and resting alongside (or “hugging”) the upper sidewalls J 14 and J 16 to that existing barrier. With the foregoing leg extensions, this variety of cap according to the invention exhibits more of a bullet, tooth, or most like, an arrowhead-shape in cross-section. See particularly, FIGS. 1 and 3 .
[0037] For the preferred mounting means of this first embodiment, there are a plurality of holes H extending from the top surface 18 and downwardly towards the top surface J 18 of the existing barrier. These holes H may be pre-formed into the respective caps during initial manufacture, or drilled into and through the bodies of same, after the fact. Each hole H is intended to have a bolt B positioned therein and downwardly into top surface J 18 for permanently affixing cap 10 to Jersey Barrier JB.
[0038] FIGS. 5 through 8 show a second variation/embodiment of cap 110 , also having its own base 112 , sidewalls 114 , 116 and top surface 118 . Since this variation has no downward extensions to its opposed sidewalls, the overall configuration is more trapezoidal in cross-section as best seen in FIGS. 5 and 7 . With no additional side support, the preferred permanent connection means for THIS variation includes a plurality of vertically-extending slats 120 , each slat having a plurality of holes H through which bolts B are installed for affixing cap 110 to its own Jersey Barrier JB.
[0039] The third variation of cap 210 in FIG. 9 shows a larger/wider configuration of slat 220 with a larger bolt configuration B, but only one top bolt and one bottom bolt permanently affixing cap 210 to Jersey Barrier JB.
[0040] The sidewalls to these cap/adapters can be specially customized to provide aesthetics and distinctiveness for a given town's highway separator system. The “fancy” sidewalls to the cap/adapter 310 of FIG. 10 , for instance, includes a plurality of raised surfaces 330 , spaced apart from one another. For greater distinctiveness, these raised surfaces can be made from multiple colors of concrete materials. Alternately, several of these raised surfaces can be provided with reflective tape or paint R. In the last described variation, FIG. 11 , the raised surfaces of cap/adapter 410 are replaced with spaced recesses 430 .
[0041] The accompanying FIGURES depict two representative mounting types, drilled and/or staked from above as per FIGS. 1-4 or attached through a plurality of commonly mounted connector/adapters (per FIGS. 5-8 ). In some instances, these connectors may be purposefully covered or otherwise hidden from view (and from the temptation of possible tampering by vandals). See, especially FIG. 9 .
[0042] Ultimately, the present invention will enable certain customizations of barrier “art” so that all barrier tops for a given community may be fitted with common decorative (in color, texture and/or pattern) inserts or raised regions. See, for example, the multiple square sequencing of FIGS. 10 and 11 . In place of, OR in addition to such patterns, it is possible to situate headlight reflectors (in strips, brackets or the like) to the common areas of each pattern, or somewhat raised between patterns, for providing the Jersey barrier caps of this invention the added benefit of nighttime reflectivity.
[0043] Each barrier cap may be further provided with suitable interconnecting means for supplementing the connection(s) made between underlying, adjacent Jersey barrier bottoms. Like the directional headlight reflectors described above, these interconnects are not shown/seen in any of the accompanying drawings, however.
[0044] No doubt, still other modifications, improvements and/or acceptable variations to the barrier caps described in this specification will arise. They should all be covered by the appended utility claims. | A barrier cap permanently connected atop an existing Jersey barrier for raising the vertical height of said existing Jersey barrier at least about ten inches. The cap comprises: a substantially flat base for resting at least partially on said existing Jersey barrier; a pair of opposed sidewalls extending upwardly from its flat base; a top surface extending between the opposed sidewalls; and means for permanently connecting the barrier cap to the existing Jersey barrier. Preferred mounting means include: a plurality of elongated bolts extending from the top surface of the concrete adapter into the top surface of the Jersey barrier; or a plurality of vertically extending slats for bolting to an upper sidewall of the Jersey barrier. | 4 |
BACKGROUND
[0001] Endoscopic procedures to treat abnormal pathologies of the gastro-intestinal (“GI”) canal system, of the biliary tree, of the vascular system and of various other body lumens are becoming increasingly common. The endoscope is basically a hollow tube that is placed at a desired location within the body to facilitate access to the relevant body ducts and lumens, etc. The endoscope itself cannot carry out many of the required procedures. To that end, the endoscope is fitted with a lumen, or internal channel, which permits the user to insert various medical devices therethrough to the location that requires treatment. Once the distal end of the inserted device has reached the tissue to be treated, it can be manipulated using controls which remain outside the body.
[0002] An hemostatic clipping tool is one of the devices which may be inserted through an endoscope so that treatment may be carried out. Hemostatic clips are deployed from the clipping tool and are used to stop internal bleeding by clamping together the edges of a wound. The clipping tool complete with clips attached to its distal end is inserted through the endoscope to the location of the bleeding. A clip is then remotely manipulated into position over the site of bleeding, clamped over the wound and detached from the tool. After a number of clips sufficient to stop the bleeding has been deployed, the tool is withdrawn from the patient's body through the endoscope. The size and shape of the clips and of the clipping tool are limited by the inner diameter of the endoscope's lumen, thus placing constraints on the design of the clip positioning and release mechanisms.
[0003] One challenge facing the endoscope operator is to properly position the hemostatic clips over the wound, so that closing the clips over the tissue will be effective in stopping the bleeding. If a clip is deployed improperly, additional clips may be required to stop the bleeding extending the time required for and the complexity of the procedure and leaving additional medical devices within the patient. It is also important for the device operator to be certain of the status of the clip during the deployment operation. For example, before withdrawing the tool from the endoscope, the operator should have positive indication that a clip has fully deployed, and has been released from the tool. At the same time the design of the tool should ensure that clips are fully released after they have been closed over the tissue.
SUMMARY OF THE INVENTION
[0004] In one aspect, the present invention is directed to an apparatus for deployment of a hemostatic clip comprising a handle assembly and a shaft connected to a distal portion of the handle assembly in combination with a clip assembly releasably coupled to a distal portion of the shaft, the clip assembly including clip arms and a capsule cooperating with the clip arms to provide a first user feedback indicating a decision configuration of the clip assembly and a control wire including a ball connector, the control wire extending from the handle assembly and coupled to the clip assembly by the ball connector to maintain the clip assembly coupled to the shaft, wherein the ball connector is detachable from the clip assembly to provide a second user feedback indicating separation of the clip assembly from the shaft.
[0005] In a different aspect, the present invention is directed to a clip assembly deployable through an endoscope, comprising a capsule releasably connected to a bushing of an elongated clip deployment device, clip arms slidable within the capsule between a distal open configuration and a proximal closed configuration, a tension member slidable with the clip arms, urging the clip arms in the open configuration, and a yoke slidable within the capsule, releasably connected to the tension member at one end, and connected to a control wire of the clip deployment device at another end. In the invention, distal movement of the control wire slides the clip arms in the open configuration, and proximal movement of the control wire slides the clip arms in the closed configuration.
[0006] In a further embodiment, the invention is directed to a method for hemostatic clipping through an endoscope. The method includes providing a shaft section connected to a clip assembly of a clipping device insertable through an endoscope working lumen, providing a handle assembly attached to the shaft section, the handle assembly allowing longitudinal movement of a control wire, and providing a connection between a distal end of the control wire and clip arms of the clip assembly, whereby longitudinal movement of the control wire moves the clip arms between an open and a closed configuration. The method also includes giving a first user feedback indicating a decision configuration of the clip assembly, and giving a second user feedback indicating separation of the clip assembly from the shaft section.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007] FIG. 1 is a schematic side view of a clipping device according to an embodiment of the present invention, with a detail view of an exemplary clip assembly;
[0008] FIG. 2 is a schematic side view of the embodiment shown in FIG. 1 , with a outer sheath;
[0009] FIG. 3 is a cut away side view of the shaft section according to an embodiment of the present invention;
[0010] FIG. 4 is a cross sectional view of the shaft section shown in FIG. 3 ;
[0011] FIG. 5 is a detail view of the distal end of the control wire according to an embodiment of the present invention;
[0012] FIG. 6 is a perspective view of an outer sheath according to an embodiment of the present invention;
[0013] FIG. 7 is an cross sectional exploded view of the handle of the outer sheath shown in FIG. 6 ;
[0014] FIG. 8 is a perspective view of an outer sheath lock according to an embodiment of the present invention;
[0015] FIG. 9 is a cross sectional side view of a distal end of a clipping device according to an embodiment of the present invention;
[0016] FIG. 10 is a cross sectional top view of a distal end of the clipping device shown in FIG. 9 ;
[0017] FIG. 11 is a perspective view of the distal end of the clipping device shown in FIG. 9 ;
[0018] FIG. 12 is a top view of the clip arms according to an embodiment of the present invention;
[0019] FIG. 13 is a perspective view of the clip arms shown in FIG. 12 , according to an embodiment of the present invention;
[0020] FIG. 14 is a perspective view of a capsule according to an embodiment of the present invention;
[0021] FIG. 15 is a cross sectional side view of the of the capsule shown in FIG. 14 ;
[0022] FIG. 16 is a top view of the distal end of a clipping device according to an embodiment of the present invention;
[0023] FIG. 17 is a side view of the distal end shown in FIG. 16 ;
[0024] FIG. 18 is a perspective view of a clip arm according to an embodiment of the present invention;
[0025] FIG. 19 is a side view of the clip arm shown in FIG. 18 ;
[0026] FIG. 20 is a top view of the clip arm shown in FIG. 18 ;
[0027] FIG. 21 is a perspective view of a bushing according to an embodiment of the present invention;
[0028] FIG. 22 is a cross sectional side view of the bushing shown in FIG. 21 ;
[0029] FIG. 23 is a perspective view of a wire stop according to an embodiment of the present invention;
[0030] FIG. 24 is a schematic side view of a clip assembly detached from a bushing, according to an embodiment of the present invention;
[0031] FIG. 25 is a side view of a tension member according to an embodiment of the present invention;
[0032] FIG. 26 is a top view of the tension member shown in FIG. 25 ;
[0033] FIG. 27 is a top view of a yoke according to an embodiment of the present invention;
[0034] FIG. 28 is a perspective view of the yoke shown in FIG. 27 ; and
[0035] FIG. 29 is a top view of a yoke with a control wire according to an embodiment of the present invention.
DETAILED DESCRIPTION
[0036] Hemostatic clips are used routinely to stop bleeding from openings created during surgery as well as wounds resulting from other trauma to tissues. In the simplest form, these clips grasp the tissue surrounding a wound and bring the wound's edges together, to allow the natural scarring process to heal the wound. In endoscopic hemostatic clips are used to stop internal bleeding due resulting from surgical procedures and/or tissue damage from disease, etc. Specialized endoscopic hemostatic clipping devices are used to bring the clips to the desired location within a patient's body and to position and deploy the clip at the appropriate place on the tissue. The clipping device is then withdrawn, leaving the clip within the patient.
[0037] Endoscopic hemostatic clipping devices are designed to reach affected tissues deep within a patient's body, such as within the GI tract, the pulmonary system, the vascular system or within other lumens and ducts. During the procedures to treat those areas, an endoscope is generally used to provide access to and visualization of the tissue which is to be treated. The clipping device may, for example, be introduced through a working lumen of the endoscope. The design and construction of such a “through the scope” endoscopic hemostatic clipping device presents several challenges. The endoscopic clipping device has to be sufficiently small to fit in the lumen of an endoscope and, at the same time, must be designed to provide for the positive placement and actuation of the hemostatic clip. Feedback to the operator is preferably also provided so that the operator will not be confused as to whether the hemostatic clip has been properly locked in place on the tissue and released from the device before the device itself is withdrawn through the endoscope.
[0038] FIG. 1 shows a side elevation view of a through the scope hemostatic clipping device according to an exemplary embodiment of the present invention. This device is a hand operated tool that is used to insert a hemostatic clip through an endoscope lumen, position the clip over a wound, clamp it and deploy it over the affected tissue. The tool is further designed to release the hemostatic clip once it has been clamped in place, and to be withdrawn through the endoscope. To more clearly explain the operation and construction of the exemplary device, it may be divided into three principal components. As shown, the hemostatic clipping device 100 comprises a handle assembly 102 , a shaft section 104 , and a clip assembly 106 . The clip assembly 106 is shown more clearly in the detail A depicted in FIG. 1 .
[0039] Handle assembly 102 forms the component that supplies a mechanical actuation force to deploy and clamp the clip. In this embodiment, the device is hand operated (i.e., the user's hands provide the force required to carry out all the functions related to the hemostatic clip). The handle assembly 102 may be constructed in a manner similar to conventional handle assemblies of the type generally employed in endoscopic biopsy devices or in similar applications. The handle assembly 102 allows the user to move a control wire 118 or other force transmission member, which extends through the shaft section 104 to the clip assembly 106 at a distal end of the device 100 . The handle assembly 102 comprises a handle body 108 which can be grasped by the user to stabilize the device and apply a force to it. A sliding spool 110 is connected to control wire 118 , so that the user can easily pull or push said wire 106 as desired.
[0040] As shown in FIGS. 1 and 2 , a sliding spool 110 is mounted on the handle body 108 so that it can slide along a slot 116 , which maintains its position within the handle assembly 102 . Because the sliding spool 110 is connected to the control wire 118 , the user may manipulate the control wire 118 by grasping the handle body 108 and moving the sliding spool 110 along the slot 116 . A return spring 112 may be provided within the handle body 108 to bias the sliding spool 110 , and thus the control wire 118 toward a desired position. In the present embodiment, the sliding spool 110 is biased to the proximal position. The handle assembly 102 may also include a connection portion 114 , which receives the control wire 118 and attaches the shaft section 104 to the handle assembly 102 .
[0041] The shaft section 104 mechanically connects the handle assembly 102 to the clip assembly 106 and, together with the clip assembly 106 , is designed to be inserted into a lumen of an endoscope. As shown in FIGS. 3 and 4 , the shaft section 104 comprises an outer flexible coil 130 which is designed to transmit a torque from the proximal end to the distal end of the device 100 and to provide structural strength to the shaft section 104 . The coil 130 may be a conventional coil used in biopsy devices and may, for example, comprise a single, coiled wire. The coiled wire may have a round, square or a rectangular cross section, and may be made of a biocompatible material such as, for example, stainless steel. Additional protective and low friction outer layers may be included on the shaft section 104 , according to known methods of construction.
[0042] The control wire 118 transmits mechanical force applied to the handle 102 to the clip assembly 106 . The control wire 118 has a proximal end which is attached to a movable part of the handle 102 , such as the sliding spool 110 , using known methods. Stainless steel or other high yield biocompatible materials may be used to manufacture the control wire 118 , so that the structural integrity of the assembly is maintained. It is also important to prevent stretching of the control wire 118 when under tension since, if the wire stretches, the handle 102 will have to travel a greater distance to carry out a desired operation. As shown in FIG. 5 , the distal end of the control wire 118 ends in a ball 140 which is used to connect the control wire 118 to the appropriate elements of the clip assembly 106 , as will be described below. In this embodiment, the diameter of the control wire 118 is substantially constant from a proximal end thereof to a proximal end of a distal tapered section 144 . The ball 140 may have a diameter which is greater than the diameter of the control wire 118 , to facilitate attachment to a yoke 204 . The control wire 118 may extend the length of the device 100 , from the yoke 204 to the sliding spool 110 , and slides longitudinally through the device 100 . It may be made, for example, of stainless steel or other biocompatible metal.
[0043] The control wire 118 may also include a reduced diameter section 142 designed to fail when a predetermined tension is applied thereto through the handle assembly 102 . The tapered section 144 may be used to transition between the main body of the control wire 118 and the reduced diameter section 142 , without steps or other discontinuities which may concentrate stress and make the fracture point more unpredictable. As will be described in greater detail below, one purpose of the reduced diameter section 142 is to facilitate the release of a hemostatic clip from the hemostatic clipping device 100 once the clip has been properly deployed. It will be apparent to those of skill in the art that the location of the reduced diameter section 142 the along control wire 118 may be varied to take into account specific requirements of the device 100 .
[0044] An inner sheath 132 may be used in the construction of the shaft section 104 , as shown in FIGS. 3 and 4 . The inner sheath 132 provides a low friction bearing surface disposed between the outer diameter of the control wire 118 , and the inner diameter of the shaft section 104 . The inner sheath 132 may be formed of a low friction material such as, for example, Teflon™, HDPE or Polypropylene. In one exemplary embodiment, the inner sheath 132 is slidable within the shaft section 104 , and the control wire 118 is slidable within the inner sheath 132 forming a low friction system of multiple bearing surfaces. To further reduce friction, a bio-compatible lubricant may be applied to the inner and outer surfaces of the inner sheath 132 , along the length of the shaft section 104 . For example, silicone lubricants may be used for this purpose.
[0045] A slidable over-sheath 150 may be included in the design of the shaft section 104 , as shown in FIGS. 1 and 2 . The over-sheath 150 is designed to protect the inner lumen of the endoscope from the metal clip assembly 106 and from the metal coil 130 while the hemostatic clipping device 100 passes through the endoscope's lumen. After the clipping device 100 and, more specifically, after the clip assembly 106 has passed through the endoscope, the over-sheath 150 may be withdrawn to expose the distal portion of the clipping device 100 . The over-sheath 150 may be formed, for example, as a single lumen plastic extrusion element slidable over the distal portions of the clipping device 100 to selectively cover and uncover the clip assembly 106 . In one embodiment, the over-sheath 150 is formed of a low friction polymer such as, for example, Teflon™, HDPE, Polypropylene, or similar materials.
[0046] The over-sheath 150 may include a grip portion 152 and an elongated body 154 . The grip portion 152 is designed as a handle making it easier for the user to slide the over-sheath 150 over the shaft of the clipping device 100 . In one exemplary embodiment, the grip portion 152 is made of a rubber-like material to provide a good gripping surface for the user. For example, an injection moldable polymer such as TPE may be used to construct the grip portion 152 . The elongated body 154 may be formed as a substantially cylindrical shell surrounding the shaft of the clipping device 100 . The elongated body 154 may be attached to the grip portion 152 using conventional methods as would be understood by those skilled in the art.
[0047] As shown in FIGS. 6 and 7 , an exemplary grip portion 152 comprises a central hollow channel 160 that may be used to receive the shaft of the clipping device 100 . The central hollow channel 160 is aligned with the elongated body 154 to provide a continuous channel containing the shaft of the clipping device 100 . The material of the grip portion 152 may have a high coefficient of friction, so that an interference fit is possible between the central hollow channel 160 and the shaft of the clipping device 100 without the use of adhesives or mechanical fastening devices. In one embodiment, friction bosses 158 may be provided on an inner diameter of the hollow channel 160 to provide additional friction between the shaft of the clipping device 100 and the over-sheath 150 assembly. The friction bosses 158 may be formed, for example, as protrusions extending from the inner diameter of the over-sheath 150 and may have a variety of stubby or elongated shapes. The amount of friction between these two components may be balanced so that no unwanted relative movement takes place while, at the same time, making it relatively easy for the user to slide the over-sheath 150 proximally and distally when necessary.
[0048] A sheath stop 156 may be provided for the clipping device 100 to prevent the over-sheath 150 from sliding away from the distal end while the clipping device 100 is inserted in the endoscope. As shown in the exemplary embodiment of FIGS. 2 and 8 , the sheath stop 156 physically blocks the grip portion 152 from sliding proximally to prevent the over-sheath 150 from being withdrawn and exposing the clip assembly 106 . The sheath stop 156 is designed to easily snap in place near the proximal end of the shaft section 104 where it can be reached and manipulated by the operator during the surgical procedure. Once the clip assembly 106 has been inserted in the endoscope and has reached the desired location in the patient's body, the sheath stop 156 may be removed from the shaft section 104 so that the user can move the grip portion 152 proximally to uncover the clip assembly 106 .
[0049] The connection between the sheath stop 156 and the shaft section 104 may include, for example, pairs of opposing fingers 162 , 164 that are designed to snap over the shaft section 104 . The fingers 162 , 164 cooperate to securely and releasably hold the body of the shaft section 104 therebetween. The fingers 162 , 164 respectively comprise guide portions 170 , 172 ; shaft channel portions 166 , 168 ; and blocking portions 174 , 176 . Insertion of the sheath stop 156 on the elongated body 154 is accomplished by pressing the body of the shaft section 104 between the guide portions 170 , 172 , to spread the fingers 162 , 164 and allow further insertion of the shaft 104 between the fingers 162 , 164 . The guide portions 170 , 172 and the blocking portions 174 , 176 are shaped so that insertion of the shaft section 104 towards the channel portions 166 , 168 requires less effort than moving the shaft section 104 in the opposite direction.
[0050] Once shaft section 104 has been placed within the channel portions 166 , 168 , the fingers 162 , 164 snap back to their non-spread position and retain the shaft section 104 in place therebetween. The shaft section 104 is removed by pulling the sheath stop 156 away from the shaft section 104 . Due to the shape of the blocking portions 174 , 176 , removing the shaft section 104 requires the application of more force than does insertion thereinto. Stops 180 may also be provided on the sheath stop 156 to limit the movement of the shaft section 104 towards the grasping portion 161 to prevent damage to the device that may be caused by excessive spreading of the fingers 162 , 164 . The sheath stop 156 may be formed of a resilient material, such as a polymer, and may be manufactured by injection molding.
[0051] The clip assembly 106 is disposed at the distal end of the clipping device 100 , and contains the mechanism that converts the proximal and distal movement of the control wire 118 into the actions necessary to deploy and release a hemostatic clip 90 . FIGS. 9 , 10 and 11 show, respectively, side, top and perspective views of the distal end of the clipping device 100 , including the clip assembly 106 having clips in the folded configuration. This configuration is used, for example, to ship the clipping device 100 and to insert the clipping device 100 through the lumen of an endoscope. Some of the components of the clip assembly 106 include a capsule 200 which provides a structural shell for the clip assembly 106 , the clip arms 208 which move between open and closed positions, a bushing 202 attached to the distal end of the control wire 118 , and a yoke 204 adapted to connect the capsule 200 to the control wire 118 .
[0052] As depicted, the proximal end of the capsule 200 slides over the distal end of the bushing 202 . A locking arrangement between these two components is provided by capsule tabs 212 , which are designed to lock into the bushing 202 so that mechanical integrity is temporarily maintained between the capsule 200 and the bushing 202 . Within the capsule 200 are contained a yoke 204 and a tension member 206 which transmit forces applied by the control wire 118 to the clip arms 208 . The ball 140 formed at the distal end of the control wire 118 is mated to a receiving socket 210 formed at the proximal end of the yoke 204 . A male C-section 214 extending from the tension member 206 is received in a corresponding female C-section 216 formed in the yoke 204 , so that the two components are releasably connected to one another, as will be described below. The clip arms 208 in the closed configuration have a radius section 300 which is partially contained within the capsule 200 to prevent opening of the arms. Each of the clip arms 208 goes over the tension member 206 and has a proximal end 222 which slips under a yoke overhang 254 , to further control movement of the arms 208 .
[0053] FIGS. 12 and 13 show a top and a perspective view of the clip assembly 106 in an open configuration with the clip arms 208 in a fully open position. The open configuration is obtained when the sliding spool 110 shown in FIG. 1 is moved distally so that the ball 140 of the control wire 118 pushes the assembly containing the yoke 204 and the tension member 206 forward, sliding within the capsule 200 . As will be described below, the distal ends of the clip arms 208 are biased toward the open position and revert to this position whenever they are not constrained by the capsule 200 . In the exemplary embodiment, a maximum opening of the clip arms 208 occurs when the clip arms 208 ride over the folded distal folding tabs 220 which extend from the distal end of the capsule 200 , as shown in FIGS. 14 and 15 . In this embodiment, the tabs 220 provide a cam surface, and the clip arms 208 act as cam followers, being deflected by the tabs 220 . In addition, the folding tabs 220 may also provide a distal stop for the tension member 206 , to retain it within the capsule 200 . Thus, by moving the sliding spool 110 distally, the user opens the clip arms 208 to prepare to grasp tissue therebetween.
[0054] When the sliding spool 110 is moved proximally by the user, the assembly within the capsule 200 also moves proximally and the clip arms 208 are withdrawn within the capsule 200 . As the clip arms 208 move proximally within the capsule 200 , clip stop shoulders (CSS) 222 contact a distal portion of the capsule 200 , for example, the folded tabs 220 . This interaction of the CSS 222 with the capsule 200 provides to the user a first tactile feedback in the form of increased resistance to movement of the sliding spool 110 . This feedback gives to the operator a positive indication that further movement of the handle control will cause the hemostatic clip 90 to be deployed from the clip assembly 106 . The operator may then decide whether the current position of the clip 90 is acceptable or not. If the position is acceptable, the operator can deploy the clip 90 by continuing to move the sliding spool 110 with increased proximal pressure to cause the clip arms 208 to close on the tissue. If not, the operator can move the sliding spool 110 distally to re-open the clip arms 208 and extend them out of the capsule 200 , reposition the clip 90 , and repeat the above steps to close the clip 90 at a more appropriate location.
[0055] When the user determines that the clipping device 100 is positioned correctly, the proximal pressure on the sliding spool 110 may be increased to continue deployment of the hemostatic clip 90 from the clip assembly 106 . FIGS. 16 and 17 show respectively a top and side view of the clipping device 100 in this condition. As the proximal tension on sliding spool 110 is increased, the control cable 118 pulls the yoke 204 proximally, away from the tension member 206 . The tension member 206 is firmly attached to the clip arms 208 which are prevented from moving proximally by the interaction of the CSS 222 with the folded tabs 220 . If sufficient pulling force is applied to the yoke 204 , the male C section 214 of the tension member 206 yields and loses integrity with the female C section 216 of the yoke 204 . This can occur because, in the exemplary embodiment, the tension member 206 is formed of a material with a lower yield strength than the material of the yoke 204 .
[0056] The force required to break the tension member 206 away from the yoke 204 may be tailored to achieve a desired feedback that can be perceived by the user. The minimum force required to break the tension member 206 free of the yoke 204 may be selected so that a tactile feedback is felt by the user, to prevent premature deployment of the hemostatic clip 90 while a maximum force may be selected so that other components of the linkage between the sliding spool 110 and the clip arms 208 do not fail before the male C section 214 and the female C section 216 disconnect from one another. In one exemplary embodiment, the tension force necessary to disconnect the two components may be in the range of approximately 4 lbf to about 12 lbf. This range may vary depending on the size of the device and the specific application. To obtain this force at the interface of the male and female C sections 214 , 216 a larger force will be applied by the user at the sliding spool 110 , since friction within the device may cause losses along the long flexible shaft.
[0057] When the male C section 214 of tension member 206 yields, several events take place within the device 100 nearly simultaneously. More specifically, the yoke 204 is no longer constrained from moving proximally by the CSS 222 abutting the capsule 200 . Thus the yoke 204 travels proximally until coming to rest against a distal bushing shoulder 250 . The tension member 206 is not affected by this movement since it is no longer connected to the yoke 204 . The proximal ends 252 of the clip arms 208 are normally biased away from a center line of the device 100 and are no longer constrained by the yoke overhangs 254 . Accordingly, the clip latches 302 are free to engage the latch windows 304 of the capsule 200 , thus maintaining the integrity of the capsule-clip arms combination after deployment. Details of the capsule 200 are shown in FIGS. 14 , 15 and details of the clip arms 208 are shown in FIGS. 18 , 19 and 20 .
[0058] As the yoke 204 moves proximally to abut against the bushing 202 , the capsule tabs 306 are bent away from the centerline of the capsule 200 by the cam surfaces of the yoke 204 . As a result, the capsule tabs 306 are no longer engaged to the corresponding bushing undercuts 350 , shown in the side and perspective views of the bushing 202 depicted in FIGS. 21 , 22 . Since the capsule 200 and the bushing 202 (which is securely connected to shaft section 104 ) are no longer connected, the clip assembly 106 is prevented from being released from the shaft section 104 only by its connection to the ball 140 of the control wire 118 .
[0059] A further result of moving the yoke 204 against the distal bushing shoulder 250 of the bushing 202 is that the distal end of the wire stop 360 (shown in FIGS. 12 , 16 ) is placed near the proximal bushing shoulder 364 (shown in FIG. 22 ). The flared fingers 362 located at the distal end of the wire stop 360 , better shown in FIG. 23 , are compressed as they pass through the central ID of the bushing 202 , but return to their normally biased open position (shown in FIG. 23 ) after passing past the proximal bushing shoulder 364 . Further distal movement of the sliding spool 110 is thus prevented since that movement would engage the fingers 362 of the wire stop 360 with the proximal bushing shoulder 364 . This feature prevents the clip assembly 106 from being pushed away from the bushing 202 before the ball 140 is separated from the control wire 118 , as will be described below.
[0060] The wire stop 360 comprises a tube with a first slotted and flared end attached to the control wire 118 by conventional means. As shown in FIG. 23 , the slots impart flexibility to the device so it can easily pass through the central lumen of the bushing 202 . Flared fingers 362 are formed by the slots, and engage the proximal bushing shoulder 364 . The wire stop 360 is made of a material that is biocompatible and that has enough resilience so that the fingers 362 re-open after passage through the bushing 202 . For example, stainless steel may be used for this application.
[0061] One feature of the exemplary embodiment of the invention described above is that the user receives both tactile and auditory feedback as the clip assembly 106 is deployed and released. The separation of the tension member 206 from the yoke 204 produces a small clicking noise and a tactile feel that is perceptible while holding the handle assembly 102 . The change in axial position of the sliding spool 110 is thus augmented by the changes in resistance to its movement and by the clicking sound and feel through the start and stop of the movement. As a result the user is always aware of the status of the clip assembly 106 , and the inadvertent deployment of a hemostatic clip 90 in an incorrect location is made less likely. It will be apparent to those of skill in the art that the order of male and female connectors in the device may be reversed or changed without affecting the operation of the device.
[0062] It may be beneficial for the user to be certain that the clip assembly 106 has been deployed before the rest of the clipping device 100 is removed from the endoscope. Injury to the tissue being treated could result if the clipping device 100 is removed from the operative site when the hemostatic clip 90 is only partially deployed. Accordingly, a large tactile feedback may be incorporated, to augment the auditory and tactile feedback stemming from the separation of the yoke 204 from the tension member 206 . FIG. 24 depicts the condition where the clip assembly 106 separates from the rest of the clipping device 100 . According to the described embodiment, this second user feedback is obtained by designing the control wire 118 so that it will separate from the end ball 140 when a predetermined tension is applied to it. In other words, the ball 140 of the control wire 118 is mechanically programmed to yield and separate from the body of the control wire 118 when a pre-set tension is applied thereto. The size of the reduced diameter section 142 can be selected so that, when the user continues to move the sliding spool 110 proximally as the programmed yield tension is reached, the ball 140 detaches from the tapered section 144 and provides a large tactile feedback to the operator.
[0063] When the ball 140 detaches, the sliding spool 110 bottoms out at the proximal end of the handle 108 , such that a full stroke of the handle assembly 102 is reached. The tension required to cause the reduced diameter section 142 to yield and release the ball 140 may vary over a range of values. However, for best results the force should be greater than the tension force required for the male C section member 214 to separate from the yoke 204 . If this condition is not satisfied, a situation may occur where the clip assembly 106 is locked in place on the patient's tissue, but cannot be released from the clipping device 100 . It will be apparent that this situation should be avoided. In one exemplary embodiment, the tension force required to separate the ball 140 from the body of the control wire 118 is in the range of between about 10 lbf and 20 lbf at the distal end of the control wire 118 . As discussed above, losses along the elongated flexible shaft may require the user to apply a force substantially greater than this to the handle body 102 .
[0064] Once the ball 140 has separated from the rest of the control wire 118 , the user can pull the rest of the clipping device 100 from the endoscope. As this is done, the yoke 204 is retained within the capsule 200 by the spring and frictional forces of the capsule tabs 306 . Prior to withdrawing the clipping device 100 , the over-sheath 150 may be moved distally by the user over the entire remaining portions of the shaft section 104 to prevent damage to the endoscope as the clipping device 100 is withdrawn therethrough. The sheath stop 156 may also be placed on the shaft section 104 proximally of the over-sheath grip 152 to prevent inadvertent sliding of the over-sheath 150 from the distal end of the device 100 .
[0065] A more detailed description of several components of the clipping device 100 follows. The clip arms 208 are shown in detail in FIGS. 18 , 19 and 20 ; the tension member 206 is shown in side and top views in FIGS. 25 , 26 ; while top and side views of the yoke 204 are shown respectively in FIGS. 27 and 28 . the clip arms 208 may be formed of a biocompatible material such as Nitinol, Titanium or stainless steel. Maximum spring properties may be obtained by using materials such as 400 series stainless or 17-7 PH. As shown, a tear drop keyway 400 is formed in the clip arm 208 to mate with a corresponding tear drop key 402 formed on the tension member 206 . This feature maintains the relative positions of these two components and of the yoke 204 substantially constant. The shape of the keyways 400 may be varied. For example, the keyway 400 may be oval or elliptical. Central portions of the clip arms 208 define a spring section 404 . When the proximal ends 252 of the clip arms 208 are under the yoke overhangs 254 , the clip arms 208 are allowed to pivot over the tension member 206 , which in turn biases the distal ends 252 towards the open configuration when no longer restrained by the capsule 200 . As a result, the proximal end 252 of each clip arm 208 springs upward and engages the latch windows 304 in the capsule 200 .
[0066] the clip arms 208 also comprise a radius section 300 that adds strength to the clip and reduces system friction. The radius of the radius section 300 approximately matches the inner diameter of the capsule 200 and has a smooth profile to avoid scratching the inner surface of the capsule 200 . A pre-load angle α is defined between the radius section 300 and the spring section 404 . The pre-load angle α determines how much interference (pre-load) exists between the two opposing clip arms 208 at their distal ends when closed. The greater the pre-load angle α, the greater the engaging force that is applied by the clip arms 208 . However, this condition also causes the greatest system friction when the hemostatic clip 90 is closed. The clip arms 208 also comprise interlocking teeth 408 disposed at their distal ends. In the exemplary embodiment, the teeth 408 are identical so that the arms may be interchangeable and will mesh smoothly with the set facing them. The teeth 408 are disposed at a nose angle β which may be between approximately 90 and 135 degrees, but in other applications may be greater or lesser than the described range.
[0067] The capsule 200 is shown in detail in FIGS. 14 and 15 and comprises alignment keyways 500 that are designed to mate with corresponding features on the bushing 202 to rotationally align the two components. The capsule tabs 306 may be bent towards the centerline of the capsule 200 to engage the bushing undercuts 350 . The engagement maintains the integrity between the capsule assembly 200 and the rest of the clipping device 100 until the yoke is pulled into the distal bushing shoulder. the capsule overhangs 502 provide added clamping strength to the deployed clip arms 208 . This is achieved by reducing the length of the portion of each clip arm 208 that is not supported by a portion of the capsule 200 . This feature does not affect the amount of tissue that may be captured by the clip arms 208 since the capsule overhangs 502 extend on a plane substantially parallel to the plane of the clip arms 208 .
[0068] Additional features of the capsule 200 include an assembly aid port which may be used to assist in aligning the components of the clip assembly 106 . Bending aids 506 facilitate a smooth bend when the distal folding tabs 220 are bent inward, as described above. The bending aids 506 , as shown, are holes aligned with the folding line of the tabs 220 , but may also include a crease, a linear indentation, or other type of stress concentrator. The capsule 200 may be formed from any of a variety of biocompatible materials. For example, stainless steel, Titanium or Nitinol or any combination thereof may be used. High strength polymers like PEEK™ or Ultem™ may also be used to form the capsule 200 , with a heat set treatment being used to adjust positionable elements.
[0069] FIGS. 25 and 26 depict additional details of the tension member 206 . As shown, tear drop keys 402 are designed to engage the tear drop keyways 400 of the clip arms 208 , as described above. Clip follower planes 508 are shaped to form a fulcrum which allows the clip arms 208 to rock between the open and closed configurations. The tension member 206 comprises a distal stop face 510 which abuts the distal folding tabs 220 of the capsule 200 to stop the distal motion of the capsule assembly 106 . In general, all surfaces and edges of the tension member 206 that are in contact with the inner surfaces of the capsule 200 preferably have a radius substantially similar to an inner radius of the capsule 200 to provide a sliding fit therein. The tension member 206 may be formed of a biocompatible polymer, monomer or thermoset. The type of mechanism selected to release the tension member 206 from the yoke 204 may determine the type of material used since a release due to fracture of the male C section 214 requires a relatively brittle material while release due to yielding without fracture calls for a softer material.
[0070] Additional details of the yoke 204 are shown in FIGS. 27-29 . When the control wire 118 is seated in the yoke 204 , it is desirable to ensure that it cannot inadvertently be removed from the control wire slot 600 . Accordingly, in the present embodiment the ball cavity 602 has a diameter sufficiently large to allow the ball 140 to pass therethrough while the wire cavity 604 is large enough to allow the control wire 118 to pass therethrough, but not large enough to allow the ball 140 pass therethrough. To assemble the control wire 118 with the yoke 204 according to the exemplary embodiment, the proximal end of wire 140 is inserted into the ball cavity 602 until the ball bottoms out, and then the control wire 118 is rotated until it is seated in the control wire cavity 604 , thus constraining further movement of the ball 140 . According to the present embodiment, the yoke 204 may be made of a biocompatible metal such as stainless steel or a high strength polymer such as Ultem™.
[0071] According to embodiments of the present invention, the clipping device 100 may be scaled to fit the requirements of different surgical procedures. In one exemplary embodiment, the clipping device 100 may be sized to fit through an endoscope having a working channel diameter of approximately 0.110 inches. The exemplary bushing may have a length of about 0.22 inches and an OD of approximately 0.085 inches. The capsule may have a length of about 0.5 inches, an OD of about 0.085 inches, and a wall thickness of about 0.003 inches. When assembled, the rigid length of the capsule 200 and the bushing 202 is approximately 0.625 inches. This length is important because if it is too great, the assembly will not pass through the bends of the flexible endoscope. In the exemplary clipping device, the outer sheath may have an ID of approximately 0.088 inches and an OD of about 0.102 inches. The overall length of the clipping device may be approximately 160 inches, while the tissue grasping portion of the clip arms 208 may be approximately 0.4 inches long.
[0072] The present invention has been described with reference to specific exemplary embodiments. Those skilled in the art will understand that changes may be made in details, particularly in matters of shape, size, material and arrangement of parts without departing from the teaching of the invention. For example, different shapes of the yoke, the tension member and the bushing may be used, and different attachments of the clip arms and control wire may be employed. Accordingly, various modifications and changes may be made to the embodiments without departing from the broadest scope of the invention as set forth in the claims that follow. The specifications and drawings are, therefore, to be regarded in an illustrative rather than a restrictive sense. | An apparatus for deployment of a hemostatic clip comprises a handle assembly, a shaft connected to a distal portion thereof and a clip assembly releasably coupled to a distal portion of the shaft. The clip assembly includes clip arms and a capsule cooperating with the clip arms to provide a first user feedback indicating a decision configuration of the clip assembly. In addition, the apparatus includes a control wire including a ball connector, the control wire extending from the handle assembly and coupled to the clip assembly by the ball connector to maintain the clip assembly coupled to the shaft, wherein the ball connector is detachable from the clip assembly to provide a second user feedback indicating separation of the clip assembly from the shaft. | 0 |
[0001] Under 35 CFR 119(e), this application claims the benefit of the filing date of a provisional application having Ser. No. 60/648,793 which was filed on Jan. 31, 2005.
[0002] This application includes material which is subject to copyright protection. The copyright owner has no objection to the facsimile reproduction of the patent disclosure, as it appears in the Patent and Trademark Office files or records, but otherwise reserves all rights.
FIELD OF THE INVENTION
[0003] The present invention relates to the field of electrical switches. More specifically, this invention relates to switches for use in alternating currents.
BACKGROUND OF THE INVENTION
[0004] Lever actuated switches are common in the art and are used to provide a means to conveniently and affirmatively switch electrical current. Many variations of switches exist that utilize a lever which acts upon a plunger or similar structure to engage or disengage electrical contacts and thereby establish or terminate electrical service to one or more loads. An example of a patented switch of this type is disclosed in U.S. Pat. No. 4,400,603. This patent discloses a switch for use in alternating current (AC) circuits wherein a pivotally mounted operating handle accepts a pivot pin at one end of a link member. A pivot pin at the other end of the link member fits into a brush lifter. Angular motion of the operating handle produces a rectilinear motion in the brush lifter which results in opening and closing of the switch contacts. An arc shield disposed within the switch encircles one out of each pair of contacts, and protects the switch mechanism from destructive effects of contact arcing.
[0005] A need exists for an improved switch that incorporates a reduced number of moving parts. This improved switch should be enabled to be produced at reduced cost. Furthermore, this switch should provides improved operational characteristics.
[0006] The present invention is directed to overcoming, or at least reducing the effects of one or more of the problems set forth above.
SUMMARY OF THE INVENTION
[0007] To address the above-discussed deficiencies of electrical switches, the present invention teaches an electrical switch that provides enhanced operational characteristics wherein the rotary motion of an operating handle is translated into a linear motion through the incorporation of a cam follower. Unique geometry of a cam operating upon the cam follower translates into a switching action which provides for an initial slow break that accelerates as the operating handle is rotated to a full open position. The cam follower then rapidly establishes contact and minimizes arcing when the switch is closed.
[0008] In particular, the operating handle having a cam is in cooperative alignment with a cam follower such that when the operating handle is rotated from an OFF position to an ON position, the cam causes the cam follower to move a bridge having coil spring into contact with at least one electrical contact. In the alternative, when the operating handle is rotated from the ON position to the OFF position, the cam causes the cam follower to separate the bridge apart from the electrical contact.
[0009] 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.
[0010] These and other features and advantages of the present invention will be understood upon consideration of the following detailed description of the invention and the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] For a more complete understanding of the present invention and the advantages thereof, reference is now made to the following description taken in conjunction with the accompanying drawings in which like reference numbers indicate like features and wherein:
[0012] FIG. 1 illustrates the top view of a three-pole switch in accordance with the present invention with the operating handle 10 in the ON position;
[0013] FIG. 2 displays a side elevation view of the switch 100 of FIG. 1 ;
[0014] FIG. 3 illustrates a cross-sectional view of switch 100 of FIG. 1 taken along Section line 3 - 3 where the cut extends through switch 100 ;
[0015] FIG. 4 is a side view of operating handle 10 ;
[0016] FIG. 5 is an end view of operating handle 10 ;
[0017] FIG. 6 depicts a cross-sectional view of switch 100 of FIG. 1 taken along Section line 6 - 6 where the cut extends through switch 100 ;
[0018] FIG. 7 is a plan view of the bottom of the switch 100 of FIG. 1 ;
[0019] FIG. 8 illustrates operating handle 10 , cam 80 and cam follower 50 in two positions to demonstrate the switch position feature; and
[0020] FIG. 9 shows the placement of insulating arc shield 90 .
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0021] The present invention will now be described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
[0022] The present invention relates to a switch having improved operational characteristics, with relatively fewer parts. Referring to the drawings, FIG. 1 illustrates the top view of a three-pole switch in accordance with the present invention with the operating handle 10 in the ON position. The switch enclosure 12 , such as of molded insulating material, is large enough to contain three poles. However, it will be understood that the invention applies as well to switches of less or greater complexity which contain a different number of poles. The cover arrangement includes switch enclosure 12 and faceplate 14 . Faceplate 14 , such as of metal, is mounted to enclosure 12 by two faceplate bolts, 24 and 26 . These faceplate bolts, 24 and 26 , serves to hold operating handle pivot pin 40 (shown in FIG. 3 ) on operating handle 10 in slots (not shown) of enclosure 12 . Mounting holes 22 and 28 are provided in face plate 14 , for mounting the switch on a control panel. Six conductor clamp bolts 16 , 18 , 20 , 30 , 32 , and 34 are shown to accommodate the three poles of the switch shown in this embodiment.
[0023] FIG. 2 is a side elevation view of the switch of FIG. 1 , showing conductor clamp bolts 30 , 32 , and 34 for a circuit which will be controlled by the switch. A like number of conductors, 16 , 18 and 20 , shown in FIG. 1 is provided on the opposite side of the switch (not shown in FIG. 2 ). Referring back to FIG. 2 , this first embodiment of the present invention comprises a base 36 and a cover arrangement including switch enclosure 12 and faceplate 14 . The switch enclosure 12 and faceplate 14 are held together by faceplate bolts 24 and 26 (shown in FIG. 1 ).
[0024] FIG. 3 depicts a cross-sectional view of switch 100 of FIG. 1 taken along Section line 3 - 3 where the cut extends through switch 100 revealing coil springs 52 - 66 , cam 80 of operating handle 10 , and cam follower 50 . As can be seen from FIG. 3 , cam 80 is integrated into operating handle 10 such that when operating handle 10 is rotated, cam 80 acts upon cam follower 50 which engages bridges 82 - 86 which is part of a contact making and contact breaking mechanism. The action of cam follower 50 upon bridges 82 - 86 causes a downward motion of bridges 82 - 86 resulting in contact opening and placing operating handle 10 in a locked position.
[0025] During the actuation of operating handle 10 to its locked position, the resultant downward movement of bridges 82 - 86 compresses coil springs 52 - 62 which remain compressed as long as operating handle 10 remains in the locked position. When the position of operating handle 10 is reversed (moved out of locked position), coil springs 52 - 62 expand and bring bridges 82 , 84 , and 86 in contact with respective conductors, 16 , 18 , 20 and, thereby establishing full contact position. These same bridges 82 , 84 , and 86 make contact with a like number of respective conductors, 30 , 32 , and 34 , shown in FIG. 1 is provided on the opposite side of the switch (not shown in FIG. 3 ). Auxiliary springs 64 and 66 located inside cam follower 50 bias follower 50 to its maximum upward position thereby separating bridge 82 - 86 from cam follower 50 and creating an over-travel position for operating handle 10 .
[0026] FIG. 4 is a side view of operating handle 10 , which shows how operating handle pivot pin 40 sits off center with respect to center line A-A. Operating handle stops 82 and 84 are also shown.
[0027] FIG. 5 is an end view of operating handle 10 , showing how operating handle pivot pin 40 extends from both sides of the operating handle 10 . Operating handle stops 86 and 88 are also shown positioned opposite operating handle stops 82 and 84 .
[0028] FIG. 6 depicts a cross-sectional view of switch 100 of FIG. 1 taken along Section line 6 - 6 where the cut extends through switch 100 revealing bridge 84 in contact with coil springs 56 , 58 , and 68 . Bridge 84 includes contacts 70 a and 70 c for making contact with another pair of contacts 70 b and 70 d . Specifically, in operation, when cam 80 of operating handle 10 is rotated to the OFF position, cam follower 50 compresses coil spring 56 which forces bridge 84 downward. The downward motion of bridge 84 compresses coil springs 58 and 68 . Contacts 70 a and 70 c separate from contacts 70 b and 70 d breaking connection with the circuits derived by conductors 32 and arm 98 , on one side, and conductor 18 and arm 99 , on the opposite side.
[0029] Accordingly, in operation, when cam 80 of operating handle 10 is rotated to the ON position, cam follower 50 is no longer held in the locked OFF position and is forced upwards by coil springs 56 , 58 and 68 . Bridge 84 is forced upwards by coil springs 58 and 68 such that contacts 70 a and 70 c meet respective contacts 70 b and 70 d . The connection through contacts 70 a and 70 b enables current to flow through arm 98 to conductor 32 and into the circuit being controlled by switch 100 . In the same like fashion, the connection through contacts 70 c and 70 d enables current to flow through arm 99 to conductor 18 and into the circuit being controlled by switch 100 when handle 10 is rotated to the ON position.
[0030] FIG. 7 is a plan view of the bottom of the switch 100 of FIG. 1 , showing faceplate bolts 24 and 26 . Six conductor clamp bolts 16 , 18 , 20 , 30 , 32 , and 34 are shown to accommodate the three poles of the switch shown in this embodiment. As earlier referenced, mounting holes 22 and 28 are provided in face plate 14 , for mounting the switch on a control panel, wherein face plate 14 extends beyond either end of base 36 .
[0031] FIG. 8 illustrates the switch position feature. When operating handle 10 pivots around pivot pin 40 , from position A to position B, cam follower 50 moves from position C to position D. Specifically, operating handle stops 82 and 84 of cam 80 ride along the ridged surface of cam follower 50 when operating handle 10 pivots around pivot pin 40 . The unique ridged surface of cam follower 50 ensures that operating handle 10 can only stop in the full ON or full OFF position. In the ON position, operating handle 10 is in position A. Referring back to FIG. 6 , cam follower 50 is no longer held in the locked OFF position and is forced upwards by coil springs 56 , 58 and 68 . In the OFF position, operating handle 10 is in position B. Accordingly, referring to FIG. 6 , cam 80 forces cam follower 50 to compress coil spring 56 which forces bridge 84 downward.
[0032] FIG. 9 shows the placement of insulating arc shield 90 around any of the stationary conductor clamp bolts 16 , 18 , 20 , 30 , 32 , and 34 shown in FIGS. 1-7 . By completely encircling stationary contact 16 , for example, the arc shield 90 provides maximum protection for structures in the vicinity of stationary contact 16 . In this embodiment, arc shield 90 is held in place by virtue of the fact that the edge 96 of the arc shield 90 fits in a gap between enclosure component 12 and base 36 , as shown in FIG. 2 .
[0033] While the invention has been described in detail and with reference to a specific embodiment thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. For example switch 100 can be manufactured as a two pole or three pole device respectively. 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.
[0034] Advantages of this design include but are not limited to an electrical switch having a high performance, simple, and cost effective design.
[0035] The reader's attention is directed to all papers and documents which are filed concurrently with this specification and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.
[0036] All the features disclosed in this specification (including any accompanying claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
[0037] The terms and expressions which have been employed in the foregoing specification are used therein as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding equivalents of the features shown and described or portions thereof, it being recognized that the scope of the invention is defined and limited only by the claims which follow. | An electrical switch is disclosed having improved operational characteristics wherein when a operating handle is rotated from an OFF position to an ON position the switch provides slow motion which accelerates as the operating handle is rotated to a full open position and then provides rapid establishment of electrical contact. The operating handle having a cam that when rotated from the ON position to the OFF position forces a cam follower downwards. As a result, a bridge having coil springs connected to the cam follower is forced downwards to separate at least one electrical contact placed in proximity to the bridge. | 7 |
Subsets and Splits
No community queries yet
The top public SQL queries from the community will appear here once available.